Process for converting unsaturated polyethylene to alkene products

Abstract

The present disclosure relates to a process for converting unsaturated polyethylene into at least alkene products. The process includes contacting the unsaturated polyethylene with two or more catalyst components in a reactor containing an alkene reactant. The two or more catalyst components include a metathesis catalyst component and an isomerization catalyst component. By the contacting, at least a portion of the unsaturated polyethylene or a product derived therefrom undergoes a metathesis reaction and an isomerization reaction to produce an effluent containing at least alkene products.

Description

【Technical Field】 【0001】 (Cross - Reference to Related Applications) This application claims the benefit of U.S. Provisional Application No. 63 / 353,327, filed Jun. 17, 2022, the entire disclosure of which is incorporated herein by reference. 【Background Art】 【0002】 Field The present disclosure relates to the chemical treatment of hydrocarbons. In particular, the present disclosure relates to a process for converting ethylene - containing materials such as polyethylene into smaller desired hydrocarbon products. 【0003】 Technical Background Hydrocarbons are starting materials that are used or are starting materials for producing plastics, fuels, and various downstream chemicals for many industrial applications. Such hydrocarbons include alkenes such as ethene, propene, and butene (commonly also referred to as ethylene, propylene, and butylene respectively). Various production processes for these lower hydrocarbons have been developed, including petroleum cracking and various synthetic processes. Polyethylene (PE) is the most widely used plastic in the world and can be manufactured into a wide variety of products. However, a process for recycling polyethylene into smaller monomers such as propylene is desired. Conventional efforts for the chemical recycling of polyethylene have generally used pyrolysis and high - temperature pyrolysis. These processes are very energy - intensive and suffer from low selectivity of the desired products and the generation of greenhouse gases (e.g., CO2, CH4). 【Summary of the Invention】 【0004】 Embodiments of the present disclosure address these and other needs by providing a process for converting polyethylene to alkene products. The processes described herein may enable two or more catalyst components within a reactor to carry out multiple different chemical reactions, such as a combination of metathesis and isomerization to produce alkene products from, for example, unsaturated polyethylene and alkene reactants. 【0005】 According to one or more other aspects of the present disclosure, a process for converting unsaturated polyethylene to an alkene product having at least the chemical formula C m H 2m wherein the process comprises contacting the unsaturated polyethylene with two or more catalyst components within a reactor, the reactor containing an alkene reactant having the chemical formula C n H 2n wherein m is an integer from 3 to 20 and n is an integer from 2 to 20. The two or more catalyst components include a metathesis catalyst component and an isomerization catalyst component. By the contacting, at least a portion of the unsaturated polyethylene or a product derived therefrom undergoes a metathesis reaction and an isomerization reaction to produce an effluent containing an alkene product having at least the chemical formula C m H 2m 【0006】 Additional features and advantages are described in the following "Detailed Description of the Invention", and some will be readily apparent to those skilled in the art from that description, or will be recognized by practicing the embodiments described in the following "Detailed Description of the Invention" and the embodiments described herein, including the "Claims". 【0007】 It should be understood that both the foregoing general description and the following detailed description are intended to provide an overview or framework for understanding the nature and characteristics of the claimed subject matter by describing various embodiments. 【Brief Description of the Drawings】 【0008】 【Figure 1】 A reactor is schematically shown according to one or more embodiments of the present disclosure. 【0009】 To describe the simplified schematic diagram and description of FIG. 1, it is used by those skilled in the art who operate specific chemical processes and does not include a number of valves, temperature sensors, electronic control devices, etc. that may be well known. Further, the accompanying components that are often included in typical chemical treatment operations, carrier gas supply systems, pumps, compressors, furnaces, or other subsystems are not shown. It should be understood that these components are within the spirit and scope of the disclosed embodiments. However, operational components such as those described in this disclosure may be added to the embodiments described in this disclosure. 【DETAILED DESCRIPTION OF THE INVENTION】 【0010】 Some conventional processes for converting polyethylene to smaller products may use separate catalysts isolated in separate catalyst zones, such as by filling each of the separate catalysts into separate reactors, which can increase the initial capital cost of the reaction system. In contrast, the processes disclosed herein can enable tandem catalysis of polyethylene by contacting polyethylene with mutually compatible catalyst components to produce the desired alkene products. The catalytic depolymerization of polyethylene under mild reaction conditions provides an advantageous and sustainable alternative for the production of hydrocarbon feedstocks, monomers, or other useful chemicals. 【0011】 Here, a detailed reference is made to an embodiment of a process for converting unsaturated polyethylene to alkene products in a reactor. As used herein, "unsaturated polyethylene" refers to a compound containing the chemical formula C x H 2x wherein x is an integer of at least 10 and at least one carbon-carbon double bond is present. In embodiments, the unsaturated polyethylene can include branched polyethylene. In embodiments, the unsaturated polyethylene can include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), or combinations thereof. In embodiments, the unsaturated polyethylene is C x H2x comprising, wherein x is an integer of 10 or more, 12 or more, or even 15 or more. In an embodiment, the unsaturated polyethylene has a number average molecular weight (M n ) of from 150 g / mol to 1,000,000 g / mol. In an embodiment, the unsaturated polyethylene can be a waste stream from a hydrocarbon treatment system or a product derived therefrom. 【0012】 In an embodiment, the reactor comprises an alkene reactant. In an embodiment, the alkene reactant has the chemical formula C n H 2n , wherein n is an integer from 2 to 20. For example, the alkene reactant can have the chemical formula C n H 2n , wherein n is an integer from 2 to 15, 2 to 10, 2 to 5, 2 to 4, or 2 to 3. In an embodiment, the alkene reactant can include ethylene, propylene, butene, pentene, or a combination thereof. In an embodiment, the alkene reactant can be selected from the group consisting of ethylene, propylene, butene, pentene, and combinations thereof. In an embodiment, the alkene reactant can include ethylene. In an embodiment, the alkene reactant can consist essentially of ethylene or consist of ethylene. In an embodiment, the alkene reactant can include ethylene and butene. In an embodiment, the alkene reactant can consist essentially of ethylene and butene or consist of ethylene and butene. 【0013】 In embodiments, the unsaturated polyethylene can be contacted with two or more catalyst components in a reactor. In other embodiments, the unsaturated polyethylene can be contacted with three or more catalyst components in a reactor. As used herein, "catalyst component" refers to any substance that accelerates the rate of a specific chemical reaction. The catalyst components described in this disclosure and the catalyst compositions made using the catalyst components can be utilized to facilitate various reactions such as, but not limited to, dehydrogenation, metathesis, isomerization, or combinations thereof. In embodiments, the catalyst composition can include at least one catalyst component or at least two catalyst components. As used herein, "catalyst composition" refers to solid fine particles containing at least one catalyst component. The catalyst composition can further include a catalyst carrier material. 【0014】 In embodiments, the catalyst component can include a metathesis catalyst component, an isomerization catalyst component, and optionally a dehydrogenation catalyst component. Without being bound by a particular theory, the metathesis catalyst can cleave the carbon chain of the unsaturated polyethylene in the presence of an alkene reactant to produce two products each having a terminal unsaturation, and further metathesis of the terminal unsaturated polyethylene intermediate product by the alkene reactant may be unproductive for further carbon chain cleavage. The isomerization catalyst component can convert the terminal unsaturation to an internal unsaturation, and it is believed that the isomerization product can further decompose into two products in the presence of the metathesis catalyst component and the alkene reactant. This cycle can continue until the desired product or group of products is produced from the process. Further, the dehydrogenation catalyst can introduce additional unsaturations into the carbon chain of the unsaturated polyethylene or a product derived therefrom, which is believed to improve the depolymerization of the unsaturated polyethylene. 【0015】 In an embodiment, the metathesis catalyst component combined with an alkene reactant such as ethylene can function to cleave an unsaturated polyethylene chain into two species. In an embodiment, the metathesis catalyst component can decompose an alkene product derived from unsaturated polyethylene. In an embodiment, the metathesis catalyst component can include one or more elements selected from Groups 5-10 of the International Union of Pure and Applied Chemistry (IUPAC). In an embodiment, the metathesis catalyst component can include rhenium, ruthenium, tungsten, molybdenum, vanadium, or a combination thereof. In an embodiment, the metathesis catalyst component can be selected from the group consisting of rhenium, ruthenium, tungsten, molybdenum, vanadium, and combinations thereof. In an embodiment, the metathesis catalyst component can include methyltrioxorhenium (MTO). 【0016】 In an embodiment, the isomerization catalyst component may be operable to move an unsaturation on unsaturated polyethylene or on a product derived therefrom from one position on the backbone to a different position. For example, in an embodiment, the isomerization catalyst component can move an unsaturation at the terminal position of unsaturated polyethylene to an internal position. In an embodiment, the isomerization catalyst component can include one or more elements selected from Groups 5-10 of the International Union of Pure and Applied Chemistry (IUPAC). In an embodiment, the isomerization catalyst component can include alumina, silica, iridium, palladium, ruthenium, or a combination thereof. In an embodiment, the isomerization catalyst component can be selected from the group consisting of alumina, silica, iridium, palladium, ruthenium, and combinations thereof. In an embodiment, the isomerization catalyst component can include modified alumina, modified silica, or a combination thereof. For example, in an embodiment, the isomerization catalyst component can include, but is not limited to, chlorinated alumina, γ-alumina, chlorinated silica, or a combination thereof. In an embodiment, the isomerization catalyst component can include [tert-butyl-POCOP]Ir[C2H4]. 【0017】 In an embodiment, the dehydrogenation catalyst component can cause additional unsaturation along the polyethylene main chain in an unsaturated polyethylene or a product derived therefrom. In an embodiment, the dehydrogenation catalyst component can cause the unsaturated polyethylene or a product derived therefrom to undergo transfer dehydrogenation. In an embodiment, the dehydrogenation catalyst component can include one or more elements selected from Groups 5-10 of the International Union of Pure and Applied Chemistry (IUPAC). In an embodiment, the dehydrogenation catalyst component can include platinum, iridium, ruthenium, rhenium, or a combination thereof. In an embodiment, the dehydrogenation catalyst component is selected from the group consisting of platinum, iridium, ruthenium, rhenium, and combinations thereof. 【0018】 In an embodiment, the reactor may include one or more catalyst compositions containing two or more catalyst components. For example, in an embodiment, the catalyst composition can include a metathesis catalyst component and an isomerization catalyst component. In an embodiment, the catalyst composition can include a dehydrogenation catalyst component and an isomerization catalyst component. In an embodiment, the catalyst composition can include a metathesis catalyst component and an isomerization catalyst component. In an embodiment, the catalyst composition can include a dehydrogenation catalyst component and a metathesis catalyst component. In an embodiment, the catalyst composition can include a dehydrogenation catalyst component, a metathesis catalyst component, and an isomerization catalyst component. In an embodiment, the catalyst composition can include a dehydrogenation catalyst component, a metathesis catalyst component, or an isomerization catalyst component. In an embodiment, the reactor can include a first catalyst composition containing a metathesis catalyst component and an isomerization catalyst component. For example, in an embodiment, the reactor can include a first catalyst component, and the first catalyst component is MTO on alumina. In an embodiment, the reactor can include a second catalyst composition containing an additional metathesis catalyst component and / or an isomerization catalyst component. In an embodiment, the reactor can include a second catalyst composition containing a dehydrogenation catalyst component and an isomerization catalyst component. For example, in an embodiment, the reactor can include a second catalyst component, and the second catalyst component can include platinum on alumina or platinum on silica. In an embodiment, the first catalyst composition and the second catalyst composition containing MTO on alumina can come into contact with unsaturated polyethylene in the reactor. 【0019】 In an embodiment, the catalyst composition is represented by the weight percentage of one or more elements selected from Groups 5 to 10 of the International Union of Pure and Applied Chemistry (IUPAC). In an embodiment, the first catalyst composition can include any one of the elements selected from Groups 5 to 10 of the IUPAC in an amount of 15 wt% or less based on the total weight of the first catalyst composition. For example, in an embodiment, the first catalyst composition can include any one of the elements selected from Groups 5 to 10 of the IUPAC in an amount of 12 wt% or less, 10 wt% or less, 8 wt% or less, 6 wt% or less, 4 wt% or less, or even 2 wt% or less based on the total weight of the first catalyst composition. In an embodiment, the first catalyst composition can include any one of the elements selected from Groups 5 to 10 of the IUPAC in an amount of more than 1 wt%, more than 2 wt%, more than 3 wt%, more than 4 wt%, more than 5 wt%, more than 6 wt%, more than 7 wt%, more than 8 wt%, or even more than 9 wt% based on the total weight of the first catalyst composition. In an embodiment, the first catalyst composition can include any one of the elements selected from Groups 5 to 10 of the IUPAC in an amount of 1 wt% to 15 wt%, 1 wt% to 12 wt%, 1 wt% to 10 wt%, 1 wt% to 5 wt%, 1 wt% to 4 wt%, 2 wt% to 15 wt%, 2 wt% to 12 wt%, 2 wt% to 10 wt%, 2 wt% to 5 wt%, 2 wt% to 4 wt%, 5 wt% to 15 wt%, 5 wt% to 12 wt%, or 5 wt% to 10 wt% based on the total weight of the first catalyst composition. 【0020】 In an embodiment, the second catalyst composition can include any one of elements selected from IUPAC groups 5-10 in an amount of 15 wt% or less based on the total weight of the second catalyst composition. For example, in an embodiment, the second catalyst composition can include any one of elements selected from IUPAC groups 5-10 in an amount of 12 wt% or less, 10 wt% or less, 8 wt% or less, 6 wt% or less, 4 wt% or less, or even 2 wt% or less based on the total weight of the second catalyst composition. In an embodiment, the second catalyst composition can include any one of elements selected from IUPAC groups 5-10 in an amount of more than 1 wt%, more than 2 wt%, more than 3 wt%, more than 4 wt%, more than 5 wt%, more than 6 wt%, more than 7 wt%, more than 8 wt%, or even more than 9 wt% based on the total weight of the second catalyst composition. In an embodiment, the second catalyst composition can include any one of elements selected from IUPAC groups 5-10 in an amount of 1 wt% - 15 wt%, 1 wt% - 12 wt%, 1 wt% - 10 wt%, 1 wt% - 5 wt%, 1 wt% - 4 wt%, 2 wt% - 15 wt%, 2 wt% - 12 wt%, 2 wt% - 10 wt%, 2 wt% - 5 wt%, 2 wt% - 4 wt%, 5 wt% - 15 wt%, 5 wt% - 12 wt%, or 5 wt% - 10 wt% based on the total weight of the second catalyst composition. 【0021】 It should be understood that according to an embodiment, the catalyst composition can be prepared by a method that results in a desired composition. Some non-limiting examples include incipient wetness impregnation, or vapor deposition of metal precursors (either essentially organic or inorganic), followed by their controlled decomposition. 【0022】 In an embodiment, by contacting an unsaturated polyethylene with two or more catalyst components in a reactor containing an alkene reactant, a metathesis reaction and an isomerization reaction are caused to occur in at least a part of the unsaturated polyethylene or a product derived therefrom, to obtain at least a chemical formula C m H 2mAn effluent containing the alkene product can be produced. For example, in an embodiment, the unsaturated polyethylene can be contacted with a metathesis catalyst component in the presence of an alkene reactant to cleave the unsaturated polyethylene to form two products, each product containing a terminal unsaturated polyethylene. The terminal unsaturated polyethylene can be contacted with an isomerization catalyst component to move the unsaturation from the terminal position to an internal position in the terminal unsaturated polyethylene to form an internal unsaturated polyethylene. Without being bound by a particular theory, it is believed that the internal unsaturated polyethylene can undergo further metathesis reactions by contacting the metathesis catalyst component in the presence of an alkene reactant. The product derived from the unsaturated polyethylene that contacts both the metathesis catalyst component and the isomerization catalyst component in the presence of an alkene reactant continues to cycle between the metathesis reaction and the isomerization reaction to produce smaller alkene products such as a compound of chemical formula C m H 2m , where m is an integer from 3 to 20 and is believed to be, for example, propylene. In an embodiment, increasing the reaction time allows for additional metathesis and isomerization reaction cycles, so the reaction time can be increased to produce an effluent containing smaller alkene products. 【0023】 In an embodiment, the reactor can be any reactor useful for contacting polyethylene with two or more catalyst components in the presence of an alkene reactant to advance a catalytic reaction, such as a batch reactor, a fixed bed reactor, a fluidized bed reactor, a continuous stirred tank reactor, a tubular plug flow reactor, a reactive extruder, or a combination thereof. In an embodiment, two or more reactors can be used, such as two or more reactors in series. In an embodiment, the reactor can include a reaction zone where contacting and catalytic reaction can occur. In an embodiment, the two or more catalyst components can be present in the same reaction zone. In other embodiments, the reactor can include two or more reaction zones. In an embodiment, the reactor can include additional processing of reactants, such as processing of the alkene reactant, unsaturated polyethylene, and / or catalyst components. In an embodiment, an effluent containing one or more products from the catalytic reaction can be further processed, such as separation of one or more products from the effluent. For example, in an embodiment, propylene can be separated from the effluent. 【0024】 In an embodiment, the pressure of the alkene reactant in the reactor, such as in the reaction zone during contacting, can be from 0 pounds per square inch gauge (psig) to 3000 psig. For example, the pressure of the alkene reactant can be from 0 psig to 3000 psig, from 0 psig to 2000 psig, from 0 psig to 1000 psig, from 0 psig to 900 psig, from 0 psig to 800 psig, from 0 psig to 700 psig, from 0 psig to 600 psig, from 0 psig to 500 psig, or from 100 psig to 3000 psig. In some embodiments, the amount of alkene reactant used can be quantified by the pressure of the alkene reactant in the reactor. In other embodiments, the amount of alkene reactant can be quantified by the space velocity of the alkene reactant. 【0025】 In an embodiment, the temperature of the reactor, such as the reaction zone during contact, can be 400 °C or lower. For example, the temperature of the reactor during contact can be 350 °C or lower, 300 °C or lower, 250 °C or lower, or even 200 °C or lower. In an embodiment, the temperature of the reactor during contact is 50 °C to 400 °C, 50 °C to 350 °C, 50 °C to 300 °C, 50 °C to 250 °C, 50 °C to 200 °C, 60 °C to 400 °C, 60 °C to 350 °C, 60 °C to 300 °C, 60 °C to 250 °C, or 60 °C to 200 °C. Without being bound by any particular theory, it is believed that a reduced reactor temperature, such as 400 °C or lower, 350 °C or lower, 300 °C or lower, or 250 °C or lower, can reduce the formation of undesirable by-products during contact. Further, a decrease in the operating temperature of the reactor can reduce the energy required for the process, which can also reduce the economic cost of operation. 【0026】 In an embodiment, the contact causes at least a portion of the unsaturated polyethylene to undergo a catalytic reaction to produce an effluent. In an embodiment, the effluent can contain hydrocarbons having an average molecular weight of 40 g / mol to 1000 g / mol. In an embodiment, the effluent contains at least the chemical formula C m H 2m and can contain alkene products. In an embodiment, the alkene product is a compound of the chemical formula C m H 2m , where m is an integer from 3 to 20. For example, the alkene product can be a compound of the chemical formula C m H 2m , where m is an integer from 3 to 15, 3 to 10, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 3 to 4, or 3. In an embodiment, the alkene product can contain propylene, butene, pentene, or a combination thereof. In an embodiment, the alkene product can be selected from the group consisting of propylene, butene, pentene, and combinations thereof. In an embodiment, the alkene product can consist essentially of or consist of propylene, butene, pentene, or a combination thereof. In an embodiment, the alkene product can consist essentially of or consist of propylene. 【0027】 In an embodiment, the effluent can contain at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, or even at least 60 wt% of alkene products. 【Examples】 【0028】 Various aspects of the present disclosure are further clarified by the following examples. These examples are illustrative in nature and should not be understood as limiting the subject matter of this application. The materials used in the examples are provided in Table 1. In Examples 1-7, the catalysts according to the present disclosure were prepared. 【0029】 【Table 1】 【0030】 Example 1. Preparation of a 4 wt% CH3ReO3 / Cl-Al2O3 catalyst composition 【0031】 The 4 wt% CH3ReO3 / Cl-Al2O3, which is the catalyst composition of Example 1, was synthesized using the following procedure. γ-Al2O3 (Strem Chemicals, Inc.) was calcined in air at 550 °C for 4 hours (h), and then evacuated overnight at 450 °C under dynamic vacuum (10 -4 Torr). This partially dehydrated and dehydroxylated alumina was chlorinated in a fixed-bed reactor at 300 °C for 1 hour in a CCl4-saturated Ar stream (Airgas, UHP, 10 mL / min). CCl4 was distilled before use. The obtained Cl-Al2O3 was evacuated overnight at 450 °C and vacuum sublimated at room temperature (about 10 -4It was modified with CH3ReO3 (MTO, Sigma - Aldrich) at (Torr) to obtain a material containing 4 wt% MTO and 4 wt% Cl based on the total weight of the material. Periodically, the solid was shaken vigorously to promote uniform deposition of MTO. After grafting MTO onto Cl - Al2O3, the catalyst was evacuated at room temperature for 30 minutes to remove physically adsorbed materials, and the catalyst was stored in a N2 - filled glove box to prevent deactivation in air. 【0032】 Example 2. Preparation of Re2O7 / γ - Al2O3 catalyst composition 【0033】 The Re2O7 / γ - Al2O3, which is the catalyst composition of Example 5, was synthesized using the following procedure. Re2O7 / γ - Al2O3 was prepared by incipient wetness impregnation of γ - Al2O3 (Strem Chemicals, Inc.) with ammonium perrhenate to obtain a material containing 10 wt% Re. Before impregnation, γ - Al2O3 was calcined at 550 °C for 4 hours within 2 hours. After impregnation, the dried material was activated by calcination in oxygen at 650 °C at 5 °C / min for 8 hours. The calcined catalyst was stored in a N2 - filled glove box until use to avoid deactivation in air. 【0034】 Comparative Example A. Preparation of 4 wt% CH3ReO3 / Cl - Al2O3 catalyst composition 【0035】 The 4 wt% CH3ReO3 / α - Al2O3, which is the catalyst composition of Comparative Example A, was synthesized using the following procedure. α - Al2O3 (Sigma Aldrich) was calcined in air at 550 °C for 4 hours (h), and then evacuated under dynamic vacuum (10 -4 Torr) at 450 °C overnight. This dehydrated α - Al2O3 was subjected to vacuum sublimation at room temperature (about 10 -4The material was modified with CH3ReO3 (MTO, Sigma - Aldrich) at (Torr) to obtain a material containing 4 wt% MTO based on the total weight of the material. Periodically, the solid was shaken vigorously to promote uniform deposition of MTO. After grafting MTO onto α - Al2O3, the catalyst was evacuated at room temperature for 30 minutes to remove physically adsorbed materials and stored in an N2 - filled glove box to prevent deactivation in air. 【0036】 Comparative Example B. Preparation of γ - Al2O3 Catalyst Composition 【0037】 The catalyst composition of Comparative Example B was prepared as follows. γ - Al2O3 (Strem Chemicals, Inc.) was calcined in air at 550 °C for 4 hours (h), and then evacuated under dynamic vacuum (10 -4 Torr) at 450 °C overnight. 【0038】 Example 3. Preparation of Ru[PPh3]3[CO][Cl]H Catalyst Composition 【0039】 Ru[PPh3]3[CO][Cl]H, the catalyst composition of Example 3, was synthesized according to Prasanna, N. Synthesis, Spectral and Electrochemical Studies of Ruthenium(II) / (III) Complexes of Alicyclic B - Ketamines, Indian J. Chem. 2001, 40, 426 - 429. 【0040】 Example 4. Preparation of Re / Al2O3 Catalyst Composition 【0041】 The 10 wt% Re / Al2O3, which is the catalyst composition of Example 4, was synthesized according to the following procedure. 1024 mg of γ-Al2O3 was placed in a round-bottom flask equipped with a stir bar, heated to 110 °C using a hot oil bath, and dried for 24 hours. 163 mg of ammonium perrhenate was added to 5 mL of deionized water to form a mixture, and the mixture was added to the dried γ-Al2O3. The slurry was stirred at 80 °C overnight. The resulting solid was calcined in a furnace under a dry air stream for 8 hours. The heating rate of the furnace was 5 °C / min up to 650 °C. The catalyst was cooled to room temperature under a helium stream and transferred to an Ar-filled glove box for storage to obtain a catalyst composition containing 10 wt% Re based on the total weight of the catalyst composition. 【0042】 Example 5. Preparation of 7 wt% CH3ReO3 / Cl-Al2O3 Catalyst Composition 【0043】 The 7 wt% CH3ReO3 / Cl-Al2O3, which is the catalyst composition of Example 5, was synthesized using the following procedure. MTO was sublimed onto 816 mg of Al2O3 / Cl (4 wt%) held at -78 °C using a liquid N2 trap over 5 hours. After complete sublimation of MTO, the mixture was stirred for 0.5 hour and warmed to room temperature under static vacuum. The solid was then left under dynamic vacuum for an additional 0.5 hour. The material was transferred inertly to an Ar-filled glove box for storage. 【0044】 Example 6. Preparation of PtRe / SiO2 Catalyst Composition 【0045】 The PtRe / SiO2, which is the catalyst composition of Example 6, was prepared using the following procedure. PtRe / SiO2 was prepared by incipient wetness impregnation of silica powder with ammonium perrhenate to obtain a material containing 1 to 5 wt% of Re. After impregnation, the material was calcined at 500 °C. Pt was deposited onto the material by incipient wetness impregnation in toluene containing platinum acetylacetonate to obtain a material containing 1 to 5 wt% of Pt. The obtained solid was dried in air at 120 °C for 4 hours, and then the temperature was raised to 210 °C over 4 hours. The material was reduced in H2 at 150 °C for 1 hour. The reduced catalyst was stored in an N2 atmosphere until use to avoid reoxidation in air. After the PtRe / SiO2 catalyst was calcined at 500 °C for 4 hours, it was reduced with H2 at 280 °C for 2 hours. The heating rate was 2 °C / min. After reduction, the catalyst was evacuated at room temperature for 30 minutes to remove physically adsorbed H2 and stored in an N2-filled glove box to prevent deactivation in air. 【0046】 Example 7. tBu Preparation of the [POCOP]Ir[C2H4] Catalyst Composition 【0047】 The catalyst composition of Example 7, tBu [POCOP]Ir[C2H4], was prepared according to "Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation-Olefin Metathesis", Science 2006, 312, 257 - 261. [C6H3-2,6-[OP(t-Bu)2]2]Ir[H][Cl] and NaO-t-Bu were weighed into an oven-dried Schlenk flask in a molar ratio of 1 to 1.2, respectively. Then, the solid was placed under an argon stream. 40 mL of toluene was added to the flask via syringe, and the resulting suspension was stirred at room temperature for 10 minutes. Ethylene was bubbled into the solution for 1 - 2 hours. The solution was cannula-filtered through a pad of celite, the volatile substances were evaporated under vacuum, and the resulting red solid was dried under vacuum overnight to obtain the product in a 60% yield. 【0048】 Example 8. Preparation of Olefin-Terminated Polyethylene 【0049】 In Example 8, the olefin-terminated polyethylene was prepared as follows. A 300 mL Parr HP 5500 Compact reactor equipped with an overhead stirrer was degassed with Ar. Then, 100 mL of toluene was transferred to the reactor and heated to 60 °C. Inside an Ar-filled glove box, 2.8 mg (5 μmol) of {κ2-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonate}nickel(II)-methylpyridine was weighed into a dried 7 mL glass vial and dissolved in 1 mL of toluene. Using an airtight syringe, the catalyst solution was transferred to the inert Parr reactor. The reactor was filled with ethylene (35 bar), and the polymerization reaction was carried out for 60 minutes. Then, the reactor was vented and cooled to room temperature. The resulting polymer solution was precipitated in excess methanol (500 mL) and recovered by vacuum filtration. The material was dried in vacuo at 43 °C. Since the product polymer contains a single unsaturated bond per polymer chain, an estimated value of the polymer molecular weight (M N ) can be obtained by normalizing the -CH2-protons by the number of olefin protons (terminal and internal). 1 1H NMR (toluene-d8), alkyl -CH2: 0.92 - 2.00 (421.5H, s), terminal -α: 4.97 (2.01, dd), internal: 5.44 (2.85, m), terminal -β: 5.8 (1.00, m). 【0050】 In Examples 9 to 11, the catalytic process according to the present disclosure was carried out in a batch reactor. Hydrocarbons in the gas fraction product (C1 - C6) were quantitatively analyzed with a Shimadzu GC-2010 gas chromatograph equipped with a capillary column (Supelco Alumina Sulfate plot, 30 m × 0.32 mm) and a flame ionization detector (FID). The signal coefficient depends on the number of carbon atoms of each hydrocarbon species. The temperatures of the injector and the detector were 200 °C. The temperature rising program was as follows. 90 °C (held for 3 minutes), rising to 150 °C at 10 °C / min (held for 20 minutes). Helium was used as the carrier gas. H2, C2H4, and C2H6 were quantified with a Shimadzu GC-8AIT gas chromatograph equipped with a packed column (ShinCarbon ST 80 / 100, 2 m × 2 mm) and a thermal conductivity detector (TCD). The linear response of the TCD signal to the injection amounts of H2, C2H4, and C2H6 was confirmed using a standard gas mixture. The response factor was obtained as the slope of the fitted line. The temperatures of the column, injector, and detector were 130 °C. The TCD current was 70 mA, and the carrier gas pressure was 300 kPa (N2). The liquid phase product (>C5) was analyzed with an Agilent 6890N network gas chromatograph equipped with a DB-5 column and an FID detector. 1 1H NMR spectra were recorded at 600 MHz in 1,1,2,2-tetrachloroethane-d2 on a Varian Unity Inova AS600 spectrometer and analyzed using MestReNova (v11.0.1, Mestrelab Research S.L.). Chemical shifts (δ, ppm) were calibrated using the residual proton signal of the solvent and referenced to tetramethylsilane (TMS). 【0051】 Example 9. Catalytic Conversion of Unsaturated Polyethylene in a Batch Reactor 【0052】 In Example 9, unsaturated polyethylene (M n= 1300 g / mol) was reacted with ethylene over one of the catalyst compositions: Comparative Example A or Example 1 in a 10 mL batch reactor (Parr reactor, series 2550) according to Table 2. Inside an N2-filled glove box, the catalyst composition, unsaturated polyethylene, and unsaturated polyethylene were loaded into a reactor equipped with a pressure gauge and a K-type thermocouple. Ethylene (99.999%, Airgas) was passed through a moisture / oxygen trap (Supelco) before use. Before introducing ethylene into the reactor, the residual air in the gas line was purged three times in 5-minute cycles. Reactor heating was started, and after reaching the desired temperature of 130 °C, the reaction time was tracked. After a reaction time of 3 hours, the reactor was cooled in an air stream. An aliquot of the gas from the reactor headspace was taken for GC analysis, and then the remaining headspace in the fume hood was evacuated. The remaining solid and liquid were transferred onto a fine glass filter (4.0 - 5.5 μm), filtered, and the insoluble substances were removed by washing with hot (50 °C) CHCl3. The soluble hydrocarbons were recovered by evaporating the solvent under reduced pressure (0.1 Torr). The insoluble substances containing hydrocarbons insoluble in the catalyst and hot CHCl3 were recovered from the filter. The solids were analyzed by GPC. The results of the product formed in Example 9 are shown in Table 3. 【0053】 【Table 2】 【0054】 【Table 3】 【0055】 Example 10. Catalytic conversion of unsaturated polyethylene at various reaction times in a batch reactor to form alkenes 【0056】 In Example 10, according to Table 4, unsaturated polyethylene (M n(with a molar mass of 1300 g / mol) was reacted with ethylene on one of the catalyst compositions: Example 1 or Example 2, in a batch reactor (Examples 10-1 and 10-2: 10 mL Parr reactor, series 2550; Examples 10-3, Comparative Examples 10A and 10B: 25 mL Parr reactor, series 4590). Inside an N2-filled glove box, the catalyst composition and the unsaturated polyethylene were loaded into a reactor equipped with a pressure gauge and a K-type thermocouple. Ethylene (99.999%, Airgas) was passed through a moisture / oxygen trap (Supelco) before use. Before introducing ethylene into the reactor, the residual air in the gas line was purged three times in 5-minute cycles. The heating of the reactor was started. After reaching the specified temperature according to Table 4, the reaction time was tracked. After the specified reaction time, the reactor was cooled in flowing air. An aliquot of the gas from the reactor headspace was taken for GC analysis, and then the remaining headspace in the ventilation hood was evacuated. The remaining solid and liquid were transferred onto a fine glass filter (4.0 - 5.5 μm), filtered, and the insoluble substances were removed by washing with hot (50 °C) CHCl3. The soluble hydrocarbons were recovered by evaporating the solvent under reduced pressure (0.1 Torr). The insoluble substances containing hydrocarbons insoluble in the catalyst and hot CHCl3 were recovered from the filter. The solid was analyzed by GPC. The results of the products formed in Example 10 are shown in Table 5. 【0057】 【Table 4】 【0058】 【Table 5】 【0059】 Example 11. Catalytic Conversion of 1-Octadecene on the Catalyst Composition of Example 1 in a Batch Reactor 【0060】 In Example 11, 1-octadecene was reacted with ethylene on the catalyst composition of Example 1 in a batch reactor (Parr reactor, Series 2550) according to Table 6. 1-Octadecene was degassed using three freeze-pump-thaw cycles and then transferred to an N2-filled glove box. The liquid was then dried over molecular sieves (3 Å). Inside the N2-filled glove box, the catalyst composition of Example 1 and 1-octadecene were loaded into a Parr reactor (10 mL, Series 2550) equipped with a pressure gauge and a Type K thermocouple. Ethylene (99.999%, Airgas) was passed through a moisture / oxygen trap (Supelco) before use. Residual air was purged from the gas line in three cycles before introducing ethylene into the reactor. After pressurizing with ethylene, it was heated to the specified temperature. After the specified reaction time, the reactor was cooled in flowing air. Gas and liquid aliquots from the reactor headspace were taken for gas chromatography analysis using a flame ionization detector (GC-FID). The remaining solid and liquid were transferred onto a fine glass filter (4.0 - 5.5 μm) and filtered by washing with 5 mL of CS2 solution to remove insoluble materials such as coke. After filtration, the filtrate was analyzed by GC-FID. The 1H NMR spectrum of the reaction product was measured. Peaks characteristic of internal olefins and terminal olefins were integrated. The ratio of internal olefins to terminal olefins was calculated. The results are shown in Table 7. 【0061】 【Table 6】 【0062】 【Table 7】 【0063】 In Example 12, as shown in Figure 1, a stirred-tank reactor was used. A 20 mL glass reaction sleeve (ID = 19.56 mm, OD = 22.15 mm) was placed inside a 40 mL stainless-steel stirred-tank reactor (ID = 22.16 mm, OD = 40 mm), and the reactor was housed inside an aluminum heating jacket. The temperature of the heating jacket was controlled by a hot plate and a thermocouple (IKA C-MAG HS7 digital). The reactor had two inlet ports, one for the liquid substrate and the other for the gaseous substrate. A Hamilton airtight syringe (5 mL) and a Kd Scientific Legato 100 Syringe Pump were used to deliver the liquid substrate to the apparatus. The gaseous substrate was supplied from a pressurized tank whose flow rate was set by an Alicat mass flow controller (MCS series). The outlet stream was directed to an Equilibar backpressure regulator used to control the reaction pressure. Downstream of the regulator, an Agilent 6850 gas chromatograph (GC) was attached. The GC was equipped with a 6-port VICI-Valco gas sampling valve. The olefin formation rate was quantified using a continuous flow of ethylene as an internal standard. The stainless-steel pipes and fittings were purchased from McMaster-Carr and Swagelok. The GC was equipped with an FID and a Petrocol DH capillary GC column (100 mm × 0.25 mm × 0.5 μm film thickness). The column was held at 45 PSI and the gas sample was split 50:1. The column conditions and product elution times are shown in Tables 8 and 9, respectively. 【0064】 【Table 8】 【0065】 【Table 9】 【0066】 In Example 12, the olefin-terminated polyethylene prepared in Example 8 was reacted with ethylene and the catalyst composition described herein in a stirred tank reactor using various reaction conditions. The maximum propylene formation rate (R C3,max ) detected while the catalyst was in operation was measured in millimoles per hour (mmol h -1 ). The maximum propylene selectivity (S C3,max ) and butylene selectivity (S C4 , max ) were measured while the catalyst was in operation. The formation rates of propylene and butylene are normalized by the cumulative olefin formation rate for a given reaction time. The average of the selectivities of propylene (S C3 , avg ) and butylene (S C4,avg ) were evaluated at each sampling point during the course of the continuous reaction for each species. The polyethylene conversion (wt%) was also estimated by calculating the mass of polyethylene consumed per olefin produced according to Equation 1. 【0067】 【Equation】 where i represents the number of carbon units in the olefin, MW i represents the molecular weight of species "i", n ci is the number of moles of species "i" formed during the experiment, m PE,o is the initial charge of polyethylene, and it is assumed that each molecule of olefin formed contains two carbons from ethylene. The results are summarized in Table 10. 【0068】 Example 12. Catalytic Conversion of Olefin-Terminated Polyethylene in a Stirred Tank Reactor for Forming Alkenes 【0069】 Example 12-1 was conducted as follows. Inside an Ar-filled glove box, 157 mg of olefin-terminated polyethylene was loaded into a stirred-tank reactor. The reactor was taken out of the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. Using a continuous flow of ethylene supplied at 5 mL / min, the Ar atmosphere inside the reactor was evacuated for at least 15 minutes. A catalyst solution was prepared inside the Ar-filled glove box by mixing 5 mL of toluene with 53.0 mg of Ultracat in a 20 mL scintillation vial. The solution was stirred for 3 - 5 minutes and then transferred to a 5 mL syringe capped with a needle and septum for inert delivery by a syringe pump. The catalyst solution (0.01 mL / min) was co-fed into the reactor with ethylene gas (2.2 mL / min) for 9 hours, and the reactor was heated and maintained at 85 °C and 5.4 atm. To monitor the progress of the reaction, samples (0.25 mL) of the gaseous effluent were analyzed by GC every 34.2 minutes over the 9-hour reaction period. 【0070】 Example 12-2 was conducted according to Example 12-1, but 100 mg of Example 6 was loaded into the stirred-tank reactor together with PE before heating, and the reaction temperature was 100 °C. Further, in Example 12-2, 250 mg of PE was used instead of 157 mg, and 51.0 mg of UltraCat was used instead of 53 mg. 【0071】 Example 12-3 was conducted according to Example 12-2, but 19.4 mg of Example 3 was loaded into the stirred-tank reactor together with PE before heating, instead of Example 6. 【0072】 Example 12-4 was conducted as follows. Inside an Ar-filled glove box, 250 mg of olefin-terminated polyethylene was loaded into a stirred-tank reactor. The reactor was removed from the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. Using a continuous flow of ethylene supplied at 5 mL / min, the Ar atmosphere inside the reactor was evacuated for at least 15 minutes. A catalyst solution was prepared inside the Ar-filled glove box by mixing 5 mL of toluene, 50.0 mg of Ultracat, and 20 mg of Example 3 in a 20 mL scintillation vial. The solution was stirred for 3 - 5 minutes and then transferred to a 5 mL syringe capped with a needle and septum for inert delivery by a syringe pump. The catalyst solution (0.01 mL / min) was co-fed into the reactor with ethylene gas (2.2 mL / min) for 8 hours, and the reactor was heated and maintained at 100 °C and 5.4 atm. To monitor the progress of the reaction, samples (0.25 mL) of the gaseous effluent were analyzed by GC every 34.2 minutes over the 8-hour reaction period. 【0073】 Example 12-5 was conducted according to Example 12-4, except that the reaction pressure was 1 atm instead of 5.4 atm. 【0074】 Example 12-6 was conducted according to Example 12-4, except that the reaction temperature was 70 °C, the pressure was 1.0 atm, and the time was 9 hours. Further, after the 9-hour reaction, the mixture was cooled and left standing for 2 days. A second catalyst feed of the same concentration was prepared in the Ar-filled glove box. Thereafter, the catalyst solution (0.01 mL / min) was co-fed into the reactor with ethylene gas (2.2 mL / min), and the reactor was heated and maintained at 70 °C and 1 atm for an additional 8 hours. To monitor the progress of the reaction, samples (0.25 mL) of the gaseous effluent were analyzed by GC every 34.2 minutes over the 8-hour reaction period. 【0075】 Example 12-7 was conducted according to Example 12-5, except that the mass of Example 3 used to prepare the catalyst solution was 103 mg instead of 20 mg. 【0076】 Example 12-8 was conducted as follows. In an Ar-filled glove box, 253 mg of the olefin-terminated polyethylene of Example 8 was charged into a stirred-tank reactor. Next, the reactor was removed from the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. Using a continuous flow of ethylene supplied at 5 mL / min, the Ar atmosphere in the reactor was evacuated for at least 15 minutes. 5 mL of toluene, 50.0 mg of UltraCat, and 42.0 mg of [Pd I [μ-Br] t Bu3P] 2- (Strem Chemicals, Inc.) were mixed in a 20 mL scintillation vial to prepare the catalyst solution in an Ar-filled glove box. The solution was stirred for 3 - 5 minutes and then transferred to a 5 mL syringe capped with a needle and septum for inert delivery by a syringe pump. Over 9 hours, the catalyst solution (0.01 mL / min) was co-fed into the reactor with ethylene gas (10.1 mL / min), and the reactor was heated and maintained at 70 °C and 1 atm. To monitor the progress of the reaction, samples (0.25 mL) of the gaseous effluent were analyzed by GC every 34.2 minutes over the 9-hour reaction period. 【0077】 Example 12-9 was conducted according to Example 12-8, but the catalyst solution was prepared using 61 mg of alkene dipper (Strem Chemicals, Inc.) instead of [Pd I [μ-Br] t Bu3P]2. 【0078】 Example 12-10 was conducted as follows. Inside an Ar-filled glove box, 253 mg of the olefin-terminated polyethylene of Example 8 and 202 mg of Example 5 were loaded into a stirred-tank reactor. Next, the reactor was taken out of the glove box, placed inside an aluminum heating jacket, and connected to an ethylene delivery source. Using a continuous flow of ethylene supplied at 5 mL / min, the Ar atmosphere inside the reactor was evacuated for at least 15 minutes. Ethylene gas (10.1 mL / min) was continuously flowed into the reactor for 20 hours, and the reactor was heated to 100 °C and 1 atm and held for 20 hours. To monitor the progress of the reaction, samples (0.25 mL) of the gaseous effluent were analyzed by GC every 34.2 minutes over a 20-hour reaction period. 【0079】 Example 12-11 was conducted according to 12-10, except that 14.5 mg of [Pd I [μ-Br] t Bu3P] 2- (Strem) was loaded into the stirred-tank reactor in addition to Example 5. The reaction was conducted for 10.5 hours instead of 20 hours. 【0080】 Example 12-12 was conducted according to Example 12-11, except that 51 mg of Example 6 was loaded into the stirred-tank reactor instead of [Pd I [μ-Br] t Bu3P]2. 149 mg of UltraCat was used instead of 202 mg. The reaction was conducted for 8 hours instead of 10.5 hours. 【0081】 Example 12-13 was conducted according to Example 12-12, except that 24.6 mg of Example 7 was loaded into the stirred-tank reactor instead of Example 6. 156 mg of UltraCat was used instead of 149 mg. The reaction was conducted for 19.5 hours instead of 8 hours. 【0082】 Examples 12 - 14 were conducted as follows. Inside an Ar-filled glove box, 150 mg of the olefin-terminated polyethylene of Example 8, 140 mg of Example 4, 150 mg of Example 6, and 0.075 mL of Me3Al (2M) dissolved in toluene were loaded into a stirred tank reactor. Next, the reactor was taken out of the glove box, placed inside an aluminum heating jacket, and connected to an ethylene delivery source. Using a continuous flow of ethylene supplied at 5 mL / min, the Ar atmosphere inside the reactor was evacuated for at least 15 minutes. Ethylene gas (2.2 mL / min) was continuously flowed into the reactor for 10 hours, and the reactor was heated and maintained at 170 °C and 6.8 atm. To monitor the progress of the reaction, samples (0.25 mL) of the gaseous effluent were analyzed by GC every 34.2 minutes over a 10-hour reaction period. 【0083】 Example 12 - 15 was conducted according to Example 12 - 14, except that 3 mg of Example 7 was loaded into the stirred tank reactor instead of Example 6. The reaction temperature was 150 °C instead of 170 °C. 【0084】 【Table 10】 【0085】 Example 13. Catalytic Conversion of Olefin-Terminated Polyethylene in a Stirred Tank Reactor for Forming Alkenes at Low Temperatures 【0086】 Example 13 - 1 was conducted as follows. Inside an Ar-filled glove box, 250 mg of olefin-terminated polyethylene was loaded into a stirred tank reactor together with 2 mL of toluene. Next, the reactor was taken out of the glove box, placed inside an aluminum heating jacket, and connected to an ethylene delivery source. Using a continuous flow of ethylene supplied at 5 mL / min, the Ar atmosphere inside the reactor was evacuated for at least 10 minutes. 3 mL of toluene, 50.0 mg of UltraCat, and 9.5 mg of [Pd I [μ-Br] tThe catalyst solution was prepared in an Ar-filled glove box by mixing [[Bu3P]2] in a 20 mL scintillation vial. The solution was stirred for 5 - 10 minutes and then transferred to a 5 mL syringe capped with a needle and septum for inert delivery by a syringe pump. The catalyst solution (0.01 mL / min) was co-fed into the reactor with ethylene gas (5.0 mL / min) for 5 hours, and the reactor was heated and maintained at 35 °C and 2 atm. To monitor the progress of the reaction, samples of the gaseous effluent (0.25 mL) were analyzed by GC every 10 minutes over a 9-hour reaction period. 【0087】 Example 13 - 2 was conducted as follows. Inside an Ar-filled glove box, 250 mg of olefin-terminated polyethylene was loaded into a stirred-tank reactor together with 1 mL of toluene. Next, the reactor was removed from the glove box, placed in an aluminum heating jacket, and heated to 70 °C for 30 minutes. Next, the reactor was connected to an ethylene and nitrogen delivery source. The Ar atmosphere inside the reactor was purged using a continuous flow of ethylene and nitrogen supplied at 5 mL / min each for at least 5 minutes. 2 mL of toluene was mixed with 30 mg of C 31 H 38 Cl2N2ORu and 2 mL of toluene was mixed with 16 mg of [Pd I [μ-Br] t Bu3P]2 in a 20 mL scintillation vial to prepare two catalyst solutions in an Ar-filled glove box. The solutions were stirred for at least 15 minutes and then transferred to two separate 5 mL syringes capped with needles and septa for inert delivery by a syringe pump. First, the [Pd I [μ-Br] t Bu3P]2 catalyst solution was fed into the reactor, followed by the C 31 H 38 Cl2N2ORu solution was fed for 5 hours (0.01 mL / min), fed into the reactor together with ethylene gas (5.0 mL / min) and nitrogen gas (5.0 mL / min), and the reactor was heated and maintained at 35 °C and 1 atm. To monitor the progress of the reaction, samples of the gaseous effluent (0.25 mL) were analyzed by GC every 10 minutes over a 9-hour reaction period. 【0088】 【Table 11】 A The maximum propylene formation rate detected while the catalyst was operating B This value indicates the maximum selectivity evaluated while the catalyst was operating. The propylene formation rate is normalized by the cumulative olefin formation rate for a given reaction time. C This value is the average of the selectivities evaluated at each sampling point during the course of the continuous reaction for a given species. D The PE conversion is estimated by calculating the mass of PE consumed per olefin produced (see Equation 1). 【0089】 Example 14. Catalytic conversion of unsaturated polyethylene in a batch reactor using propylene as the alkene reactant 【0090】 In Example 14, according to Table 12, unsaturated polyethylene (M n= 1300 g / mol, dispersity = 11) was reacted with various amounts of propylene over the catalyst composition of Example 1 for various time periods in a 10 mL batch reactor (Parr reactor, series 2550). Inside an N2-filled glove box, the catalyst composition and unsaturated polyethylene were loaded into a reactor equipped with a pressure gauge and a K-type thermocouple. Propylene (99.8%, Praxair) was passed through a moisture / oxygen trap (Supelco) before use. Before introducing propylene into the reactor, the gas line was thoroughly purged to remove residual air. Reactor heating was started, and after reaching the desired temperature of 130 °C, the reaction time was tracked. After a reaction time of 1 or 5 hours, the reactor was cooled in an air stream. An aliquot of the gas from the reactor headspace was taken for GC analysis, and then the remaining headspace in the ventilation hood was evacuated. The remaining solid was transferred to a 20 mL vial containing xylene at 110 °C to dissolve the product from the catalyst. The xylene solution was mixed with 180 mL of methanol at room temperature to precipitate the extracted product, which was separated from the methanol by vacuum filtration. Comparative Example 14-4 was prepared in the same manner as Example 14-1, except that saturated polyethylene was used instead of unsaturated polyethylene. The product was analyzed by GPC. The results of the product formed in Example 14 are shown in Table 33. 【0091】 【Table 12】 【0092】 【Table 13】 【0093】 Example 15. Catalytic Conversion of Unsaturated Polyethylene in a Batch Reactor over the Catalyst Composition of Example 1 in a Batch Reactor 【0094】 In Example 15, according to Table 14, in a 10 mL batch reactor (Parr reactor, series 2550), unsaturated polyethylene (M n(with a molecular weight of 1300 g / mol and a dispersity of 11) was reacted with ethylene over a mixture of MTO / Cl-Al2O3 and Cl-Al2O3. Inside an N2-filled glove box, the catalyst composition mixture, unsaturated polyethylene, and unsaturated polyethylene were loaded into a reactor equipped with a pressure gauge and a K-type thermocouple. Ethylene (99.999%, Airgas) was passed through a moisture / oxygen trap (Supelco) before use. Before introducing ethylene into the reactor, the residual air was purged three times from the gas line in 5-minute cycles. Reactor heating was initiated, and after reaching the desired temperature of 130 °C, the reaction time was tracked. After a reaction time of 3 hours, the reactor was cooled in an air stream. An aliquot of the gas from the reactor headspace was taken for GC analysis, and then the remaining headspace in the ventilation hood was exhausted. The remaining solid was transferred to a 20 mL vial containing xylene at 110 °C to dissolve the product from the catalyst. The xylene solution was mixed with 180 mL of methanol at room temperature to precipitate the extracted product, which was separated from the methanol by vacuum filtration. The product was analyzed by GPC. The results of the product formed in Example 15 are shown in Table 3 of Table 15. 【0095】 【Table 14】 【0096】 【Table 15】 【0097】 Example 16. Catalytic conversion of 1-octadecene over the catalyst composition of Example 1 in a batch reactor 【0098】 In Example 16, 1-octadecene was reacted with ethylene in a batch reactor (Parr reactor, series 2550) over a mixture of MTO / Cl-Al2O3 and Cl-Al2O3 according to Table 16. 1-Octadecene was degassed using three freeze-pump-thaw cycles and then transferred to an N2-filled glove box. The liquid was then dried over molecular sieves (3 Å). Inside the N2-filled glove box, the catalyst composition of Example 1 and 1-octadecene were loaded into a Parr reactor (10 mL, series 2550) equipped with a pressure gauge and a type K thermocouple. Ethylene (99.999%, Airgas) was passed through a moisture / oxygen trap (Supelco) before use. Residual air was purged from the gas line in 3 cycles before introducing ethylene into the reactor. After pressurizing with ethylene, it was heated to the specified temperature. After the specified reaction time, the reactor was cooled in flowing air. Gas and liquid aliquots from the reactor headspace were taken for gas chromatography analysis using a flame ionization detector (GC-FID). The remaining solid and liquid were transferred onto a fine glass filter (4.0 - 5.5 μm) and filtered by washing with 5 mL of CS2 solution to remove insoluble materials such as coke. After filtration, the filtrate was analyzed by GC-FID. The results of the product formed in Example 16 are shown in Table 3 of Table 17. 【0099】 【Table 16】 【0100】 【Table 17】 【0101】 Example 17. Catalytic conversion of 1-octadecene using an alkene reactant other than ethylene over the catalyst composition of Example 1 in a batch reactor 【0102】 In Example 17, according to Table 18, 1-octadecene was reacted with propylene or 2-butene on the catalyst composition of Example 1 in a batch reactor (Parr reactor, series 2550). 1-Octadecene was degassed using three freeze-pump-thaw cycles and then transferred to an N2-filled glove box. The liquid was then dried over molecular sieves (3 Å). Inside the N2-filled glove box, the catalyst composition of Example 1 and 1-octadecene were loaded into a Parr reactor (10 mL, series 2550) equipped with a pressure gauge and a type K thermocouple. Propylene (99.8%, Praxair) was passed through a moisture / oxygen trap (Supelco) before use. 2-Butene (>99%, Sigma Aldrich) was used as received. Before introducing the alkene reactant into the reactor, the gas line was evacuated to remove residual air. After pressurizing with the alkene reactant, it was heated to the specified temperature. After the specified reaction time, the reactor was cooled in flowing air. Gas and liquid aliquots from the reactor headspace were taken for gas chromatography analysis using a flame ionization detector (GC-FID). The remaining solid and liquid were transferred onto a fine glass filter (4.0 - 5.5 μm) and filtered by washing with 5 mL of a CS2 solution to remove insoluble materials such as coke. After filtration, the filtrate was analyzed by GC-FID. The results are shown in Table 19. 【0103】 【Table 18】 【0104】 【Table 19】 【0105】 Example 18. Catalytic conversion of 1-pentene on the catalyst composition of Example 1 in a batch reactor 【0106】 In Example 18, 1-pentene was reacted with ethylene over a mixture of MTO / Cl-Al2O3 and Cl-Al2O3 in a batch reactor according to Table 6. 1-Pentene (Aldrich, 98.5%) was degassed using three freeze-pump-thaw cycles and vacuum distilled (about 10 -4It was transferred to an N₂-filled glove box, where the liquid was stored on molecular sieves (Aldrich, 3 Å, activated overnight at 300 °C in vacuo). Inside the glove box, 1-pentene (1 mL) was sealed in a 1-mL Schlenk flask equipped with a Teflon stopper. A gas valve partially filled with molecular sieves (Aldrich, 3 Å, activated overnight at 300 °C in vacuo) was filled with 900 mbar of ethylene (Praxair, UN1964, lot number 304325039305) containing 2 mol% of propane as an internal standard. The catalyst composition of Example 1 was loaded into a 120-mL Pyrex reactor in an Ar-filled glove box. The reactor, the ethylene gas valve, and the pentene flask were attached to a vacuum line. After evacuating the connecting line to remove air / water, the reactor was evacuated and heated to 100 °C. The reactor was sealed and the connecting line was filled with ethylene. After resealing the ethylene valve (to prevent cross-contamination), the 1-pentene storage flask was opened to generate a mixture of pentene and ethylene (after the reaction, the ethylene present in the 1-pentene flask was removed by freeze-pump-thaw cycles). A mixture of 1-pentene and ethylene (23 mol C₂ / mol C₅) was placed in the evacuated reactor, and the reactor pressure was set to 170 mbar. An aliquot of the headspace gas was removed at time intervals with a gastight syringe by placing a portion of the headspace gas into the evacuated part of the vacuum line equipped with a rubber septum. The progress of the reaction was monitored by GC-FID (Shimadzu GC-2010 equipped with a Supelco Alumina Sulfate plot column, 30 m × 0.32 mm) using propane present in ethylene as an internal standard. The column temperature was kept constant at 90 °C. After the reaction, the non-volatile products were recovered by extraction from the catalyst using room-temperature CHCl₃. The extracted products were analyzed by GC-MS using a Shimadzu GC2010 gas chromatograph equipped with an Agilent DB-1 capillary column (dimethylpolysiloxane, 30 m × 0.25 mm × 0.25 μm) connected to a QP2010 mass spectrometer. The temperatures of the injector and the detector were 250 °C.The temperature increase program was set to increase at 25°C / min up to 40°C (held for 3 minutes) and 250°C (held for 10 minutes). The results are shown in Table 21. 【0107】 【Table 20】 【0108】 【Table 21】 【0109】 It should be noted that one or more of the following claims utilize the terms "where" or "in which" as transitional phrases. For the purpose of defining the present technology, this term is introduced into the claims as an unrestricted transitional phrase used to introduce a list of a series of features of the structure and should be construed in the same manner as the more commonly used unrestricted preamble term "comprising". For the purpose of defining the present technology, the transitional phrase "consisting of" may be introduced into the claims as a closed preamble term that limits the claims to the recited components or steps and any naturally occurring impurities. For the purpose of defining the present technology, the transitional phrase "consisting essentially of" can be introduced into the claims to limit one or more of the claims to the recited elements, components, materials, or method steps, and any unrecited elements, components, materials, or method steps that do not substantially affect the novel features of the claimed subject matter. The transitional phrases "consisting of" and "consisting essentially of" can be construed as a subset of the non-limiting transitional phrases such as "comprising" and "including", and thus any use of a non-limiting phrase to introduce a list of a series of elements, components, materials, or steps should be construed as also disclosing a list of a series of elements, components, materials, or steps using the closed terms "consisting of" and "consisting essentially of". For example, a description of a composition "comprising" components A, B, and C should be construed as also disclosing a composition "consisting of" components A, B, and C, as well as a composition "consisting essentially of" components A, B, and C.Any quantitative value expressed in this application can be considered to include open-ended embodiments that coincide with the transitional phrase "comprising" or "including", as well as closed or partially closed embodiments that coincide with the transitional phrases "consisting of" and "consisting essentially of". 【0110】 As used in this specification and the appended claims, the singular forms "a", "an", and "the" include the plural referents unless the context clearly dictates otherwise. The verb "comprises" and its conjugations should be interpreted as referring to elements, components, or steps non-exclusively. The recited elements, components, or steps may be present, used, or combined with other elements, components, or steps that are not explicitly recited. 【0111】 It should be understood that any two quantitative values assigned to a property can constitute a range of that property, and all combinations of ranges formed from all the recited quantitative values of a given property are contemplated in this disclosure. The subject matter of this disclosure has been described in detail with reference to specific embodiments. It should be understood that any detailed description of the components or features of one or more embodiments does not necessarily mean that such components or features are essential to a particular embodiment or any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and changes can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

Claims

[Claim 1] Unsaturated polyethylene is at least chemical formula C ｍ H ２ｍ A process for converting to an alkene product, wherein the process includes contacting the unsaturated polyethylene with two or more catalyst components in a reactor, the reactor having chemical formula C ｎ H ２ｎ The alkene reaction product is included, During the ceremony, m is an integer between 3 and 20. n is an integer between 2 and 20. The two or more catalyst components mentioned above include a metathesis catalyst component and an isomerization catalyst component. Upon contact, at least a portion of unsaturated polyethylene or products derived therefrom undergoes metathesis and isomerization reactions, resulting in at least one product of chemical formula C ｍ H ２ｍ A process that generates effluent containing alkene products. [Claim 2] The process according to claim 1, wherein the pressure of the alkene reactant in the reactor during contact is between 0 pounds per square inch gauge (psig) and 3000 psig. [Claim 3] The process according to claim 1, wherein the temperature of the reactor during the contact is 400°C or less. [Claim 4] The process according to claim 1, wherein the alkene reactant comprises ethylene, propylene, butene, pentene, or a combination thereof. [Claim 5] The process according to claim 1, wherein the alkene product comprises propylene, butene, pentene, or a combination thereof. [Claim 6] The process according to claim 1, wherein the metathesis catalyst component comprises an element selected from Groups 5 to 10 of the International Union of Pure and Applied Chemistry (IUPAC). [Claim 7] The process according to claim 1, wherein the metathesis catalyst component includes rhenium, ruthenium, tungsten, molybdenum, vanadium, or a combination thereof. [Claim 8] The process according to claim 1, wherein the metathesis catalyst component comprises methyltrioxolenium (MTO). [Claim 9] The process according to claim 1, wherein the isomerization catalyst component comprises an element selected from Groups 5 to 10 of the IUPAC. [Claim 10] The process according to claim 1, wherein the isomerization catalyst component includes alumina, silica, iridium, palladium, ruthenium, or a combination thereof. [Claim 11] The process according to claim 1, wherein the first catalyst composition comprises the metathesis catalyst component and the isomerization catalyst component, and the first catalyst composition comprises MTO on alumina. [Claim 12] The process according to claim 1, wherein a first catalyst composition comprising MTO on alumina and a second catalyst composition comprising ruthenium, palladium, platinum, or a combination thereof are in contact with the unsaturated polyethylene in the reactor. [Claim 13] The process according to claim 1, wherein the process comprises contacting the unsaturated polyethylene with three or more catalyst components, the three or more catalyst components comprising a metathesis catalyst component, an isomerization catalyst component, and a dehydrogenation catalyst component. [Claim 14] The process according to claim 13, wherein the dehydrogenation catalyst component comprises an element selected from IUPAC Groups 5 to 10. [Claim 15] The process according to claim 13 or 14, wherein the dehydrogenation catalyst component includes platinum, iridium, ruthenium, rhenium, or a combination thereof.

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