Method of increasing alpha-olefin content

Abstract

To provide methods for purifying α-olefins, which may be used to form drag reducing agents for improving flow of hydrocarbons through pipelines.SOLUTION: In one implementation, there is provided a method of increasing α-olefin content. The method includes providing an olefin feedstock composition having an α-mono-olefin and at least one of a diolefin having an equal number of carbon atoms to the α-mono-olefin and / or a triolefin having an equal number of carbon atoms to the α-mono-olefin. The method further includes contacting the olefin feedstock composition with ethylene in the presence of a catalyst composition including an olefin metathesis catalyst. The method further includes reacting the olefin feedstock composition and ethylene at metathesis reaction conditions to produce an α-olefin product comprising the α-mono-olefin and α-olefins having fewer carbon atoms than the α-mono-olefin.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 62 / 515,975, filed June 6, 2017, and U.S. Publication No. 15 / 981,021, filed May 16, 2018. [Background technology]

[0002] Field The practice described herein generally relates to methods for purifying alpha-olefins for use, inter alia, in drag reduction agents, to improve the flow of hydrocarbons through conduits, particularly pipelines.

[0003] 2. Description of Related Art The flow of liquids in conduits, such as pipelines, typically results in frictional energy losses. Because of this energy loss, the pressure of the liquid in the conduit decreases along the conduit in the direction of flow. For a conduit of fixed diameter, this pressure drop increases with increasing flow rate. When the flow in the conduit is turbulent (e.g., when the Reynolds number is greater than about 2100), certain ultra-high molecular weight polymers can be added to the liquid flowing through the conduit to reduce the frictional energy losses and change the relationship between pressure drop and flow rate. Such polymers, sometimes called drag reducing agents ("DRAs"), interact with the turbulent flow process and reduce the frictional pressure losses, resulting in a lower pressure drop for a given flow rate or a higher flow rate for a given pressure drop. Because DRAs reduce frictional energy losses, they can improve the flow capability of pipelines, hoses, and other conduits through which liquids flow. DRAs also reduce the cost of pumping the fluid, the cost of the equipment used to pump the fluid, and provide for the use of smaller pipe diameters for a given flow capacity. Thus, there is a continuing need to form improved drag reducing materials.

[0004] Generally, many commercial oil pipeline DRAs are primarily amorphous or non-crystalline ultra-high molecular weight polyalphaolefin polymers, highly linear polymers produced from various alpha-olefin monomers. These alpha-olefin monomers are typically made by oligomerization of ethylene, chemical conversion of selected vegetable oils, or other manufacturing processes, and are the feedstock for making DRA. However, in addition to the alpha-olefin monomers, the feedstock for ethylene oligomerization or other alpha-olefin manufacturing processes may also result in other isomers or by-products with the same number of carbon atoms. The presence of such other isomers may interfere with the polymerization to form DRA. Therefore, there is a need to increase the alpha-olefin content in the feedstock for making DRA, among others. There is also a need to increase the alpha-olefin content in the feedstock for other olefinic compounds. Summary of the Invention

[0005] The implementations described herein generally relate to methods for purifying alpha-olefins. Alpha-olefins can be used, among other things, to form drag reducers for improving the flow of hydrocarbons through conduits, particularly pipelines. In one implementation, a method for increasing alpha-olefin content is provided. The method includes providing an olefin feed composition having an alpha-mono-olefin and at least one of a diolefin having the same number of carbon atoms as the alpha-mono-olefin and / or a triolefin having the same number of carbon atoms as the alpha-mono-olefin. The method further includes contacting the olefin feed composition with ethylene in the presence of a catalyst composition comprising an olefin metathesis catalyst. The method further includes reacting the olefin feed composition with ethylene under metathesis reaction conditions to produce an alpha-olefin product comprising the alpha-mono-olefin and one or more alpha-olefins having fewer carbon atoms than the alpha-mono-olefin. Separation, such as by distillation, results in a fraction highly enriched in alpha-mono-olefins.

[0006] In another implementation, a method for increasing alpha-olefin content is provided. The method includes providing an olefin feed composition having alpha-mono-olefins and vinylidene olefins. The method further includes reacting the olefin feed composition in the presence of an isomerization catalyst to form an isomerized olefin feed having branched internal olefins formed from the vinylidene olefins and the alpha-mono-olefins. The method further includes contacting the isomerized olefin feed composition with ethylene in the presence of a catalyst composition having an olefin metathesis catalyst. The method further includes reacting the isomerized olefin feed composition with ethylene under metathesis reaction conditions to produce an alpha-olefin product having the alpha-mono-olefins, linear and branched olefins having fewer carbon atoms than the alpha-mono-olefins. Separation, such as by distillation, provides a fraction highly enriched in the alpha-mono-olefins.

[0007] In yet another implementation, a method for increasing alpha-olefin content is provided. The method includes providing an olefin feed composition comprising 1-decene and at least one diolefin having at least 10 carbon atoms and / or triolefin having at least 10 carbon atoms. The method further includes contacting the olefin feed composition with ethylene in the presence of a catalyst composition comprising an olefin metathesis catalyst. The method further includes reacting the olefin feed composition with ethylene under metathesis reaction conditions to produce an alpha-olefin product comprising 1-decene and at least one of a terminal olefin having less than 10 carbon atoms and a diolefin having less than 10 carbon atoms. Separation, such as by distillation, provides a fraction highly enriched in 1-decene.

[0008] In yet another implementation, a method for increasing alpha-olefin content is provided. The method includes providing an olefin feed composition having 1-decene and vinylidene olefins. The method further includes reacting the olefin feed composition in the presence of a zeolite catalyst to form an isomerized olefin feed having 1-decene and branched internal olefins formed from the vinylidene olefins. The method further includes contacting the isomerized olefin feed composition with ethylene in the presence of a catalyst composition having an olefin metathesis catalyst. The method further includes reacting the isomerized olefin feed composition with ethylene under metathesis reaction conditions to produce an alpha-olefin product having 1-decene, linear and branched olefins having less than 10 carbon atoms. Separation, such as by distillation, provides a fraction highly enriched in 1-decene.

[0009] In yet another implementation, a method for increasing alpha-olefin content is provided. The method includes providing an olefin feed composition having linear internal mono-olefins and, optionally, at least one of alpha-olefins, vinylidene olefins, diolefins, and / or triolefins having more than 10 carbon atoms. The method further includes providing a catalyst composition comprising an olefin metathesis catalyst. The method further includes reacting the olefin feed composition with ethylene in the presence of the catalyst composition under metathesis reaction conditions to produce an alpha-olefin product comprising the alpha-mono-olefins and one or more alpha-olefins having fewer carbon atoms than the alpha-mono-olefins. Separation, such as by distillation, provides a fraction highly enriched in alpha-mono-olefins.

[0010] In yet another implementation, a method for increasing alpha-olefin content is provided. The method includes providing an olefin feed composition having 3-dodecene and, optionally, at least one of an alpha-olefin, a vinylidene olefin, a diolefin, and / or a triolefin. The method further includes contacting the olefin feed composition with ethylene in the presence of a catalyst composition comprising an olefin metathesis catalyst. The method further includes reacting the olefin feed composition with ethylene under metathesis reaction conditions to produce an alpha-olefin product having 1-decene, linear and branched olefins having less than 10 carbon atoms. Separation, such as by distillation, provides a fraction highly enriched in 1-decene. [Brief description of the drawings]

[0011] So that the above-mentioned features of the present disclosure can be understood in detail, a more particular description of the implementations briefly summarized above can be had by reference to the drawings of the implementations, some of which are illustrated in the accompanying drawings. It should be noted, however, that since the present disclosure may admit of other equally effective implementations, the accompanying drawings illustrate only typical implementations of the present disclosure and therefore should not be considered as limiting the scope of the disclosure. [Figure 1] 1 shows a first example of a reaction scheme for increasing olefin content in accordance with one or more implementations of the present disclosure. [Diagram 2] FIG. 2 shows a second example of a reaction scheme for increasing olefin content in accordance with one or more implementations of the present disclosure. [Diagram 3] FIG. 1 shows a third example of a reaction scheme for increasing olefin content in accordance with one or more implementations of the present disclosure.

[0012] To facilitate understanding, the same reference numbers have been used, where possible, for identical components that are common between the figures. It is contemplated that components and features of one implementation may be beneficially incorporated in other implementations without further recitation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The following disclosure describes methods for increasing alpha-olefin content, more specifically, for increasing the purity of alpha-olefins in an olefin feedstock, and for forming drag reducers incorporating alpha-olefins. Although described in the context of drag reducers, the implementations described herein are also applicable to other processes in which high purity alpha-olefins are desired. In order to provide a thorough understanding of the various implementations of the present disclosure, certain details are described in the following description. Other details describing well-known details (often associated with isomerization, metathesis, and distillation processes) are not described in the following disclosure to avoid unnecessarily obscuring the description of the various implementations.

[0014] Different aspects, implementations and features are defined in detail herein, and each aspect, implementation or feature so defined can be combined with other (desirable, advantageous or other) aspect, implementation or feature(s), unless expressly stated otherwise.

[0015] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0016] As used herein, the terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0017] As used herein, the term "alpha-olefin" refers to an olefin having a double bond between a first and a second carbon atom. The term "alpha-olefin" includes linear and branched alpha-olefins unless otherwise specified. In the case of branched alpha-olefins, the branching may be at the 2-position (vinylidene olefins) and / or the 3-position or higher relative to the olefinic double bond. The term "alpha-olefin" itself does not indicate the presence or absence of heteroatoms and / or the presence or absence of other carbon-carbon double bonds unless expressly indicated. The term "hydrocarbon alpha-olefin" or "alpha-olefin hydrocarbon" refers to an alpha-olefin compound containing only hydrogen and carbon. The terms "alpha-olefin" and "terminal olefin" may be used interchangeably.

[0018] As used herein, the term "alpha-mono-olefin" refers to an olefin having a double bond between a first and a second carbon atom. Examples of alpha-mono-olefins include 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, and the like. The terms "alpha-mono-olefin" and "1-olefin" can be used interchangeably.

[0019] As used herein, the term "diolefin" refers to an olefin having an unsaturated hydrocarbon containing two pairs of carbon atoms joined by a double bond.

[0020] As used herein, the term "triolefin" refers to an olefin having an unsaturated hydrocarbon containing three pairs of carbon atoms joined by double bonds.

[0021] As used herein, the term "olefin metathesis catalyst" includes any catalyst or catalyst system that catalyzes an olefin metathesis reaction.

[0022] As used herein, the term "internal olefin" refers to an olefin having a double bond at any position other than between the first and second carbon atoms. An "internal olefin" may be linear or branched. A "branched internal olefin" has a branch at one of the carbon atoms of the internal double bond and / or has a branch at any carbon atom other than the one involved in the carbon atom internal olefin double bond. The term "internal olefin" does not indicate the presence or absence of other groups, branches, heteroatoms, or double bonds in the "internal olefin" unless expressly indicated (e.g., internal mono-olefin). A "linear internal olefin", whenever used in the specification and claims, refers to a linear olefin in which the double bond is not a terminal double bond (e.g., only one organyl group attached to each carbon atom). The term "linear internal olefin" does not indicate the presence or absence of other groups, heteroatoms, or double bonds unless expressly indicated (e.g., linear internal mono-olefin).

[0023] As used herein, the term "feed olefins" or "olefin feed composition" refers to the olefinic compounds originally present in the feed composition or olefin feed composition prior to contact with the metathesis catalyst. As used herein, the term "feed olefins" or "olefin feed composition" does not include new olefinic compounds (which were not originally present in the "olefin feed") that are produced during the metathesis reaction (via metathesis and / or isomerization reactions).

[0024] As used herein, the term "alpha-olefin product" refers to an organic material produced by a metathesis reaction. The term "alpha-olefin product" refers to a material produced by a metathesis reaction having a carbon number equal to or less than the carbon number of the original feed olefin having the highest number of carbon atoms present in an amount of at least 3 weight percent. The term "alpha-olefin product" includes internal olefins (which may not be alpha-olefins).

[0025] As used herein, the terms "isomerization," "isomerizes," or "isomerizing" may refer to the shifting of a carbon-carbon double bond to another position within a molecule.

[0026] As used herein, the term "vinylidene olefin," whenever used in the specification and claims, refers to an alpha-olefin having a branch at the 2-position relative to the olefinic double bond. Vinylidene olefins have the structure (R1)(R2)C=CH2, where R1 and R2 are the same or, more commonly, different alkyl groups. Examples of vinylidene olefins include 2-methyl-1-butene, 2-methyl-1-pentene, 2-ethyl-1-octene, 2-ethyl-1-decene, 2-methyl-1-nonene, 2-butyl-1-decene, 2-propyl-1-octene, 2-ethyl-1-dodecene, 2-hexyl-1-decene, 2-ethyl-1-tetradecene, 2-ethyl-1-hexadecene, 2-methyl-1-heptadecene, 2-ethyl-1-octadecene, 2-butyl-1-hexadecene, 2-ethyl-1-eicosene, 2-butyl-1-octadecene, 2-ethyl-1-docosene, and the like.

[0027] Alpha-olefins are typically made by oligomerization of ethylene, chemical conversion of selected vegetable oils, or other manufacturing methods, and are the feedstock for making drag-reducing polymers. The alpha-olefins (also known as 1-alkenes) in the oligomerization or conversion mixture are most effective in making drag-reducing polymers, and all other isomers present (e.g. diolefins, triolefins, vinylidene olefins, or internal olefins) usually interfere with the polymerization to make ultra-high molecular weight drag-reducing polymers. Usually, these other isomers are also detrimental to other chemical reactions of the alpha-olefins. Thus, while the purity of the alpha-olefins in the feed is often 95% or higher, an increase in the alpha-olefin content is desired. One known method is to improve the alpha-olefin feedstock by isomerizing 2-ethyl-1-alkenes to branched internal olefins using a zeolite catalyst. However, these resulting branched olefins are no longer useful in olefin polymerization to make drag-reducing polymers than the precursors, nor are the branched olefins removed.

[0028] One implementation of the present disclosure includes a method for purifying an alpha-olefin feed stream by taking the isomerized olefin feed resulting from zeolite processing and performing an olefin metathesis reaction with ethylene followed by removal of the low boiling fragments. The olefin metathesis with ethylene converts the internal olefins and isomerization products to low boiling, low carbon olefins. The alpha-olefins are essentially unreacted. Although the alpha-olefins can undergo metathesis with ethylene, it is a futile reaction returning the same alpha-olefins and ethylene. The by-product olefins can be removed by distillation to provide a feed with increased alpha-olefin content. An additional advantage of this method is that it can also be used to produce odd carbon number alpha-olefins by further processing the low boiling stream. Additionally, other specialty olefins can be isolated using the implementations described herein.

[0029] Implementations of the present disclosure relate to a process for producing an olefin feedstock having high purity alpha-olefins. In one implementation, the alpha-olefin content in the olefin feedstock composition is increased by contacting an alpha-olefin feedstock containing diolefin and / or triolefin impurities with ethylene in the presence of an olefin metathesis catalyst and distilling off the low boiling products. In another implementation, the alpha-olefin content in the olefin feedstock composition is increased by contacting an alpha-olefin feedstock containing vinylidene olefin impurities with an isomerization catalyst in the presence of an olefin metathesis catalyst and then contacting it with ethylene and distilling off the low boiling products.

[0030] The process / method features, such as the olefin feedstock, the feed composition comprising the olefin feedstock, the olefin constraints (if any) of the olefin feedstock, the olefin metathesis catalyst, the olefin catalyst composition comprising the olefin metathesis catalyst, the olefin metathesis catalyst constraints (if any), the isomerized olefin feedstock, the isomerized feed composition comprising the isomerized olefin feedstock, the olefin constraints (if any) of the isomerized olefin feedstock, the zeolite catalyst, the zeolite catalyst composition comprising the zeolite catalyst, the zeolite catalyst constraints (if any), the alpha-olefin product, the constraints on the alpha-olefin product, the olefin metathesis reaction conditions, the constraints on the olefin metathesis reaction conditions, the isomerization reaction conditions, the constraints on the isomerization reaction conditions, the constraints on the isomerization reaction conditions, the features of the process / method, as well as other methods, features and / or steps, are described independently herein. These features may be utilized in any combination necessary to describe a process / method for producing an alpha-olefin product having a desired alpha-olefin purity.

[0031] In one implementation, the method includes (1) providing an olefin feed composition having an alpha-mono-olefin and at least one of a diolefin having the same number of carbon atoms as the alpha-mono-olefin and / or a triolefin having the same number of carbon atoms as the alpha-mono-olefin. The method further includes (2) providing a catalyst composition having an olefin metathesis catalyst. The method further includes (3) reacting the olefin feed composition with ethylene in the presence of the olefin metathesis composition under metathesis reaction conditions to produce an alpha-olefin product comprising the alpha-mono-olefin and one or more alpha-olefins having fewer carbon atoms than the alpha-mono-olefin. Separation by a method such as distillation provides a fraction highly enriched in the alpha-mono-olefins. Without being bound by theory, it is believed that the alpha-mono-olefins pass through the metathesis reaction unchanged, while the diolefins and triolefins react under the metathesis reaction conditions to form lower molecular weight olefins and diolefins that can be easily removed by distillation.

[0032] FIG. 1 illustrates a first example of a reaction scheme 100 for increasing olefin content according to one or more implementations of the present disclosure. In another implementation of FIG. 1, the method includes (1) providing an olefin feed composition having 1-decene and at least one of a diolefin having at least 10 carbon atoms and / or a triolefin having at least 10 carbon atoms. The method further includes (2) providing a catalyst composition having an olefin metathesis catalyst. The method further includes (3) reacting the olefin feed composition with ethylene in the presence of the catalyst composition under metathesis reaction conditions to produce an alpha-olefin product composition having 1-decene and one or more alpha-olefins having less than 10 carbon atoms.

[0033] An olefinic feedstock may generally comprise or consist essentially of any olefinic compound. Additional characteristics that may be used to describe the olefins, among other olefinic feedstock characteristics described herein, include the types of olefins present, the carbon number of the olefins present, the average molecular weight of the olefins, and / or the content (i.e., weight percent or mole percent) of a particular type of olefin present. These characteristics of an olefinic feedstock are described independently herein and may be used in any combination to describe the olefins of the olefinic feedstock.

[0034] In some implementations, the olefins of the olefin feedstock may comprise or consist of aliphatic olefins, aromatic olefins, or combinations thereof, or aliphatic olefins; or aromatic olefins. In some implementations, the olefins of the olefin feedstock (aliphatic or aromatic) may comprise or consist essentially of linear olefins, branched olefins, or combinations thereof, or linear olefins; or branched olefins. In other implementations, the olefins of the olefin feedstock (aliphatic or aromatic, linear or branched, or combinations thereof) may comprise or consist essentially of acyclic olefins, cyclic olefins, or combinations thereof; or acyclic olefins, or cyclic olefins. In some implementations, the olefins of the olefin feedstock (aliphatic or aromatic, linear or branched, cyclic or acyclic, or combinations thereof) may comprise or consist essentially of hydrocarbon olefins. In some implementations, the olefins of the olefin feedstock (aliphatic or aromatic, linear or branched, cyclic or acyclic, hydrocarbon, or combinations thereof) may comprise or consist essentially of alpha-olefins. In some implementations, the olefins of the olefin feedstock (aliphatic or aromatic, cyclic or acyclic, hydrocarbon, or combinations thereof) may comprise or consist essentially of linear alpha-olefins and branched alpha-olefins, where the branch(es) are on the 3rd or higher carbon atom relative to the olefinic double bond; or linear alpha-olefins; or branched alpha-olefins having branches at the 3rd or higher carbon atom relative to the olefinic double bond. In some implementations, the olefins of the olefin feedstock (aliphatic or aromatic, linear or branched, cyclic or acyclic, hydrocarbon, or combinations thereof) may comprise or consist essentially of hydrocarbon alpha-olefins. In some implementations, the olefins of the olefin feedstock may comprise or consist essentially of linear hydrocarbon alpha-olefins; or normal alpha-olefins.

[0035] In some implementations, the olefins of the olefin feedstock (aliphatic or aromatic, linear or branched, cyclic or acyclic, hydrocarbon, alpha-olefins, or combinations thereof) may comprise or consist essentially of mono-olefins, diolefins, and / or triolefins. In some implementations, the olefins of the olefin feedstock (aliphatic or aromatic, linear or branched, cyclic or acyclic, alpha-olefins, or combinations thereof) may comprise or consist essentially of hydrocarbon mono-olefins, diolefins, and / or triolefins. In some implementations, the olefins of the olefin feedstock (aliphatic or aromatic, linear or branched, cyclic or acyclic, hydrocarbon, or alpha-olefins, normal alpha-olefins, mono-olefins, diolefins, triolefins, or combinations thereof) may comprise or consist essentially of olefins having an even number of carbon atoms; or olefins having an odd number of carbon atoms.

[0036] In some implementations, the olefin feedstock may comprise or consist essentially of olefins having at least 4 carbon atoms, or at least 6 carbon atoms, or at least 8 carbon atoms, or at least 10 carbon atoms, or at least 12 carbon atoms, or at least 14 carbon atoms, or at least 16 carbon atoms, or at least 18 carbon atoms. In some implementations, the olefin feedstock may comprise or consist essentially of olefins having from 4 to 20 carbon atoms, or from 6 to 16 carbon atoms, or from 8 to 14 carbon atoms, or from 10 to 12 carbon atoms, or mixtures thereof.

[0037] In some implementations, the olefin feedstock may comprise or consist essentially of alpha-mono-olefins having at least 4 carbon atoms; or at least 6 carbon atoms; or at least 8 carbon atoms; or at least 10 carbon atoms; or at least 12 carbon atoms; or at least 14 carbon atoms; or at least 16 carbon atoms; or at least 18 carbon atoms. In some implementations, the olefin feedstock may comprise or consist essentially of alpha-mono-olefins having from 4 to 20 carbon atoms; or from 6 to 16 carbon atoms; or from 8 to 14 carbon atoms; or from 10 to 12 carbon atoms; or mixtures thereof. In some implementations, the alpha-mono-olefin is 1-decene.

[0038] In some implementations, the olefin feed composition comprises an alpha-mono-olefin and at least one of a diolefin having the same number of carbon atoms as the alpha-mono-olefin and / or a triolefin having the same number of carbon atoms as the alpha-mono-olefin. In some implementations, the olefin feed composition further comprises at least one of a diolefin having a different number of carbon atoms compared to the alpha-mono-olefin and / or a triolefin having a different number of carbon atoms compared to the alpha-mono-olefin. In some implementations, the olefin feed composition further comprises a second alpha-mono-olefin having a different number of carbon atoms compared to the first alpha-mono-olefin.

[0039] In one implementation, the olefin feed composition comprises 93.5-96 wt % (eg, 94-96 wt %) alpha-mono-olefins, 1-6 wt % diolefins, and 0-4 wt % (eg, 0.5-4 wt %) triolefins.

[0040] In some implementations, the olefin feed composition includes alpha-mono-olefins and at least one of a diolefin having at least 10 carbon atoms and / or a triolefin having at least 10 carbon atoms. In some implementations, the olefin feed composition includes 93.5-96 wt % (e.g., 94-96 wt %) 1-decene, 1-6 wt % diolefin, and 0-4 wt % (e.g., 0.5-4 wt %) triolefin.

[0041] At a minimum, the feed composition comprising an olefinic feedstock may comprise any desired olefinic feedstock as described herein. In some implementations, the feed composition comprising an olefinic feedstock may further comprise a solvent or diluent. In some implementations, the feed composition comprising an olefinic feedstock may consist essentially of any olefinic feedstock as described herein; or may consist essentially of any olefinic feedstock as described herein and any solvent or diluent as described herein. Solvents or diluents that may be utilized in the feed composition comprising an olefinic feedstock are described herein. In other implementations, the feed composition comprising an olefinic feedstock may be substantially devoid of a solvent or diluent.

[0042] In some implementations, the olefin feed composition is contacted with ethylene in the presence of an olefin metathesis catalyst. The ethylene may be fed to a reactor containing the olefin metathesis catalyst. In some implementations, the ethylene and the olefin feed composition flow into the reactor simultaneously. In some implementations, the ethylene and the olefin feed composition flow into the reactor sequentially.

[0043] In general, any olefin metathesis catalyst capable of producing an alpha-olefin product having the desired purity of alpha-mono-olefins can be used, although a particular type(s) of olefin metathesis catalyst may be preferred in a particular case depending on other metathesis reaction parameters (e.g., olefin feedstock characteristics and / or metathesis reaction conditions).

[0044] Olefin metathesis catalysts and / or olefin metathesis catalyst systems can be classified into compounds of olefin metathesis catalysts contacted with the olefin feedstock or into recognized initial olefin metathesis catalyst types. Once the metathesis reaction is initiated, the initial catalyst species is converted to other species, so it can often be difficult to determine the true catalyst species. Those skilled in the art will readily recognize the type of olefin metathesis catalyst or olefin metathesis catalyst system based on the compounds contacted with the olefin feedstock. In some implementations, a precursor of the olefin metathesis catalyst or olefin metathesis catalyst system may be contacted with the olefin feedstock first to create the olefin metathesis catalyst or olefin metathesis catalyst system in situ. Those skilled in the art will readily recognize the specific type of olefin metathesis catalyst and / or olefin metathesis catalyst system from the materials added with / contacted with the olefin feedstock. Non-limiting examples of suitable olefin metathesis catalysts include Grubbs' catalyst, Hoveyda's catalyst, and Schrock's catalyst, which are known in the art.

[0045] Olefin metathesis is the metal-catalyzed redistribution of olefinic (alkenyl) carbon-carbon double bonds between two or more reactants. Much of this work was pioneered by Grubbs and Schrock, who shared the Nobel Prize in 2005, and many of the catalyst species utilized in the aforementioned reactions are named after them. For example, “Olefin Metathesis,” Tetrahedron, vol. 60, pp. 7117-7140 (2004); RR Schrock et al., “Molybdenum and Tungsten Imido Alkylidene Complexes as Efficient Olefin-Metathesis Catalysts,” Angew. Chem. Int. Ed., vol. 42, pp. 4592-4633 (2003); and Trnka et al., “The Development of L2X2Ru=CHR Olefin Metathesis Catalysts: An Organometallic Success Story,” Acc. Chem. Res., vol. 34, pp. 18-29 (2001).

[0046] The olefin metathesis catalyst is a transition metal complex comprising a metal selected from the group consisting of Ni, W, Ru, Mo, Re, and combinations thereof. In some implementations, the olefin metathesis catalyst is a transition metal complex comprising Ru.

[0047] In certain implementations, the olefin metathesis catalyst can be a metal oxide-based olefin metathesis catalyst system, a metal halide-based olefin metathesis catalyst system, or a metal carbene-based olefin metathesis catalyst system. In some implementations, the olefin metathesis catalyst can be a metal oxide-based olefin metathesis catalyst system, or a metal halide-based olefin metathesis catalyst system. In other implementations, the olefin metathesis catalyst can be a metal oxide-based olefin metathesis catalyst system; or a metal halide-based olefin metathesis catalyst system; or a metal carbene-based olefin metathesis catalyst system.

[0048] Examples of suitable metal oxide-based olefin metathesis catalysts or catalyst systems (hereinafter "metal oxide olefin metathesis catalysts") can include cobalt oxide, molybdenum oxide, tungsten oxide, rhenium oxide, or combinations thereof. In some implementations, the metal oxide olefin metathesis catalyst further comprises a support; alternatively, the metal oxide olefin metathesis catalyst can be unsupported. Suitable metal oxide olefin metathesis catalyst supports include alumina, silica, silica-alumina, and aluminum phosphate. In further implementations, the metal oxide olefin metathesis catalyst further comprises a metal alkyl activator. Suitable metal alkyl activators for metal oxide olefin metathesis catalysts are described herein. Non-limiting examples of suitable metal oxide olefin metathesis catalysts include molybdenum oxide on alumina (MoO3 / Al2O3), tungsten oxide on silica (WO3 / SiO2), rhenium oxide on alumina (Re2O7 / Al2O3), cobalt and molybdenum oxides on alumina (CoO / MoO3 / Al2O3), and rhenium oxide on alumina activated with tetramethyltin (Re2O7 / Al2O3 / SnMe4). Other suitable metal oxide metathesis catalysts will be known to those skilled in the art.

[0049] Suitable metal halide-based olefin metathesis catalysts and / or catalyst systems (hereinafter referred to as "metal halide metathesis catalysts") may include halides of tungsten, molybdenum, or mixtures thereof. In some implementations, the halides of the metal halide olefin metathesis catalysts may be chlorides, bromides, or iodides; alternatively chlorides; alternatively bromides; alternatively iodides. In some implementations, the metal halide olefin metathesis catalysts may include tungsten chloride, molybdenum chloride, or mixtures thereof. In other implementations, the metal halide olefin metathesis catalysts include tungsten chloride or molybdenum chloride. Typically, the metal halide olefin metathesis catalysts further include a metal alkyl activator. Suitable metal alkyl activators for the metal halide olefin metathesis catalysts are described herein. The metal halide olefin metathesis catalysts may further include other agents, such as, for example, alcohols or oxygen, in addition to the metal halide and metal alkyl activator to provide and / or increase metathesis activity. Non-limiting examples of metal halide olefin metathesis catalysts include tungsten chloride / tetrabutyltin (WCl6 / SnMe4), tungsten chloride / ethylaluminum dichloride (WCl6 / EtAlCl2), tungsten chloride / ethylaluminum dichloride / ethyl alcohol (WCl6 / EtAlCl2 / EtOH), molybdenum chloride / triethylaluminum (MoCl5 / AlEt3), and molybdenum chloride / triethylaluminum / O2 (MoCl5 / AlEt3 / O2). Other suitable metal halide metathesis catalysts will be known to those skilled in the art.

[0050] Typically, the metal alkyl activator for metal oxide metathesis catalysts or metal halide metathesis catalysts may comprise or consist essentially of any metal alkyl. Suitable metal alkyl compounds may include alkyllithium, alkylmagnesium, alkylaluminum, alkyltin compounds, and mixtures thereof. In some implementations, the metal alkyl compound may be an alkyllithium compound; or an alkylmagnesium compound; or an alkylaluminum compound; or an alkyltin compound. Suitable alkylaluminum compounds may include trialkylaluminum compounds and / or alkylaluminum halide compounds. Suitable alkyl groups for the metal alkyl include C1-C 10 or a C1-C5 hydrocarbyl group. In some implementations, the alkyl group of the metal alkyl may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl; or methyl, ethyl, n-butyl, sec-butyl, or tert-butyl; or methyl; or ethyl; or n-butyl; or sec-butyl; or tert-butyl. Examples of suitable trialkylaluminum compounds include trimethylaluminum, triethylaluminum, and tributylaluminum. The halide of the alkylaluminum halide compound may be a chloride, bromide, or iodide; or a chloride; or a bromide; or an iodide. Examples of suitable alkylaluminum halides include ethylaluminum dichloride, diethylaluminum chloride, and ethylaluminum sesquichloride. Suitable alkyltin compounds include tetramethyltin, tetraethyltin, and tetrabutyltin.

[0051] Metal carbene olefin metathesis catalysts and / or catalyst systems (hereinafter referred to as "metal carbene olefin metathesis catalysts") are characterized by the presence of a metal-carbon double bond. In contrast to metal oxide and metal halide olefin metathesis catalysts, metal carbene olefin metathesis catalysts can be compounds that have a stable metal-carbon double bond or that can form a metal-carbon double bond in situ from a metal precursor that has a stable metal-carbon single bond.

[0052] The metal of a suitable metal carbene olefin metathesis catalyst can comprise or consist essentially of tungsten, tantalum, osmium, molybdenum, or ruthenium. In some implementations, the metal carbene olefin metathesis catalyst can be a tungsten carbene olefin metathesis catalyst, a molybdenum carbene olefin metathesis catalyst, or a ruthenium carbene olefin metathesis catalyst; or a ruthenium carbene olefin metathesis catalyst or a molybdenum carbene olefin metathesis catalyst. In some implementations, the metal carbene olefin metathesis catalyst can be a tungsten carbene olefin metathesis catalyst; or an osmium carbene olefin metathesis catalyst; or a ruthenium carbene olefin metathesis catalyst; or a molybdenum carbene olefin metathesis catalyst.

[0053] In some implementations, the ruthenium carbene metathesis catalyst can have the structure L1L2X2Ru=CHR, where L1 and L2 can be organic ligands, X is a halide, and R represents hydrogen or a hydrocarbyl group. Further implementations of groups L1, L2, X, and R are described independently herein. In general, the ruthenium carbene metathesis catalyst having the structure L1L2X2Ru=CHR can be described using any combination of L1 as described herein, L2 as described herein, and R as described herein.

[0054] In some implementations, L1 and L2 of the ruthenium carbene metathesis catalyst having the structure L1L2X2Ru=CHR can be independently R'3P, an imidazolinylidene group, or an imidazolidinylidene group. In some implementations, L1 and L2 are R'3P; or L1 is R'3P and L2 is an imidazolinylidene group or an imidazolidinylidene group; or L1 is R'3P and L2 is an imidazolidinylidene group; or L1 is R'3P and L2 is an imidazolidinylidene group; or L1 and L2 are imidazolinylidene groups; or L1 and L2 are imidazolidinylidene groups.

[0055] In some embodiments, the R' of R'3P can be a hydrocarbyl group. In some embodiments, each R' of R'3P can be the same; or each R' of R'3P can be different; or one R' of R'3P can be different from the other two R'. In some embodiments, each R' of R'3P can be a C1-C 15 Hydrocarbyl group; or C1-C 10In other implementations, each hydrocarbyl R' of R'3P may be independently an alkyl group or an aromatic group; alternatively, an alkyl group; alternatively, an aromatic group. In some implementations, each alkyl R' of R'3P may be independently a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a neo-pentyl group, a cyclopentyl group, or a cyclohexyl group. In some implementations, one or more R' of R'3P may be a phenyl group; alternatively, a substituted phenyl group. In some implementations, the substituent of the substituted phenyl group in R'3P may be a C1-C5 organyl group(s); alternatively, a C1-C5 hydrocarbyl group(s). In some implementations, R'3P may be a trialkylphosphine or triphenylphosphine; alternatively, a trialkylphosphine; alternatively, a triphenylphosphine. In some implementations, R'3P can be trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-tert-butylphosphine, tri-neopentylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, or triphenylphosphine; or triisopropylphosphine, tri-tert-butylphosphine, tri-neopentylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, or triphenylphosphine; or tricyclopentylphosphine, tricyclohexylphosphine, or triphenylphosphine; or tricyclopentylphosphine or tricyclohexylphosphine; or tricyclopentylphosphine; or tricyclohexylphosphine; or triphenylphosphine.

[0056] In some embodiments, the imidazolinylidene or imidazolidinylidene group is a C 80 Imidazolinylidene group or imidazolidinylidene group; or C3-C 50 Imidazolinylidene group or imidazolidinylidene group; or C5-C 40It may be an imidazolinylidene group or an imidazolidinylidene group. In some embodiments, the imidazolinylidene group may be a 1,3-disubstituted imidazolinylidene group. In some embodiments, the imidazolidinylidene group may be a 1,3-disubstituted imidazolidinylidene group. In some embodiments, each 1,3-substituent of the 1,3-disubstituted imidazolinylidene group or the 1,3-disubstituted imidazolidinylidene group may be a hydrocarbyl group. In some embodiments, the 1,3-substituent of the 1,3-disubstituted imidazolinylidene group or the 1,3-disubstituted imidazolidinylidene group may be a C1-C 30 In some embodiments, each 1,3-substituent in the 1,3-disubstituted imidazolinylidene or 1,3-disubstituted imidazolidinylidene group is independently a C6 to C6 hydrocarbyl group. 20 Aromatic group or C1-C 10 In another embodiment, the 1,3-substituent of the 1,3-disubstituted imidazolinylidene group or the 1,3-disubstituted imidazolidinylidene group is a C6 to C 20 Aromatic group; or C1-C 10It may be an alkyl group. In some implementations, the aromatic group(s) of the 1,3-disubstituted imidazolinylidene or 1,3-disubstituted imidazolidinylidene group may be a substituted aromatic group. In some implementations, the substituted aromatic group of the 1,3-disubstituted imidazolinylidene or 1,3-disubstituted imidazolidinylidene group may be a 2-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group; or a 2,6-disubstituted phenyl group; or a 2,4,6-trisubstituted phenyl group. Suitable substituents of the substituted phenyl group(s) in the 1,3-disubstituted imidazolinylidene or 1,3-disubstituted imidazolidinylidene group include any C1-C10 hydrocarbyl group; or any C1-C5 hydrocarbyl group. In some implementations, each hydrocarbyl group(s) of the substituted phenyl group(s) within the 1,3-disubstituted imidazolinylidene or 1,3-disubstituted imidazolidinylidene group can independently be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; alternatively, a methyl group, an ethyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an isopropyl group; or alternatively, a tert-butyl group. In some implementations, the 1,3-substituent of the 1,3-disubstituted imidazolinylidene or 1,3-disubstituted imidazolidinylidene group can be a 2,6-diisopropylphenyl group or a 2,4,6-trimethylphenyl group; alternatively, a 2,6-diisopropylphenyl group; or alternatively, a 2,4,6-trimethylphenyl group.

[0057] In some implementations, each X in the ruthenium carbene metathesis catalyst having the structure L1L2X2Ru=CHR can be independently chloride, bromide, or iodide. In some implementations, X can be chloride, bromide, or iodide.

[0058] In some embodiments, R of the ruthenium carbene metathesis catalyst having the structure L1L2X2Ru=CHR is hydrogen or C1-C 20 Hydrocarbyl group; or C1-C 20In some implementations, the hydrocarbyl group R may be a methyl group (--CH), an ethyl group (--CHCH), an isopropyl group (--CH(CH)), a tert-butyl group (--C(CH)), a phenyl group (--CH), a 2-methyl-2-propene group (--CH=C(CH)), or a 2,2-diphenylethene group (--CH=C(CH)). In other implementations, R can be a tert-butyl group (--C(CH3)3, a phenyl group (--C6H5), a 2-methyl-2-propene group (--CH=C(CH3)2, or a 2,2-diphenylethene group (--CH=C(C6H5)2); or hydrogen; or a tert-butyl group (--C(CH3)3); or a phenyl group (--C6H5); or a tert-butyl group (--C(CH3)3); or a phenyl group (--C6H5); or a 2-methyl-2-propene group (--CH=C(CH3)2); or a 2,2-diphenylethene group (--CH=C(C6H5)2).

[0059] In some non-limiting implementations, the ruthenium carbene metathesis catalyst can be dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium, dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine)ruthenium, dichloro(3-methyl-2-butenylidene)bis(tricyclopentylphosphine)ruthenium, 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)-dichloro(tricyclohexylphosphine)ruthenium, or 1,3-bis-(2,6-diiso-propylphenyl)-2-(imidazolidinylidene)(phenylmethylene)-dichloro(tricyclohexylphosphine)ruthenium. In some implementations, the ruthenium metal carbene metathesis catalyst can be di-chloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium; or dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine)ruthenium; or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)-dichloro(tricyclohexylphosphine)ruthenium; or 1,3-bis-(2,6-diisopropylphenyl)-2-(imidazolidinylidene)(phenylmethylene)-dichloro(tricyclohexylphosphine)ruthenium.

[0060] In some implementations, the molybdenum carbene metathesis catalyst may have the structure Mo(=CHR)(NAr)(OR')2, where R is hydrogen or a hydrocarbyl group, Ar is a substituted aromatic ring, and R' is a hydrocarbyl group or a halogenated hydrocarbyl group. Further implementations of the groups R, Ar, and R' are described independently herein. In general, the molybdenum carbene metathesis catalyst having the structure Mo(=CHR)(NAr)(OR')2 can be described using any combination of R as described herein, Ar as described herein, and R' as described herein.

[0061] In some embodiments, R of the molybdenum carbene metathesis catalyst having the structure Mo(=CHR)(NAr)(OR')2 is hydrogen or C1-C20 Hydrocarbyl group; or C1-C 20 In some implementations, the hydrocarbyl group R may be a methyl group (--CH), an ethyl group (--CHCH), an isopropyl group (--CH(CH)), a tert-butyl group (--C(CH)), a phenyl group (--CH), a 2-methyl-2-propene group (--CH=C(CH)), or a 2,2-diphenylethene group (--CH=C(CH)). In other implementations, R can be a tert-butyl group (--C(CH3)3, a phenyl group (--C6H5), a 2-methyl-2-propene group (--CH=C(CH3)2, or a 2,2-diphenylethene group (--CH=C(C6H5)2); or a tert-butyl group (--C(CH3)3) or a phenyl group (--C6H5); or a hydrogen; or a tert-butyl group (--C(CH3)3); or a phenyl group (--C6H5); or a 2-methyl-2-propene group (--CH=C(CH3)2); or a 2,2-diphenylethene group (--H=C(C6H5)2).

[0062] In one embodiment, the substituted aromatic ring, Ar, of the molybdenum carbene metathesis catalyst having the structure Mo(=CHR)(NAr)(OR')2 is a C6-C 30 Aromatic group; or C6~C 20 In some implementations, the substituted aromatic ring, Ar, is a C6 to C 20 In one embodiment, each substituent of the substituted aromatic ring, Ar, of the molybdenum carbene metathesis catalyst having the structure Mo(=CHR)(NAr)(OR')2 is independently selected from the group consisting of C1 to C6. 10hydrocarbyl group; or a C1-C5 hydrocarbyl group. In some implementations, the substituted aromatic ring, Ar, of the molybdenum carbene metathesis catalyst having the structure Mo(=CHR)(NAr)(OR')2 can be a 2-substituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group. In some implementations, each substituent on the substituted aromatic ring can independently be a methyl group (--CH3), an ethyl group (--CH2CH3), an isopropyl group (--CH(CH3)2), a tert-butyl group (--C(CH3)3), or a neopentyl group (--CH2C(CH3)3); or a methyl group (--CH3), an isopropyl group (--CH(CH3)2), or a tert-butyl group (--C(CH3)3); or a methyl group (--CH3), or an isopropyl group (--CH(CH3)2). In some implementations, each substituent of the substituted aromatic ring can be independently a methyl group (-CH3); or an isopropyl group (--CH(CH3)2); or a tert-butyl group (--C(CH3)3). In some non-limiting implementations, the substituted aromatic ring, Ar, of the molybdenum carbene metathesis catalyst having the structure Mo(=CHR)(NAr)(OR')2 can be a 2-tert-butylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, or a 2,4,6-trimethylphenyl group; or a 2-tert-butylphenyl group; or a 2,6-dimethylphenyl group; or a 2,6-diisopropylphenyl group; or a 2,4,6-trimethylphenyl group.

[0063] In one embodiment, each R' of a molybdenum carbene metathesis catalyst having the structure Mo(=CHR)(NAr)(OR')2 is independently selected from the group consisting of C1 to C 10 or a C1-C5 organic group. In some implementations, 10Alternatively, the C1-C5 organic group may be a hydrocarbylhalyl group (a group consisting of hydrogen, carbon, and halogen atoms); or a hydrocarbylfluoryl group (a group consisting of hydrogen, carbon, and fluorine atoms); or a hydrocarbyl group. In some implementations, the halogen atoms of the hydrocarbylhalyl group may be fluorine, chlorine, bromine, iodine, or combinations thereof; or fluorine; or chlorine; or bromine; or iodine. In some implementations, each R' of the molybdenum carbene metathesis catalyst having the structure Mo(=CHR)(NAr)(OR')2 may independently be a tert-butyl group (--C(CH3)3), or a hexafluoro-tert-butyl group (--C(CF3)2(CH3)) group. In other implementations, (OR')2 may represent a single organic group, and the two R' groups bonded to the oxygen atom are connected via a bond between any divalent, trivalent, or tetravalent atom within the R' group. In a further implementation, (OR')2 can represent a single organic group, and the two R' groups bonded to the oxygen atom are connected via a carbon-carbon bond of any carbon atom of the two R' groups.

[0064] In one embodiment, the molybdenum carbene metathesis catalyst can be Mo(=CH-C(CH3)3)(N-2,6-diisopropylphenyl)(OC(CH3)3), Mo(=CH-C(CH3)2(C6H5))(N-2,6-diisopropylphenyl)(OC(CH3)3), Mo(=CH-C(CH3)3)(N-2,6-diisopropylphenyl)-(OC(CH3)(CF3)2), or Mo(=CH--C(CH3)2(C6H5))(N-2,6-diisopropylphenyl)-(OC(CH3)(CF3). In other embodiments, the molybdenum carbene metathesis catalyst can be Mo(=CH-C(CH3)3)(N-2,6-diisopropylphenyl)-(OC(CH3)(CF3). In the practice, the molybdenum metathesis catalyst can be Mo(=CH--C(CH3)3)(N-2,6-diisopropylphenyl)-(OC(CH3)3); or Mo(=CH--C(CH3)2(C6H5))(N-2,6-diisopropylphenyl)-(OC(CH3)3); or Mo(=CH--C(CH3)3)(N-2,6-diisopropylphenyl)-(OC(CH3)(CF3)2); or Mo(=CH--C(CH3)2(C6H5))(N-2,6-diisopropylphenyl)-(OC(CH3)(CF3)2).

[0065] In some implementations, the metal carbene metathesis catalyst may be attached to a support. The metal carbene metathesis catalyst may be attached to a support via any ligand that does not contain a metal-carbon double bond. In some implementations, the metal carbene catalyst support is a polymer.

[0066] At a minimum, the catalyst composition includes a metathesis catalyst (and / or a metathesis catalyst system component). In some implementations, the catalyst composition may consist essentially of the metathesis catalyst (or a metathesis catalyst system component). In some implementations, the catalyst composition including the metathesis catalyst may further include a solvent or diluent. In some implementations, the catalyst composition including the metathesis catalyst consists essentially of the metathesis catalyst (or a metathesis catalyst system component); or consists essentially of the metathesis catalyst (or a metathesis catalyst system component) and a solvent or diluent. Solvents or diluents that may be utilized in the catalyst composition including the metathesis catalyst are described herein. In other implementations, the catalyst composition including the metathesis catalyst (or a metathesis catalyst system component) is substantially devoid of a solvent or diluent.

[0067] The metathesis process can be carried out under any conditions suitable to produce the desired alpha-olefin product having the desired purity of alpha-mono-olefin alpha mono-olefin. For example, stoichiometry, atmosphere, solvent, temperature and pressure can be selected by one skilled in the art to produce the desired product and minimize undesired by-products. The metathesis process may be carried out under an inert atmosphere. Similarly, when the reagents are supplied as gases, an inert gas diluent can be used. The inert atmosphere or inert gas diluent is typically an inert gas, meaning that the gas does not interact with the metathesis catalyst and does not substantially interfere with the catalytic action. For example, a particular inert gas is selected from the group consisting of helium, neon, argon, nitrogen, individually or in combination.

[0068] In some implementations, the metathesis catalyst is dissolved in a solvent before carrying out the metathesis reaction. In certain embodiments, the solvent selected can be selected to be substantially inert to the metathesis catalyst. Substantially inert solvents include, but are not limited to, aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic solvents including pentane, hexane, heptane, cyclohexane, etc.; and chlorinated alkanes such as dichloromethane, chloroform, dichloroethane, etc. In some implementations, the solvent comprises toluene.

[0069] The metathesis reaction temperature is a rate controlling variable selected to provide the desired alpha-olefin product having the desired purity of 1-olefin at an acceptable rate. In some implementations, the metathesis reaction temperature is greater than about -40 degrees Celsius, greater than about -20 degrees Celsius, greater than about 0 degrees Celsius, or greater than about 10 degrees Celsius. In some implementations, the metathesis reaction temperature is less than about 150 degrees Celsius, less than about 120 degrees Celsius. In some implementations, the metathesis reaction temperature is between about 10 degrees Celsius and about 120 degrees Celsius. In some implementations, the metathesis reaction temperature ranges from the melting point of the olefin feed composition to 120 degrees Celsius.

[0070] The metathesis reaction can be carried out under any desired pressure. In general, it will be desirable to maintain a total pressure that keeps the reaction solution processable. The total pressure can be selected to be greater than about 0.1 atm (10 kPa), in some embodiments greater than about 0.3 atm (30 kPa), or greater than about 1 atm (100 kPa). Typically, the reaction pressure is about 70 atm (7000 kPa) or less, and in some embodiments about 30 atm (3000 kPa) or less. Non-limiting examples of pressure ranges for metathesis reactions are from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

[0071] Generally, the metathesis reaction may be carried out for a duration that can provide an alpha-olefin product having the desired purity of alpha-mono-olefin. The duration of the metathesis reaction may depend on, among other metathesis reaction parameters (e.g., the olefin feedstock), the metathesis catalyst used, the molar ratio of metathesis catalyst moieties to moles of olefin feedstock, and the metathesis reaction temperature. In some implementations, the duration of the metathesis reaction may range from 1 minute to 48 hours. In some implementations, the duration of the metathesis reaction may range from 10 minutes to 30 hours. In other implementations, the duration of the metathesis reaction may range from 15 minutes to 24 hours; or 15 minutes to 12 hours; or 15 minutes to 6 hours; or 15 minutes to 4 hours.

[0072] In some implementations, the alpha-olefin products produced by these metathesis reaction conditions have an increased alpha-mono-olefin content compared to the alpha-mono-olefin content of the olefin feed composition, hi some implementations, the alpha-olefin products have an alpha-mono-olefin content of about 95% or more, about 96% or more, about 97% or more, about 98% or more, or about 99% or more by weight of the total weight of the alpha-olefin products.

[0073] In some implementations, the alpha-olefin products include alpha-mono-olefins, alpha-olefins having less than 10 carbon atoms, and branched internal olefins. In some implementations, the alpha-olefins have less than 10 carbon atoms. In some implementations, the alpha-olefins are linear terminal olefins. In some implementations, the alpha-olefins having less than 10 carbon atoms include C4-C7 terminal olefins.

[0074] In some implementations, the alpha-mono-olefins in the alpha-olefin product are separated from the alpha-olefin product by a distillation process that removes low boiling fragments from the alpha-olefin product and increases the purity of the remaining alpha-mono-olefins.

[0075] In some implementations where it is desirable to obtain higher purity, the metathesis and distillation process can be repeated.

[0076] In another implementation, the method includes: (1) providing an olefin feed composition comprising alpha-mono-olefins and vinylidene olefins; (2) reacting the olefin feed composition in the presence of an isomerization catalyst to form an isomerized olefin feed comprising alpha-mono-olefins and branched internal olefins formed from the vinylidene olefins; (3) providing a catalyst composition having an olefin metathesis catalyst; and (4) reacting the isomerized olefin feed composition with ethylene in the presence of an olefin metathesis catalyst under metathesis reaction conditions to produce an alpha-olefin product comprising the alpha-mono-olefins, linear and branched olefins having fewer carbon atoms than the olefin feed.

[0077] FIG. 2 shows a second example of a reaction scheme 200 for increasing olefin content according to one or more implementations of the present disclosure. The second reaction scheme 200 is similar to the first reaction scheme 100, except that it includes an additional isomerization process carried out before contacting the isomerized olefin feed composition with ethylene in the presence of a catalyst composition comprising an olefin metathesis catalyst. The alpha-olefin feed used in addition to 1-decene in reaction scheme 200 includes vinylidene olefins. The isomerization is preferably accomplished using a catalyst that does not isomerize the desired 1-decene product but readily converts the vinylidene olefins to branched internal olefins. Examples of catalysts that can be used in the implementations described herein are disclosed in U.S. Pat. No. 6,730,750, which is incorporated herein by reference in its entirety. Without wishing to be bound by theory, it is believed that alpha-mono-olefins (e.g., 1-decene) pass through the metathesis reaction unchanged, while the vinylidene olefins and internal olefins react under the metathesis reaction conditions to form lower molecular weight olefins that can be easily removed by distillation.

[0078] With reference to FIG. 2, in another implementation, the method includes: (1) providing an olefin feed composition comprising 1-decene and vinylidene olefins; (2) reacting the olefin feed composition in the presence of a zeolite catalyst to form an isomerized olefin feed comprising 1-decene and branched internal olefins formed from the vinylidene olefins; (3) contacting the isomerized olefin feed composition with ethylene in the presence of a catalyst composition comprising an olefin metathesis catalyst; and (4) reacting the isomerized olefin feed composition with ethylene under metathesis reaction conditions to produce products comprising 1-decene, linear and branched olefins having less than 10 carbon atoms.

[0079] The olefin feed composition may be an olefin feed composition as described herein above. In some embodiments, the olefin feed composition comprises a 1-olefin and a vinylidene olefin. In some embodiments, the olefin feed composition comprises 90-97 wt% (e.g., 92-96 wt%; or 92-94 wt%) of a 1-olefin, 1-8% of a vinylidene olefin, and optionally 0.5-4% of a linear i-internal olefin. In some embodiments, the olefin feed composition comprises 90-97 wt% (e.g., 92-96 wt%; or 92-94 wt%) of a 1-decene, 1-8% of a vinylidene olefin, and optionally 0.5-4% of a linear i-internal olefin.

[0080] In some implementations, the olefin feedstock may comprise or consist essentially of vinylidene olefins having at least 4 carbon atoms; or at least 6 carbon atoms; or at least 8 carbon atoms; or at least 10 carbon atoms; or at least 12 carbon atoms; or at least 14 carbon atoms; or at least 16 carbon atoms; or at least 18 carbon atoms; or mixtures thereof. In some implementations, the olefin feedstock may comprise or consist essentially of vinylidene olefins having from 4 to 20 carbon atoms; or from 6 to 16 carbon atoms; or from 8 to 14 carbon atoms; or from 10 to 12 carbon atoms. In some implementations, the vinylidene olefins include vinylidene olefins having C 10 Vinylidene olefins are included.

[0081] In some implementations, the olefinic feedstock may comprise or consist essentially of linear internal olefins having at least 4 carbon atoms; or at least 6 carbon atoms; or at least 8 carbon atoms; or at least 10 carbon atoms; or at least 12 carbon atoms; or at least 14 carbon atoms; or at least 16 carbon atoms; or at least 18 carbon atoms; or mixtures thereof. In some implementations, the olefinic feedstock may comprise or consist essentially of linear internal olefins having from 4 to 20 carbon atoms; or from 6 to 16 carbon atoms; or from 8 to 14 carbon atoms; or from 10 to 12 carbon atoms. In some implementations, the linear internal olefins include C 10 Linear internal olefins are included.

[0082] In one implementation, the olefin feed composition is reacted in the presence of an isomerization catalyst to form an isomerized olefin feed comprising alpha-mono-olefins, branched internal olefins formed from vinylidene olefins, and optionally linear internal olefins. It is contemplated that any isomerization process that converts substantially all of the vinylidene olefins to branched internal olefins while leaving the alpha-mono-olefins unreacted can be utilized in accordance with the present disclosure. Examples of isomerization processes and catalysts that can be used in the implementations described herein are described in U.S. Patent No. 6,730,750.

[0083] In one embodiment, the isomerization of the olefin feed composition can be carried out by contacting the olefin feed composition with a zeolite catalyst. In one embodiment, the zeolite catalyst comprises LZ-Y52 zeolite under olefin isomerization reaction conditions. LZ-Y52 zeolite catalyst material is commercially available from Union Carbide. The LZ-Y52 material is a cubic ordered synthetic crystalline aluminosilicate having a density of 1.3 g / cc and the formula: Na 56 [(AlO2) 56 (SiO2) 136 ] 264 H2O

[0084] LZ-Y52 is manufactured and commercially available in a variety of shapes. LZ-Y52 is available, for example, as 1 / 8 inch or fractional (1 / 16) inch extruded pellets.

[0085] LZ-Y52 has been described as a Y zeolite, specifically a sodium Y zeolite, and is an excellent starting material when high ion exchange capacity is desired. The sodium content of LZ-Y52 can be reduced by 80% by cation exchange of ammonium for sodium, converting LZ-Y52 to LZ-Y62. The chemical and physical properties of LZ-Y52 compared to LZ-Y62 are as follows: Na2O, 13 wt% vs. 2.5 wt% for LZ-Y62; (NH4)2O, none vs. 9.8 wt% for LZ-Y62; Na + Molar ratio of Al: 0.934 vs. 0.18:NH 4+ molar ratio of Al, zero vs. 0.862 for LZ-Y62; 02 volume, 33.6 wt% vs. 34.0 for LZ-Y62; and cell dimension "a", 24.68 for LZ-Y52 vs. 24.73 for LZ-Y62.

[0086] In some implementations, a suitable temperature for use in the isomerization process is between 10 degrees Celsius and 150 degrees Celsius (e.g., between 30 degrees Celsius and 120 degrees Celsius, or between 35 degrees Celsius and 100 degrees Celsius). In some implementations, a suitable pressure for use in the isomerization process of the present disclosure is between 1 and 5000 psia (e.g., between 10 and 100 psia; or between 15 and 45 psia). In some implementations, a suitable weight hourly space velocity (WHSV) for use in the isomerization process of the present invention is between 0.1 and 100 (between 1 and 50; or between 2 and 20). WHSV is calculated by dividing the weight of feed to the reactor per hour by the weight of catalyst in the reactor.

[0087] In some implementations, the isomerized olefin feedstock includes alpha-mono-olefins, branched internal olefins formed from vinylidene olefins, and optionally linear internal olefins. In some implementations, the branched internal olefins have the same number of carbon atoms as the vinylidene olefins. In some implementations, the branched internal olefins include C 10 In some embodiments, the isomerized olefin feedstock further comprises a linear internal olefin. In some embodiments, the linear internal olefin has the same number of carbon atoms as the alpha-mono-olefin. In some embodiments, the linear internal olefin includes the C 10 Linear internal olefins are included.

[0088] In some implementations, the isomerized olefin feed composition is contacted with ethylene in the presence of a catalyst composition comprising an olefin metathesis catalyst. The ethylene may be fed to a reactor containing the olefin metathesis catalyst. In some implementations, the ethylene and the olefin feed composition flow into the reactor simultaneously. In some implementations, the ethylene and the olefin feed composition flow into the reactor sequentially.

[0089] In general, any olefin metathesis catalyst capable of producing an alpha-olefin product having the desired purity of alpha-mono-olefins can be used. However, depending on other metathesis reaction parameters (e.g., olefin feedstock characteristics and / or metathesis reaction conditions), a particular type(s) of olefin metathesis catalyst may be preferred in a particular case. Suitable olefin metathesis catalysts are described herein above.

[0090] The isomerized olefin feed composition is reacted with ethylene under metathesis reaction conditions to produce the desired alpha-olefin products. Suitable metathesis reaction conditions are also described previously herein.

[0091] In some implementations, the alpha-olefin product includes alpha-mono-olefins, linear and branched olefins having fewer carbon atoms than the remaining alpha-mono-olefins in the olefin feed composition. In some implementations, the linear olefins have fewer than 10 carbon atoms. In some implementations, the linear olefins include C4-C9 linear olefins. In some implementations, the branched olefins have fewer than 10 carbon atoms. In some implementations, the branched olefins include C4-C9 branched olefins.

[0092] In some implementations, the alpha-olefin products include 1-decene, linear and branched olefins having less than 10 carbon atoms.

[0093] In some implementations, the alpha-olefin products include alpha-mono-olefins, terminal olefins, and branched olefins having fewer carbon atoms than the alpha-mono-olefins. In some implementations, the terminal olefins and branched olefins have fewer than 10 carbon atoms. In some implementations, the terminal olefins are linear terminal olefins. In some implementations, the terminal olefins include C4-C9 terminal olefins.

[0094] In some implementations, the alpha-mono-olefins in the alpha-olefin product are separated from the linear and branched olefins having fewer carbon atoms than the alpha-mono-olefins by a distillation process that removes low boiling fragments from the alpha-olefin product and increases the purity of the remaining alpha-mono-olefins (e.g., 1-decene).

[0095] In some implementations, the purified alpha-olefin product has an alpha-mono-olefin content of about 95% or more, about 96% or more, about 97% or more, about 98% or more, or about 99% or more by weight of the total weight of the alpha-olefin product.

[0096] In some implementations where it is desirable to obtain higher purity, the isomerization, metathesis and distillation process can be repeated.

[0097] In some implementations, the alpha-olefin product can be used to form a drag reducer. The drag reducer can be formed by methods known in the art. In some implementations, the drag reducer can be produced by bulk polymerization of the alpha-olefin product in the presence of a catalyst. The bulk polymerization can be carried out using any olefin polymerization catalyst. In some implementations, the bulk polymerization is carried out in the presence of a Ziegler-Natta catalyst. In some implementations, the catalyst system includes a transition metal catalyst and a cocatalyst mixture. The catalyst and cocatalyst can be added as additives at any time during the polymerization process. The optimal catalyst concentration depends on the size of the reaction vessel.

[0098] In one implementation, the catalyst and alpha-olefin product are combined in a reaction vessel and stirred at ambient conditions for a time sufficient to increase the viscosity of the reactants sufficiently to suspend the catalyst, and then placed in a cold environment to allow the reaction to proceed. The cold environment is typically maintained at a temperature of about -20 degrees Celsius to about 25 degrees Celsius, allowing the reaction to proceed at a relatively steady pace while heat is removed to form the ultra-high molecular weight polymer. After bulk polymerization, the material is reduced in size by methods such as cryogenic grinding and slurried in water, alcohol, or water-alcohol dispersion media to obtain a drag reducer having the desired viscosity. Additional additives such as surfactants, biocides, and antifoaming agents can be added to the drag reducer as needed.

[0099] 3 illustrates a third example of a reaction scheme 300 for increasing olefin content according to one or more implementations of the present disclosure. The third reaction scheme 300 is similar to the first reaction scheme 100, except that the olefin feed composition used in the reaction scheme 300 is different. With reference to FIG. 3, in another implementation, the method includes (1) providing an olefin feed composition comprising a linear internal mono-olefin (e.g., 3-dodecene) and, optionally, at least one of an alpha-olefin having more than 10 carbon atoms (e.g., 1-dodecene), a diolefin (e.g., internal diolefin), a triolefin (e.g., internal triolefin), and a vinylidene (e.g., 2-ethyl-1-decene). In one implementation, the olefin feed composition comprises 3-dodecene and at least one of an alpha-olefin having at least 12 carbon atoms, a diolefin having at least 12 carbon atoms, a triolefin having at least 12 carbon atoms, and / or a vinylidene having at least 12 carbon atoms. The method further includes (2) providing a catalyst composition having an olefin metathesis composition. The method further includes (3) reacting the olefin feed composition with ethylene in the presence of the catalyst composition under metathesis reaction conditions to produce a product composition comprising an alpha-mono-olefin product (e.g., 1-decene) and one or more alpha-olefins having less than 10 carbon atoms. In some implementations, the product composition further comprises at least one of an alpha-olefin having more than 10 carbon atoms and a vinylidene. Separation, such as by distillation, provides a fraction highly enriched in the alpha-mono-olefin product (e.g., 1-decene).

[0100] In some implementations, a method is provided that includes providing an olefin feed composition comprising an alpha-mono-olefin and at least one of a diolefin having the same number of carbon atoms as the alpha-mono-olefin and / or a triolefin having the same number of carbon atoms as the alpha-mono-olefin. The method further includes providing a catalyst composition comprising an olefin metathesis catalyst. The method further includes reacting the olefin feed composition with ethylene in the presence of the catalyst composition under metathesis reaction conditions to produce an alpha-olefin product comprising the alpha-mono-olefin and one or more alpha-olefins having fewer carbon atoms than the alpha-mono-olefin.

[0101] In one or more implementations described herein, the method further includes separating the alpha-mono-olefins in the alpha-olefin product from the alpha-olefin product using a distillation process.

[0102] In one or more implementations described herein, the one or more alpha-olefins having fewer carbon atoms than the alpha-mono-olefins include C4-C7 alpha-olefins.

[0103] In one or more implementations described herein, the one or more alpha-olefins having fewer carbon atoms than the alpha-mono-olefin include at least one of an alpha-mono-olefin and a diolefin.

[0104] In one or more implementations described herein, the olefin feed composition comprises 93.5-96 wt. % alpha-mono-olefins, 1-6 wt. % diolefins, and 0.5-4 wt. % triolefins.

[0105] In one or more implementations described herein, the olefin metathesis catalyst is a transition metal complex comprising a metal selected from the group consisting of Ni, W, Ru, Mo, Re, and combinations thereof.

[0106] In one or more implementations described herein, the olefin metathesis catalyst is a Ru-containing transition metal complex.

[0107] In one or more implementations described herein, the olefin metathesis catalyst is a Grubbs catalyst, a Schrock catalyst, or a Hoveyda catalyst.

[0108] In one or more implementations described herein, the olefin metathesis catalyst is selected from a ruthenium carbene metathesis catalyst and a molybdenum carbene metathesis catalyst.

[0109] In one or more implementations described herein, the olefin metathesis catalyst is dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)-dichloro(tricyclohexylphosphine)ruthenium.

[0110] In one or more implementations described herein, the metathesis reaction conditions include a metathesis reaction temperature ranging from the melting point of the olefin feedstock to 120 degrees Celsius.

[0111] In one or more implementations described herein, the method includes polymerizing an alpha-olefin product in the presence of a catalyst to form a drag reducer.

[0112] In one or more implementations described herein, the alpha-mono-olefin has from 4 to 20 carbon atoms.

[0113] In one or more implementations described herein, the alpha-mono-olefin has 6 to 16 carbon atoms.

[0114] In one or more implementations described herein, the alpha-mono-olefin has 8 to 14 carbon atoms.

[0115] In one or more implementations described herein, the alpha-mono-olefin has 10 to 12 carbon atoms.

[0116] In one or more implementations described herein, the alpha-mono-olefin has 10 carbon atoms.

[0117] In one or more implementations described herein, the olefin feed composition further comprises at least one of a diolefin having a different number of carbon atoms compared to the alpha-mono-olefin and / or a triolefin having a different number of carbon atoms compared to the alpha-mono-olefin.

[0118] In one or more implementations described herein, the olefin feed composition further comprises a second alpha-mono-olefin having a different number of carbon atoms compared to the first alpha-mono-olefin.

[0119] In some implementations, a method is provided. The method includes providing an olefin feed composition comprising alpha-mono-olefins and vinylidene olefins. The method further includes reacting the olefin feed composition in the presence of an isomerization catalyst to form an isomerized olefin feed comprising alpha-mono-olefins and branched internal olefins formed from the vinylidene olefins. The method includes reacting the isomerized olefin feed composition with ethylene in the presence of a catalyst composition comprising an olefin metathesis catalyst under metathesis reaction conditions to produce alpha-olefin products comprising alpha-mono-olefins, linear and branched olefins having fewer carbon atoms than the olefins in the olefin feed composition.

[0120] In one or more implementations described herein, the olefin feed composition further comprises a linear internal olefin.

[0121] In one or more implementations described herein, the method further includes separating alpha-mono-olefins in the alpha-olefins from linear and branched olefins having fewer carbon atoms using a distillation process.

[0122] In one or more implementations described herein, the linear olefin comprises a C4 to C9 linear olefin.

[0123] In one or more implementations described herein, the branched olefins include C5 to C9 branched olefins.

[0124] In one or more implementations described herein, the olefin feed composition comprises 90-97 wt. % alpha-mono-olefins and 1-8% vinylidene olefins.

[0125] In one or more implementations described herein, the olefin metathesis catalyst is a transition metal complex comprising a metal selected from the group consisting of Ni, W, Ru, Mo, Re, and combinations thereof.

[0126] In one or more implementations described herein, the olefin metathesis catalyst is a Ru-containing transition metal complex.

[0127] In one or more implementations described herein, the olefin metathesis catalyst is a Grubbs catalyst, a Schrock catalyst, or a Hoveyda catalyst.

[0128] In one or more implementations described herein, the olefin metathesis catalyst is selected from a ruthenium carbene metathesis catalyst and a molybdenum carbene metathesis catalyst.

[0129] In one or more implementations described herein, the olefin metathesis catalyst is dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)-dichloro(tricyclohexylphosphine)ruthenium.

[0130] In one or more implementations described herein, the metathesis reaction conditions include a metathesis reaction temperature ranging from the melting point of the olefin feedstock to 120 degrees Celsius.

[0131] In one or more implementations described herein, the isomerization catalyst is a zeolite catalyst.

[0132] In one or more implementations described herein, the zeolite catalyst has a density of 1.3 g / cc and has the formula Na 56 [(AlO2) 56 (SiO2) 136 ] 264 It is a synthetic crystalline aluminosilicate with a cubic arrangement, having HO.

[0133] In one or more implementations described herein, the method includes polymerizing an alpha-olefin product in the presence of a catalyst to form a drag reducer.

[0134] In one or more implementations described herein, the alpha-mono-olefin has from 4 to 20 carbon atoms.

[0135] In one or more implementations described herein, the alpha-mono-olefin has 6 to 16 carbon atoms.

[0136] In one or more implementations described herein, the alpha-mono-olefin has 8 to 14 carbon atoms.

[0137] In one or more implementations described herein, the alpha-mono-olefin has 10 to 12 carbon atoms.

[0138] In one or more implementations described herein, the alpha-mono-olefin has 10 carbon atoms.

[0139] In one or more implementations described herein, the olefin feed composition further comprises at least one of a diolefin and / or a triolefin.

[0140] While the above is directed to practices of the present disclosure, other and further implementations of the present disclosure may be devised without departing from the basic scope thereof, the scope of the present disclosure being determined by the following claims.

Claims

1. providing an olefin feed composition comprising alpha-mono-olefins and vinylidene olefins; reacting the olefin feed composition in the presence of an isomerization catalyst to form an isomerized olefin feed comprising alpha-mono-olefins and branched internal olefins formed from vinylidene olefins; and reacting an isomerized olefin feed composition with ethylene under metathesis reaction conditions in the presence of a catalyst composition comprising an olefin metathesis catalyst to produce alpha-olefin products comprising alpha-mono-olefins, linear and branched olefins having fewer carbon atoms than the olefins in the olefin feed composition. A method comprising:

2. 10. The process of claim 1, wherein the olefin feed composition further comprises a linear internal olefin.

3. 10. The process of claim 1 further comprising separating alpha-mono-olefins in the alpha-olefin product from linear and branched olefins having fewer carbon atoms using a distillation process.

4. Linear olefin is C ４ ~C ９ 10. The process of claim 1 comprising a linear olefin.

5. Branched olefin is C ５ ~C ９ 5. The process of claim 4 comprising a branched olefin.

6. The process of claim 1, wherein the olefin feed composition comprises from 90 to 97 wt. % alpha-mono-olefins and from 1 to 8% vinylidene olefins.

7. 2. The process of claim 1, wherein the isomerization catalyst is a zeolite catalyst.

8. 2. The process of claim 1, wherein the olefin metathesis catalyst is Grubbs' catalyst, Schrock's catalyst, or Hoveyda's catalyst.

9. 2. The process of claim 1, wherein the olefin metathesis catalyst is selected from a ruthenium carbene metathesis catalyst and a molybdenum carbene metathesis catalyst.

10. The process of claim 1, wherein the olefin metathesis catalyst is dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)-dichloro(tricyclohexylphosphine)ruthenium.

11. 10. The method of claim 1, wherein the metathesis reaction conditions include a metathesis reaction temperature ranging from the melting point of the olefin feedstock to 120 degrees Celsius.

12. 10. The method of claim 1, further comprising polymerizing the alpha-olefin product in the presence of a catalyst to form the drag reducer.

13. The process of claim 1, wherein the alpha-mono-olefin has from 4 to 20 carbon atoms.

14. 10. The method of claim 1, wherein the olefin metathesis catalyst is a transition metal complex comprising a metal selected from the group consisting of Ni, W, Ru, Mo, Re, and combinations thereof.

15. 15. The method of claim 14, wherein the olefin metathesis catalyst is a transition metal complex comprising Ru.

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