Synthesis of normal alpha olefins using decarbonylative olefination

Abstract

An alpha olefin synthesis process comprising (i) subjecting a first normal alpha olefin to hydroformylation in the presence of carbon monoxide and hydrogen to form a first linear aldehyde, (ii) subjecting the first linear aldehyde to decarbalkenolation to form a linear internal olefin, (iii) subjecting the linear internal olefin to isomerization-hydroformylation in the presence of carbon monoxide and hydrogen to form a second linear aldehyde, and (iv) subjecting the second linear aldehyde to hydrogenation to form a linear alcohol followed by dehydration to form a second normal alpha olefin, or subjecting the second linear aldehyde to combined hydrogenation-dehydration in a single step to form a second normal alpha olefin. Using this process, for example, ethylene can be converted to 1-hexene, and 1-butene can be converted to 1-decene.

Description

Technical Field

[0001] The present invention generally relates to a process for producing n-alpha olefins in a multi-step synthetic scheme, which may include a hydroformylation step, a decarbonylation step, an isomerization-hydroformylation step, a hydrogenation step, and a dehydration step. Background Technology

[0002] The synthesis of n-alpha olefins with specific carbon numbers (especially 1-hexene, 1-octene, and 1-decene) is of great importance in the chemical industry. However, using existing catalysts and reaction processes, it is difficult to selectively produce only the desired alpha olefin fraction, rather than a complex mixture of olefin products. Developing new methods for producing specific n-alpha olefins with specific carbon numbers would be beneficial. Therefore, this invention is generally aimed at these objectives. Summary of the Invention

[0003] The present invention is provided to introduce, in a simplified form, the selected concepts further described herein. The present invention is not intended to identify essential or necessary features of the claimed subject matter. Nor is the present invention intended to limit the scope of the claimed subject matter.

[0004] The processes disclosed and described herein may include (i) in the presence of carbon monoxide and hydrogen, causing a structure (C) to be formed. n The first normal-α olefin with -C=C undergoes hydroformylation to form a structure containing C(C). n+1 (ii) a first composition of a first straight-chain aldehyde containing CH (=O), and (ii) decarbonylating the first straight-chain aldehyde to form a composition containing C. 2n+5 A second composition of a linear intra-chain olefin, (iii) isomerizing-hydroformylating the linear intra-chain olefin in the presence of carbon monoxide and hydrogen to form a compound containing a C(C) structure. 2n+4 A third composition of a second straight-chain aldehyde containing CH (=O), and (iv-a) hydrogenating and dehydrating the second straight-chain aldehyde to form a composition containing a structure (C). 2n+4 A product composition of a second normal-α olefin with -C=C structure, or (iv-b1) hydrogenating a second straight-chain aldehyde to form a product containing a C(C) structure. 2n+4 A fourth composition of a straight-chain alcohol containing C(OH), and (iv-b2) dehydrating the straight-chain alcohol to form a compound containing the structure (C). 2n+4 The product composition of the second normal-α olefin with -C=C. In this process, n is an integer in the range of 0 to 30.

[0005] In one aspect of the disclosed process, the first n-α olefin may include ethylene, and the second n-α olefin may include 1-hexene. In another aspect, the first n-α olefin may include propylene, and the second n-α olefin may include 1-octene. In yet another aspect, the first n-α olefin may include 1-butene, and the second n-α olefin may include 1-decene.

[0006] The foregoing summary and the following detailed description are provided as examples and are merely illustrative. Therefore, the foregoing summary and the following detailed description should not be considered limiting. Furthermore, features or variations may be provided in addition to those set forth herein. For example, certain aspects may relate to various combinations and sub-combinations of features described in the detailed description. Attached Figure Description

[0007] The following drawings form part of this specification and are included to further illustrate certain aspects of the invention. A better understanding of the invention can be achieved by referring to the drawings in conjunction with the detailed description.

[0008] Figure 1 The present disclosure describes a reaction scheme for converting 1-butene to 1-decene and ethylene to 1-hexene.

[0009] While the invention disclosed herein is susceptible to various modifications and alternatives, only a few specific aspects are illustrated in the accompanying drawings, and these aspects are described in detail below. The drawings and the detailed description of these specific aspects are not intended to limit the concept of the invention or the breadth or scope of the appended claims in any way. Rather, the drawings and detailed description are provided to illustrate the concept of the invention to those skilled in the art, and to enable such persons to acquire and use the concept of the invention.

[0010] definition

[0011] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise specified, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition applies uncertain or invalid. If any definition or usage provided in any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0012] In this document, the features of the subject matter are described such that combinations of different features can be conceived within a particular aspect. For each aspect and / or feature disclosed herein, all combinations are considered, with or without an explicit description of a particular combination, that will not adversely affect the design, composition, process, and / or method described herein. Furthermore, unless expressly stated otherwise, any aspect and / or feature disclosed herein may be combined to describe inventive features consistent with this disclosure.

[0013] In this disclosure, while processes are generally described as “comprising” individual steps, processes may also be described as “substantially consisting of individual steps” or “consisting of individual steps” unless otherwise stated. Unless otherwise stated, the terms “a / an” and “the” are intended to include multiple alternatives, such as at least one. For example, unless otherwise stated, the disclosure of “first n-α olefin” is intended to cover one first n-α olefin, or a combination of more than one first n-α olefin.

[0014] Typically, elemental families use Chemical and Engineering News The numbering scheme indicated in the version of the periodic table published in 1985, 63(5), 27, indicates the group of elements. In some cases, the group of elements may be indicated by 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.

[0015] For any particular compound or group disclosed herein, unless otherwise stated, 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 enantiomers or racemic forms, and mixtures of stereoisomers, as known to those skilled in the art. For example, a general reference to a hexene (or more hexenes) includes all straight-chain or branched, acyclic or cyclic hydrocarbon compounds having six carbon atoms and one carbon-carbon double bond; a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and a general reference to butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0016] Unless otherwise stated, the term "submitted" is used herein to describe process steps that bring materials into contact or together in any order, in any manner, and for any duration. For example, materials may be blended, mixed, slurried, dissolved, reacted, treated, impregnated, compounded, or otherwise brought into contact or in some other manner or by any suitable method or technique.

[0017] Whenever used in this specification and claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of a specific group in a hydrocarbon (e.g., a halohydrocarbon indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in a hydrocarbon). Similarly, the term "alkane" refers to a saturated hydrocarbon compound.

[0018] 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 specified, the term "olefin" includes aliphatic and aromatic, cyclic and acyclic, and / or straight-chain and branched hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Olefins having only one, 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 the carbon-carbon double bond. 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 chain. Unless otherwise explicitly stated, the term "α-olefin" includes straight-chain and branched α-olefins and α-olefins that may have more than one non-aromatic carbon-carbon double bond. The term "normative α-olefin" refers to a straight-chain aliphatic hydrocarbon monoolefin having a carbon-carbon double bond between the first and second carbon atoms. The term "linear intra-olefin" refers to a linear aliphatic hydrocarbon monoolefin having a double bond not between the first and second carbon atoms.

[0019] This document discloses various numerical ranges. Unless otherwise stated, when any type of range is disclosed or claimed, the intent is to individually disclose or claim every possible number that such range can reasonably cover, including the endpoints of the range and any sub-ranges and combinations thereof covered therein. As a representative example, this disclosure states that the molar ratio of carbon monoxide to hydrogen in step (i) or step (iii) of the process can be within a certain range. By disclosing that this molar ratio can be in the range of 5:1 to 1:5, the purpose is to state that the molar ratio can be any ratio within that range, and can include, for example, any range or combination of ranges from 5:1 to 1:5, such as 2:1 to 1:2, or 1.5:1 to 1:1.5, etc. Similarly, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0020] Generally, quantities, sizes, formulations, parameters, ranges, or other quantities or characteristics are expressed as “about” or “approximately”, whether or not explicitly stated. Claims include equivalents of quantities or characteristics, regardless of whether they are modified by the terms “about” or “approximately”.

[0021] Although any methods and materials similar to or equivalent to those described herein may be used in the practice or testing of this invention, typical methods and materials are described herein.

[0022] All publications and patents mentioned herein are incorporated herein by reference in their entirety for the purpose of describing and disclosing, for example, the constructs and methods described in the publications and patents, which may be used in conjunction with the inventions described herein. Detailed Implementation

[0023] This article discloses processes for the production of n-α-olefins, and particularly atomically efficient processes for converting n-α-olefins to higher carbon-number n-α-olefins. Advantageously, these processes offer high carbon preservation and low byproduct formation, and can utilize syngas as a reactant in two independent steps of the process.

[0024] Synthesis of normal-type α-olefins

[0025] Various aspects of the present invention relate to a process that may include the following steps (or substantially consist of or comprise the following steps): (i) in the presence of carbon monoxide and hydrogen, causing a structure (C) to be formed. n The first normal-α olefin with -C=C undergoes hydroformylation to form a structure containing C(C). n+1 (ii) a first composition of a first straight-chain aldehyde containing CH (=O), and (ii) decarbonylating the first straight-chain aldehyde to form a composition containing C. 2n+5 A second composition of a linear intra-chain olefin, (iii) isomerizing-hydroformylating the linear intra-chain olefin in the presence of carbon monoxide and hydrogen to form a compound containing a C(C) structure. 2n+4 A third composition of a second straight-chain aldehyde containing CH (=O), and (iv-a) hydrogenating and dehydrating the second straight-chain aldehyde to form a composition containing a structure (C). 2n+4 A product composition of a second normal-α olefin with -C=C structure, or (iv-b1) hydrogenating a second straight-chain aldehyde to form a product containing a C(C) structure. 2n+4 A fourth composition of a straight-chain alcohol containing C(OH), and (iv-b2) dehydrating the straight-chain alcohol to form a compound containing the structure (C). 2n+4 The product composition of the second normal-α olefin with -C=C. In this process, n is an integer in the range of 0 to 30.

[0026] Typically, the features of this process (e.g., hydroformylation steps, decarbonylation steps, isomerization-hydroformylation steps, combined hydrogenation-dehydration steps, hydrogenation and dehydration steps, and other features) are described independently herein, and these features may be combined in any combination to further describe the n-alpha olefin synthesis process. Furthermore, unless otherwise stated, additional process steps may be performed before, during, and / or after any step of this process.

[0027] As described herein, n can be an integer in the range of 0 to 30. In one aspect consistent with the present invention, n can be an integer from 0 to 18, while in another aspect, n can be an integer from 0 to 12. However, in another aspect, n can be an integer from 0 to 8, and in yet another aspect, n can be an integer from 0 to 6. For example, n can be equal to 0, equal to 1, equal to 2, equal to 3, equal to 4, equal to 5, equal to 6, etc.

[0028] In some aspects of the invention, the first normal α-olefin may include (or substantially consist of) ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadene, or any combination thereof. For example, the first normal α-olefin may include (or substantially consist of) ethylene; optionally propylene; optionally 1-butene; optionally 1-pentene; optionally 1-hexene; optionally 1-heptene; optionally 1-octene; optionally 1-nonene; optionally 1-decene; optionally 1-dodecene; optionally 1-tetradecene; optionally 1-hexadecene; or optionally 1-octadene. In other aspects, the first normal α-olefin may include (or substantially consist of) ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or any combination thereof.

[0029] In one aspect of the invention, the first normal α-olefin may comprise ethylene (or substantially composed of or composed of therefrom), and the second normal α-olefin may comprise 1-hexene (or substantially composed of or composed of therefrom). In another aspect, the first normal α-olefin may comprise propylene (or substantially composed of or composed of therefrom), and the second normal α-olefin may comprise 1-octene (or substantially composed of or composed of therefrom). In another aspect, the first normal α-olefin may comprise 1-butene (or substantially composed of or composed of therefrom), and the second normal α-olefin may comprise 1-decene (or substantially composed of or composed of therefrom). In another aspect, the first normal α-olefin may comprise 1-pentene (or substantially composed of or composed of therefrom), and the second normal α-olefin may comprise 1-dodecene (or substantially composed of or composed of therefrom). In another aspect, the first normal α-olefin may comprise 1-hexene (or substantially composed of or composed of therefrom), and the second normal α-olefin may comprise 1-tetradecene (or substantially composed of or composed of therefrom). In another aspect, the first normal α-olefin may include 1-heptene (or consist substantially of or be composed of therein), and the second normal α-olefin may include 1-hexadecene (or consist substantially of or be composed of therein). In another aspect, the first normal α-olefin may include 1-octene (or consist substantially of or be composed of therein), and the second normal α-olefin may include 1-octadecene (or consist substantially of or be composed of therein).

[0030] This document describes an integer n, a first normal α-olefin, and a second normal α-olefin, and their characteristics can be used without limitation to further describe the normal α-olefin synthesis process disclosed herein. Other suitable values ​​for the integer n and the choice of the first and second normal α-olefins are apparent from this disclosure.

[0031] The process step (i) disclosed herein is commonly referred to as the hydroformylation step, and in this step, a structure (C) can be formed in the presence of carbon monoxide and hydrogen. n The first normal-α olefin with -C=C undergoes hydroformylation to form a structure containing C(C). n+1The first composition of the first straight-chain aldehyde of CH (=O). Thus, in one aspect, the hydroformylation step can convert the first n-alpha olefin (such as ethylene or 1-butene) into the first straight-chain aldehyde (such as propionaldehyde or 1-pentanaldehyde). As those skilled in the art will recognize from this disclosure and, for example, Behr et al., Journal of Molecular Catalysis A: Chemical 206 (2003), 179-184; Vogl et al., Journal of Molecular Catalysis A: Chemical 232 (2005), 41-44; Jorke et al., Chemical Engineering Journal, December 12, 2016, 1-34; Peng et al., U.S. Patent No. 7,196,230; and Yan et al., JACS 2006, 128, 16058-16061, any suitable hydroformylation catalyst system for step (i) and any suitable conditions for the hydroformylation reaction in step (i) can be used.

[0032] Although not limited thereto, the hydroformylation in step (i) can utilize a rhodium-based catalyst system. In this respect, the rhodium-based catalyst system may include rhodium and a phosphorus-containing ligand, and the Rh:P elemental ratio is typically in the range of 1:1 to 1:15, more typically falling within the range of 1:2 to 1:10, or 1:2 to 1:6, etc. There are no particular limitations on the specific phosphorus-containing ligand, but BiPhePhos (CAS No. 121627-17-6) is well-suited for use in rhodium-based catalyst systems for hydroformylation reactions.

[0033] In one aspect, the molar ratio of the first n-α-olefin to rhodium in step (i) can fall within the range of 100:1 to 500,000:1; in another aspect, the molar ratio of the first n-α-olefin to rhodium can fall within the range of 100:1 to 10,000:1; and in yet another aspect, the molar ratio of the first n-α-olefin to rhodium can fall within the range of 100:1 to 1000:1. As will readily be appreciated by those skilled in the art, the molar ratio of the α-olefin to rhodium can change as the hydroformylation reaction proceeds. Therefore, these molar ratio ranges are intended to cover the initial ratio and any molar ratio of the first n-α-olefin to rhodium encountered as the hydroformylation reaction proceeds.

[0034] Furthermore, in the hydroformylation reaction of step (i), the molar ratio of carbon monoxide to hydrogen (H2) is generally in the range of 5:1 to 1:5 or 2:1 to 1:2 in some respects, and in other respects in the range of 1.5:1 to 1:1.5 or 1.1:1 to 1:1.1. The sources of carbon monoxide and hydrogen used in step (i) are not limited, but in certain aspects of the invention, the source of carbon monoxide and hydrogen in step (i) may be syngas. As those skilled in the art will recognize, syngas is a mixture primarily containing carbon monoxide and hydrogen. Syngas may also contain small amounts of carbon dioxide and methane.

[0035] There are no particular limitations on the temperature and pressure conditions used for the hydroformylation step. However, generally, the hydroformylation temperature can be in the range of 80 to 200°C; optionally 80 to 160°C; or optionally 100 to 130°C. The hydroformylation pressure can be in the range of 5 to 70 bar; optionally 10 to 50 bar; or optionally 20 to 45 bar. These temperature and pressure ranges are also intended to cover cases where step (i) is carried out at a range of different temperatures and pressures rather than at a single fixed temperature and pressure, wherein at least one temperature and pressure falls within the respective range.

[0036] If desired, and depending on the first n-α olefin (e.g., its carbon number), the hydroformylation temperature and pressure, and other considerations, the hydroformylation reaction in step (i) may optionally be carried out in a diluent. Illustrative and non-limiting examples of diluents that may be used include toluene, propylene carbonate, dimethylformamide, dodecane, and mixtures or combinations thereof (see, for example, Stein, Molecular Catalysis 503, 2021, 111429). Any suitable amount of diluent may be used relative to the amount of the first n-α olefin.

[0037] Typically, hydroformylation is used in step (i) to produce both straight-chain and branched aldehydes, but primarily straight-chain aldehydes are produced. Therefore, the first composition produced via hydroformylation in step (i) may contain a structure having C(C) n+1 The first straight-chain aldehyde of CH (=O), and a small amount of branched-chain aldehyde, and (if used) a diluent. Optionally, prior to step (ii), the process may also include the step of separating an aldehyde composition comprising at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of the first straight-chain aldehyde from the first composition. Any suitable technique may be used, such as extraction, filtration, evaporation, distillation, etc., and any combination thereof.

[0038] Now, referring to step (ii) of the process, the first linear aldehyde formed in step (i) is decarbonylated to form a C-containing compound.2n+5 A second composition of linear intra-chain olefins. Step (ii) of this process is generally referred to as the decarbonylation step. Thus, in step (ii), decarbonylation can convert the first linear aldehyde (such as propionaldehyde or 1-pentanal) into linear intra-chain olefins (such as 2-pentene or 4-nonene), respectively. As those skilled in the art will recognize from this disclosure and, for example, Ainembabazi et al., Journal of the American Chemical Society 2020, 142, 696-699, any suitable decarbonylation catalyst system for step (ii) and any suitable conditions for the decarbonylation reaction in step (ii) can be used.

[0039] Although not limited thereto, the decarbonylation in step (ii) can utilize a palladium-based catalyst system. In this respect, the palladium-based catalyst system can be a supported palladium catalyst, and non-limiting examples include Pd / hydrotalcite, Pd / alumina, Pd / γ-alumina, Pd / silica, Pd / carbon, or Pd / magnesium oxide, and combinations thereof. Any suitable amount of palladium can be used, such as 0.01 to 10 mol%, more typically 0.05 to 5 mol%, or 0.05 to 1 mol%, etc.

[0040] There are no particular limitations on the reaction conditions used for the decarbonylation step. However, in one respect, the decarbonylation reaction temperature can be in the range of 80 to 200 °C, while in another respect, the reaction temperature can be in the range of 100 to 190 °C, and in yet another respect, the reaction temperature can be in the range of 150 to 180 °C. These temperature ranges are also intended to cover the case where step (ii) is carried out at a series of different temperatures rather than at a single fixed temperature, wherein at least one temperature falls within the respective temperature range.

[0041] The decarbonylation in step (ii) produces the desired linear intra-olefin, but may also produce carbon monoxide, water, or both. Therefore, the second composition obtained from step (ii) may contain a linear intra-olefin, carbon monoxide, and water. Thus, prior to step (iii), the process may optionally include the step of separating an intra-olefin composition containing at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of a linear intra-olefin from the second composition. As described above, any suitable technique, such as extraction, filtration, evaporation, distillation, etc., and any combination thereof, may be used.

[0042] Now, referring to step (iii) of the process, in the presence of carbon monoxide and hydrogen, the linear intra-olefin formed in step (ii) isomerizes-hydroformylates to form a product containing the structure C(C). 2n+4The third composition of the second straight-chain aldehyde of CH (=O). Step (iii) of this process is commonly referred to as the isomerization-hydroformylation step. In step (iii), isomerization-hydroformylation can convert the straight-chain olefin (such as 2-pentene or 4-nonene) into the second straight-chain aldehyde (such as 1-hexanal or 1-decanal).

[0043] The isomerization-hydroformylation step (iii) of this process can utilize any catalyst system and reaction conditions disclosed herein for the hydroformylation step (i) of this process, and as disclosed in the references of Behr, Vogl, Jorke, Peng, and Yan. Therefore, the isomerization-hydroformylation in step (iii) can utilize a rhodium-based catalyst system, which may include rhodium and a phosphorus-containing ligand (such as BiPhePhos), with any Rh:P elemental ratio ranging from 1:1 to 1:15.

[0044] Similar to step (i), the molar ratio of carbon monoxide to hydrogen (H2) in the isomerization-hydroformylation reaction of step (iii) can be any molar ratio from 5:1 to 1:5, and the source of carbon monoxide and hydrogen used in step (iii) can be syngas, but is not limited to this. Likewise, the temperature and pressure conditions used for the isomerization-hydroformylation step include the same temperature and pressure conditions as in step (i), and any temperature in the range of 80 to 200 °C and any pressure in the range of 5 to 70 bar can be utilized. Furthermore, similar to step (i), the isomerization-hydroformylation reaction of step (iii) can be carried out in any suitable diluent and using any amount of diluent.

[0045] In one aspect, the molar ratio of the linear olefin to rhodium in step (iii) can fall within the range of 100:1 to 500,000:1, while in another aspect, the molar ratio of the linear olefin to rhodium can fall within the range of 100:1 to 10,000:1, and in yet another aspect, the molar ratio of the linear olefin to rhodium can fall within the range of 100:1 to 1000:1. As will readily be appreciated by those skilled in the art, the molar ratio of the linear olefin to rhodium can change as the isomerization-hydroformylation reaction proceeds. Therefore, these molar ratio ranges are intended to cover the initial ratio as well as any molar ratio of the linear olefin to rhodium encountered as the isomerization-hydroformylation reaction proceeds.

[0046] The isomerization-hydroformylation in step (iii) produces both straight-chain and branched-chain aldehydes, but primarily straight-chain aldehydes. Therefore, the third composition produced via the isomerization-hydroformylation in step (iii) may contain a structure C(C). 2n+4The process may also include a second straight-chain aldehyde of CH (=O) and a small amount of branched-chain aldehyde, and (if used) a diluent. Optionally, prior to step (iv-a) or (iv-b1), the process may further include the step of separating the second aldehyde composition from the third composition containing at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of the second straight-chain aldehyde. This can be achieved by any suitable technique, and non-limiting examples include extraction, filtration, evaporation, distillation, etc. Combinations of two or more techniques may be used.

[0047] Once a second straight-chain aldehyde (with a C(C) structure) is formed... 2n+4 The synthetic process for normal-type α-olefins disclosed in this paper has two alternative pathways to form second normal-type α-olefins (with the structure (C)). 2n+4 -C=C). In one pathway (via step (iv-a)), the second straight-chain aldehyde is hydrogenated-dehydrated, with combined hydrogenation and dehydration carried out in a single combined step to form a compound containing the structure (C). 2n+4 A product composition of a second normal-α-olefin with -C=C structure. Alternatively, a second straight-chain aldehyde (iv-b1) is hydrogenated to form a product containing a C(C) structure. 2n+4 A fourth composition of a straight-chain alcohol containing C(OH) is then formed by dehydrating the straight-chain alcohol (iv-b2) to form a compound containing the structure (C). 2n+4 Composition of products of a second normal-α olefin with -C=C.

[0048] Referring now to the latter approach and steps (iv-b1) and (iv-b2) of this process, step (iv-b1) is generally referred to as the hydrogenation step, and step (iv-b2) is generally referred to as the dehydration step. Therefore, in step (iv-b1), hydrogenation can convert a second straight-chain aldehyde (such as 1-hexanol or 1-decanal) into a straight-chain alcohol (such as 1-hexanol or 1-decanol), respectively. Next, in step (iv-b2), dehydration can convert the straight-chain alcohol (such as 1-hexanol or 1-decanol) into a second n-alpha olefin (such as 1-hexene or 1-decene), respectively.

[0049] As those skilled in the art will recognize from this disclosure and, for example, Chetty et al., American Chemical Society Omega 2018, 3, 7911-7924; and U.S. Patent No. 5,093,535, referring firstly to step (iv-b1), any suitable hydrogenation catalyst system for step (iv-b1) and any suitable conditions for the hydrogenation reaction in step (iv-b1) can be used.

[0050] Although not limited thereto, the hydrogenation in step (iv-b1) can utilize a copper-based catalyst system. Such a copper-based catalyst system can comprise Cu / alumina having any suitable amount of copper based on the weight of the supported catalyst, such as 1 to 35 wt% copper. In some aspects, the amount of copper in the Cu / alumina catalyst falls within the range of 2 to 30 wt% or 5 to 25 wt%, etc.

[0051] There are no particular limitations on the temperature and pressure conditions used for the hydrogenation step. However, generally, the hydrogenation temperature can range from 80 to 200°C; optionally from 90 to 190°C; or optionally from 100 to 180°C. The hydrogenation pressure can range from 10 to 70 bar; optionally from 20 to 50 bar; or optionally from 25 to 45 bar. These temperature and pressure ranges are also intended to cover cases where step (iv-b1) is carried out at a range of different temperatures and pressures rather than at a single fixed temperature and pressure, wherein at least one temperature and pressure falls within the respective range.

[0052] In one aspect, the molar ratio of hydrogen (H2) to the second straight-chain aldehyde in step (iv-b1) can fall within the range of 0.5:1 to 5:1, while in another aspect, the molar ratio can fall within the range of 0.75:1 to 3:1, and in yet another aspect, the molar ratio can fall within the range of 1:1 to 2:1. As will be readily apparent to those skilled in the art, the molar ratio of hydrogen (H2) to the second straight-chain aldehyde can change as the hydrogenation reaction proceeds. Therefore, these molar ratio ranges are intended to cover the initial ratio as well as any molar ratio of hydrogen to the second straight-chain aldehyde encountered as the hydrogenation reaction proceeds.

[0053] The hydrogenation in step (iv-b1) primarily produces the desired straight-chain alcohol, but may form other byproducts of the hydrogenation reaction. Therefore, optionally, prior to step (iv-b2), the process may also include the step of separating an alcohol composition from the fourth composition comprising at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of a straight-chain alcohol. As described herein, this can be achieved via any suitable technique, and non-limiting examples include extraction, filtration, evaporation, distillation, etc., and any combination thereof.

[0054] As those skilled in the art will recognize from this disclosure and, for example, Kim et al., Fuel 256 (2019), 115957, 1-8; and Millet et al., U.S. Patent No. 10,071,937 (2018), with reference now to step (iv-b2), any suitable dehydration catalyst system for step (iv-b2) and any suitable conditions for the dehydration reaction in step (iv-b2) can be used.

[0055] While not limited to this, in one respect, the dehydration in step (iv-b2) can utilize an alumina-based catalyst system, and in another respect, the dehydration in step (iv-b2) can utilize a metal phosphate-based catalyst system. If an alumina-based catalyst system is used, the alumina can be calcined at any suitable temperature prior to step (iv-b2). Typical ranges of calcination temperatures include, for example, 100 to 1200 °C, 250 to 1000 °C, or 400 to 600 °C. If a metal phosphate-based catalyst system is used, suitable metals include lanthanum, neodymium, gadolinium, samarium, and other metals.

[0056] There are no particular restrictions on the reaction conditions used for the dehydration step. However, in one respect, the dehydration reaction temperature can be in the range of 200 to 500 °C, while in another respect, the reaction temperature can be in the range of 250 to 450 °C, and in yet another respect, the reaction temperature can be in the range of 300 to 400 °C. These temperature ranges are also intended to cover the case where step (iv-b2) is carried out at a series of different temperatures rather than at a single fixed temperature, wherein at least one temperature falls within the corresponding temperature range.

[0057] The dehydration in step (iv-b2) produces the desired second n-α-olefin, but may also produce water. Therefore, the product composition obtained from step (iv-b2) may contain the second n-α-olefin and water. Thus, the process may also include a step of purifying the product composition to separate an α-olefin composition containing at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of the second n-α-olefin. Suitable techniques include, for example, extraction, filtration, evaporation, distillation, and combinations thereof.

[0058] Now, referring to the pathway via step (iv-a), the second straight-chain aldehyde is subjected to a combined (single-step) hydrogenation-dehydration to form a structure containing (C). 2n+4 The product composition of the -C=C second normal α-olefin. Step (iv-a) of this process is generally referred to as the hydrogenation-dehydration step. In step (iv-a), hydrogenation-dehydration can convert the second straight-chain aldehyde (such as 1-hexanal or 1-decanal) into the second normal α-olefin (such as 1-hexene or 1-decene), respectively.

[0059] As those skilled in the art will recognize from this disclosure and the aforementioned related hydrogenation and dehydration processes and catalyst systems, any suitable hydrogenation-dehydration catalyst system and any suitable conditions for the hydrogenation-dehydration reaction in step (iv-a) can be used. It is advantageous if this step is not conducive to complete hydrogenation, thus forming a product composition containing less than 10% by weight or less than 5% by weight of alkanes, such as n-alkanes; thus, producing unsaturated second n-alpha olefins in high yield.

[0060] Each step of the disclosed process for synthesizing n-α-olefins can be carried out independently in any suitable reactor or vessel. Non-limiting examples of reactors include fixed-bed reactors, stirred tank reactors, plug flow reactors, circulating reactors, and tubular reactors, including more than one reactor in series or parallel, and any combination of reactor types and arrangements. Each step can be carried out independently in batches or continuously.

[0061] Referring now to the accompanying drawings, a first reaction scheme illustrates the conversion of 1-butene to 1-decene according to the disclosed process, and a second reaction scheme illustrates the conversion of ethylene to 1-hexene according to the disclosed process. In the first reaction scheme, 1-butene is hydroformylated in the presence of carbon monoxide and hydrogen to form 1-pentanal, followed by decarbonylation of 1-pentanal to form 4-nonene. Next, 4-nonene is isomerizes and hydroformylates in the presence of carbon monoxide and hydrogen to form 1-decanal, which is then hydrogenated to form 1-decanol, and finally dehydrated to form 1-decene. Similarly, in the second reaction scheme, ethylene is hydroformylated in the presence of carbon monoxide and hydrogen to form propional, followed by decarbonylation of propional to form 2-pentene. Next, 2-pentene is isomerized-hydroformylated in the presence of carbon monoxide and hydrogen to form 1-hexanal, 1-hexanal is hydrogenated to form 1-hexanol, and finally 1-hexanol is dehydrated to form 1-hexene.

[0062] Example

[0063] The present invention is further illustrated by the following embodiments, which should not be construed as limiting the scope of the invention in any way. After reading this description, those skilled in the art will be able to conceive of various other aspects, modifications, and equivalents of the invention without departing from the spirit of the invention or the scope of the appended claims.

[0064] Constructive Example 1

[0065] Based on the process and the first reaction scheme disclosed herein and in the accompanying drawings, Constructive Example 1 illustrates a representative and non-limiting example of the conversion of 1-butene to 1-decene. First, 1-butene is mixed with a rhodium-BiPhePhos catalyst system in a reactor. The elemental ratio of Rh:P is 1:1.1, and the molar ratio of 1-butene to rhodium is 10,000:1. Carbon monoxide and hydrogen (H2) are added to the reactor at a total pressure of 30 bar, with a carbon monoxide to hydrogen molar ratio of 1:1. The reactor is heated to 150°C, and the reactor contents are stirred for 1 hour to produce a first composition containing 1-pentanal. After cooling, an aldehyde composition containing 82 mol% 1-pentanal is separated from the first composition by distillation.

[0066] The aldehyde composition containing 1-pentanal was decarbonylated by mixing the aldehyde composition with a Pd / alumina catalyst containing 0.3 mol% palladium in a reactor at 180°C for 2 hours. A second composition containing 4-nonene, carbon monoxide, and water was produced. Upon cooling, the carbon monoxide was discharged, and the 4-nonene was separated from the water by distillation or decantation to form an internal olefin composition containing 80 mol% 4-nonene.

[0067] Using the aforementioned rhodium-BiPhePhos catalyst system, the 4-nonene-containing inner olefin composition was isomerized-hydroformylated in a manner similar to 1-butene hydroformylation (although different catalysts can be used to improve selectivity). The second aldehyde composition containing 82 mol% 1-decanal was separated by distillation.

[0068] In a reactor, a second aldehyde composition containing 1-decanal was mixed with a Cu / alumina catalyst containing 10% by weight copper. Hydrogen (H2) was added to the reactor at a total pressure of 50 bar, with a hydrogen to 1-decanal molar ratio of 1.5:1. The reactor was heated to 140°C, and the reactor contents were subjected to a reaction at 18 hr. -1 The mixture was contacted at a liquid hourly space velocity (LHSV) to produce a fourth composition containing 1-decanol. After cooling, the alcohol composition containing 90 mol% 1-decanol was separated from 1-decanol by distillation.

[0069] An alcohol composition containing 1-decyl alcohol was dehydrated by mixing the alcohol composition with pre-calcined alumina at 300°C for 2 hours to form a product composition containing 1-decene. After cooling, the product composition was purified to separate an α-olefin composition containing at least 60 mol% 1-decene by distillation.

[0070] Constructive Example 2

[0071] Using a procedure similar to that of Constructive Example 1, Constructive Example 2 converts ethylene to 1-hexene, as shown in the second reaction scheme in the accompanying drawings.

[0072] The invention has been described herein with reference to many aspects and specific embodiments. Many variations will occur to those skilled in the art based on the detailed description. All such obvious variations are within the full scope of the appended claims. Other aspects of the invention may include, but are not limited to, the following aspects (which are described as “comprising” but may alternatively be “substantially constitute” or “composed of”):

[0073] Aspect 1. A process comprising:

[0074] (i) In the presence of carbon monoxide and hydrogen, it gives rise to a structure (C). n The first normal-α olefin with -C=C undergoes hydroformylation to form a structure containing C(C). n+1 The first composition of the first straight-chain aldehyde of CH (=O);

[0075] (ii) Decarbonylating the first straight-chain aldehyde to form a compound containing C 2n+5 A second composition of linear intra-chain olefins;

[0076] (iii) Isomerizing-hydroformylating the linear intra-chain olefin in the presence of carbon monoxide and hydrogen to form a structure containing C(C). 2n+4 The third composition of the second straight-chain aldehyde of CH (=O); and

[0077] (iv-a) Hydrogenate-dehydrate the second linear aldehyde to form a structure containing (C). 2n+4 Product compositions of -C=C second normal α-olefins; or

[0078] (iv-b1) Hydrogenate the second straight-chain aldehyde to form a structure containing C(C). 2n+4 A fourth composition of straight-chain alcohols of C(OH); and

[0079] (iv-b2) Dehydrate the straight-chain alcohol to form a product containing the structure (C). 2n+4 Product compositions of -C=C second normal α-olefins;

[0080] Where n is an integer from 0 to 30.

[0081] Aspect 2. The process as described in aspect 1, wherein n is an integer from 0 to 18.

[0082] Aspect 3. The process as described in aspect 1, wherein n is an integer from 0 to 6.

[0083] Aspect 4. The process as described in Aspect 1, wherein the first n-alpha olefin comprises ethylene, 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.

[0084] Aspect 5. The process as described in Aspect 1, wherein the first n-alpha olefin comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or any combination thereof.

[0085] Aspect 6. The process as described in Aspect 1, wherein the first n-alpha olefin comprises ethylene, and the second n-alpha olefin comprises 1-hexene.

[0086] Aspect 7. The process as described in Aspect 1, wherein the first n-alpha olefin comprises propylene, and the second n-alpha olefin comprises 1-octene.

[0087] Aspect 8. The process as described in Aspect 1, wherein the first n-alpha olefin comprises 1-butene, and the second n-alpha olefin comprises 1-decene.

[0088] Aspect 9. The process as described in Aspect 1, wherein the first n-alpha olefin comprises 1-pentene, and the second n-alpha olefin comprises 1-dodecene.

[0089] Aspect 10. The process as described in Aspect 1, wherein the first n-alpha olefin comprises 1-hexene, and the second n-alpha olefin comprises 1-tetradecene.

[0090] Aspect 11. The process as described in aspect 1, wherein the first n-alpha olefin comprises 1-heptene, and the second n-alpha olefin comprises 1-hexadecene.

[0091] Aspect 12. The process as described in Aspect 1, wherein the first n-alpha olefin comprises 1-octene, and the second n-alpha olefin comprises 1-octadecene.

[0092] Aspect 13. The process as described in any one of Aspects 1-12, wherein the hydroformylation in step (i) utilizes a rhodium-based catalyst system.

[0093] Aspect 14. The process as described in aspect 13, wherein the rhodium-based catalyst system comprises rhodium and a phosphorus-containing ligand, and the Rh:P elemental ratio is in any suitable range, for example 1:1 to 1:15, 1:2 to 1:10 or 1:2 to 1:6.

[0094] Aspect 15. The process as described in aspect 14, wherein the phosphorus-containing ligand comprises BiPhePhos.

[0095] Aspect 16. The process of any one of Aspects 13-15, wherein the molar ratio of the first n-α olefin to rhodium is in any suitable range, for example 100:1-500,000:1, 100:1-10,000:1 or 100:1-1000:1.

[0096] Aspect 17. The process as described in any one of Aspects 1-16, wherein the molar ratio of carbon monoxide to hydrogen in step (i) is in any suitable range, for example 5:1-1:5, 2:1-1:2 or 1.5:1-1:1.5.

[0097] Aspect 18. The process as described in any one of Aspects 1-17, wherein the carbon monoxide and hydrogen in step (i) are sourced from syngas.

[0098] Aspect 19. The process as described in any one of Aspects 1-18, wherein the hydroformylation in step (i) is carried out at any suitable pressure, such as 5 to 70 bar, 10 to 50 bar or 20 to 45 bar.

[0099] Aspect 20. The process of any one of Aspects 1-19, wherein the hydroformylation in step (i) is carried out at any suitable temperature, for example, 80 to 200°C, 80 to 160°C or 100 to 130°C.

[0100] Aspect 21. The process of any one of Aspects 1-20, wherein the hydroformylation in step (i) is carried out in any suitable diluent, such as toluene, propylene carbonate, dimethylformamide, dodecane or a combination thereof.

[0101] Aspect 22. The process of any one of Aspects 1-21, wherein the first composition further comprises a diluent.

[0102] Aspect 23. The process of any one of Aspects 1-22, further comprising, prior to step (ii), separating from the first composition an aldehyde composition comprising at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of the first linear aldehyde by any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation, or any combination thereof.

[0103] Aspect 24. The process as described in any one of Aspects 1-23, wherein the decarbonylation in step (ii) utilizes a palladium-based catalyst system.

[0104] Aspect 25. The process as described in aspect 24, wherein the palladium-based catalyst system comprises Pd / hydrotalcite, Pd / alumina, Pd / γ-alumina, Pd / silica, Pd / carbon, Pd / magnesium oxide or combinations thereof, having any suitable amount of palladium, for example 0.01-10 mol%, 0.05 to 5 mol%, or 0.05 to 1 mol.

[0105] Aspect 26. The process of any one of Aspects 1-25, wherein the decarbonylation in step (ii) is carried out at any suitable temperature, for example, 80 to 200°C, 100 to 190°C or 150 to 180°C.

[0106] Aspect 27. The process of any one of Aspects 1-26, wherein the second composition further comprises carbon monoxide and / or water.

[0107] Aspect 28. The process of any one of Aspects 1-27, further comprising, prior to step (iii), separating from the second composition, via any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation or any combination thereof, the internal olefin composition comprising at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of the linear internal olefin.

[0108] Aspect 29. The process of any one of Aspects 1-28, wherein the isomerization-hydroformylation in step (iii) utilizes a rhodium-based catalyst system.

[0109] Aspect 30. The process as described in aspect 29, wherein the rhodium-based catalyst system comprises rhodium and a phosphorus-containing ligand, and the Rh:P elemental ratio is in any suitable range, for example 1:1 to 1:15, 1:2 to 1:10 or 1:2 to 1:6.

[0110] Aspect 31. The process as described in aspect 30, wherein the phosphorus-containing ligand comprises BiPhePhos.

[0111] Aspect 32. The process of any one of Aspects 29-31, wherein the molar ratio of the linear intra-olefin to rhodium is in any suitable range, for example 100:1-500,000:1, 100:1-10,000:1 or 100:1-1000:1.

[0112] Aspect 33. The process as described in any one of Aspects 1-32, wherein the molar ratio of carbon monoxide to hydrogen in step (iii) is in any suitable range, for example 5:1-1:5, 2:1-1:2 or 1.5:1-1:1.5.

[0113] Aspect 34. The process as described in any one of Aspects 1-33, wherein the carbon monoxide and hydrogen in step (iii) are sourced from syngas.

[0114] Aspect 35. The process of any one of Aspects 1-34, wherein the isomerization-hydroformylation in step (iii) is carried out at any suitable pressure, such as 5 to 70 bar, 10 to 50 bar or 20 to 45 bar.

[0115] Aspect 36. The process of any one of Aspects 1-35, wherein the isomerization-hydroformylation in step (iii) is carried out at any suitable temperature, for example, 80 to 200°C, 80 to 160°C or 100 to 130°C.

[0116] Aspect 37. The process of any one of Aspects 1-36, wherein the isomerization-hydroformylation in step (iii) is carried out in any suitable diluent, such as toluene, propylene carbonate, dimethylformamide, dodecane or a combination thereof.

[0117] Aspect 38. The process of any one of Aspects 1-37, wherein the third composition further comprises a diluent.

[0118] Aspect 39. The process of any one of Aspects 1-38, further comprising, prior to step (iv-a) or (iv-b1), separating from the third composition a second aldehyde composition comprising at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of the second linear aldehyde by any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation, or any combination thereof.

[0119] Aspect 40. The process as described in any one of Aspects 1-39, wherein the hydrogenation in step (iv-b1) utilizes a copper-based catalyst system.

[0120] Aspect 41. The process as described in aspect 40, wherein the copper-based catalyst system comprises Cu / alumina having any suitable amount of copper, such as 1-35 wt%, 2 to 30 wt%, or 5 to 25 wt%.

[0121] Aspect 42. The process as described in any one of Aspects 1-41, wherein the hydrogenation in step (iv-b1) is carried out at any suitable temperature, for example, 80 to 200°C, 90 to 190°C or 100 to 180°C.

[0122] Aspect 43. The process as described in any one of Aspects 1-42, wherein the hydrogenation in step (iv-b1) is carried out at any suitable pressure, such as 10 to 70 bar, 20 to 50 bar or 25 to 45 bar.

[0123] Aspect 44. The process of any one of Aspects 1-43, wherein the hydrogenation in step (iv-b1) is carried out at any suitable molar ratio of hydrogen to the second linear aldehyde, for example 0.5:1-5:1, 0.75:1-3:1 or 1:1-2:1.

[0124] Aspect 45. The process of any one of Aspects 1-44, further comprising, prior to step (iv-b2), separating from the fourth composition an alcohol composition comprising at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of the straight-chain alcohol by any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation, or any combination thereof.

[0125] Aspect 46. The process as described in any one of Aspects 1-45, wherein the dehydration in step (iv-b2) utilizes an alumina-based catalyst system.

[0126] Aspect 47. The process as described in aspect 46, wherein prior to step (iv-b2), the alumina is calcined at any suitable temperature, such as 100 to 1200°C, 250 to 1000°C, or 400 to 600°C.

[0127] Aspect 48. The process as described in any one of Aspects 1-45, wherein the dehydration in step (iv-b2) utilizes a metal phosphate-based catalyst system.

[0128] Aspect 49. The process as described in any one of Aspects 1-48, wherein the dehydration in step (iv-b2) is carried out at any suitable temperature, for example, 200 to 500°C, 250 to 450°C or 300 to 400°C.

[0129] Aspect 50. The process of any one of Aspects 1-49, wherein the product composition further comprises water.

[0130] Aspect 51. The process of any one of Aspects 1-50, further comprising the step of purifying the product composition by any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation or any combination thereof, to separate the α-olefin composition comprising at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 96 mol% of the second n-α-olefin.

Claims

1. A process for producing n-alpha olefins, comprising: (i) In the presence of carbon monoxide and hydrogen, it gives rise to a structure (C). n The first normal-α olefin with -C=C undergoes hydroformylation to form a structure containing C(C). n+1 The first composition of the first straight-chain aldehyde of CH (=O); (ii) Decarbonylating the first straight-chain aldehyde to form a compound containing C 2n+5 A second composition of a straight-chain intra-olefin, wherein the decarbonylation is performed using a palladium-based catalyst system; (iii) Isomerizing-hydroformylating the linear intra-chain olefin in the presence of carbon monoxide and hydrogen to form a structure containing C(C). 2n+4 The third composition of a second straight-chain aldehyde of CH (=O), wherein the isomerization-hydroformylation utilizes a rhodium-based catalyst system; as well as (iv-a) Hydrogenate-dehydrate the second linear aldehyde to form a structure containing (C). 2n+4 Product compositions of -C=C second normal α-olefins; or (iv-b1) Hydrogenate the second straight-chain aldehyde to form a structure containing C(C). 2n+4 The fourth composition of straight-chain alcohols of C(OH); as well as (iv-b2) Dehydrate the straight-chain alcohol to form a product containing the structure (C). 2n+4 Product compositions of -C=C second normal α-olefins; Where n is an integer from 0 to 18.

2. The process of claim 1, wherein n is an integer from 0 to 6.

3. The process of claim 1, wherein the first n-alpha olefin comprises ethylene, and the second n-alpha olefin comprises 1-hexene.

4. The process of claim 1, wherein the first n-alpha olefin comprises propylene, and the second n-alpha olefin comprises 1-octene.

5. The process of claim 1, wherein the first n-alpha olefin comprises 1-butene, and the second n-alpha olefin comprises 1-decene.

6. The process of claim 1, wherein the hydroformylation in step (i) utilizes a rhodium-based catalyst system.

7. The process of claim 6, wherein the molar ratio of the first n-alpha olefin to rhodium is in the range of 100:1 to 500,000:

1.

8. The process as described in claim 1, wherein: The carbon monoxide and hydrogen in step (i) are sourced from syngas; and The hydroformylation in step (i) is carried out in a diluent.

9. The process of claim 1, further comprising, prior to step (ii), separating an aldehyde composition comprising at least 85 mol% of the first linear aldehyde from the first composition.

10. The process of claim 1, wherein the palladium-based catalyst system comprises Pd / hydrotalcite, Pd / alumina, Pd / silica, Pd / carbon, Pd / magnesium oxide, or a combination thereof.

11. The process of claim 10, wherein the Pd / alumina is Pd / γ-alumina.

12. The process of claim 1, wherein: The second composition further comprises carbon monoxide and / or water; and The process further includes, prior to step (iii), separating the intraolefinic composition comprising at least 85 mol% of the linear intraolefinic olefin from the second composition.

13. The process of claim 1, wherein the rhodium-based catalyst system comprises rhodium and a phosphorus-containing ligand, and the elemental ratio of Rh:P is in the range of 1:1 to 1:

15.

14. The process of claim 13, wherein the phosphorus-containing ligand comprises BiPhePhos.

15. The process of claim 1, wherein the molar ratio of carbon monoxide to hydrogen in step (iii) is in the range of 5:1 to 1:

5.

16. The process of claim 1, wherein the process includes step (iv-b1) and step (iv-b2).

17. The process of claim 16, wherein the hydrogenation in step (iv-b1) utilizes a copper-based catalyst system.

18. The process of claim 16, wherein the hydrogenation in step (iv-b1) is carried out at a molar ratio of hydrogen to the second linear aldehyde in the range of 0.5:1 to 5:

1.

19. The process of claim 16, wherein the dehydration in step (iv-b2) utilizes an alumina-based catalyst system or a metal phosphate-based catalyst system.

20. The process of claim 1, further comprising the step of purifying the product composition to separate the α-olefin composition containing at least 85 mol% of the second n-α-olefin.

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