Process for converting unsaturated polyethylene to olefin products

Abstract

The present disclosure relates to processes for converting unsaturated polyethylene to at least one olefin product. The process comprises contacting the unsaturated polyethylene with two or more catalyst components in a reactor comprising olefin reactants. The two or more catalyst components comprise a metathesis catalyst component and an isomerization catalyst component. The contacting causes at least a portion of the unsaturated polyethylene or a product derived therefrom to undergo a metathesis reaction and an isomerization reaction to produce an effluent comprising at least the olefinic product.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 353,327, filed on June 17, 2022, the entire disclosure of which is hereby incorporated by reference into this document. Background Art Technical Field

[0003] The present disclosure relates to chemical processing of hydrocarbons. In particular, the present disclosure relates to processes for converting ethylene-containing materials such as polyethylene into smaller desired hydrocarbon products. Background Art

[0005] For many industrial applications, hydrocarbons are used for or as starting materials to produce plastics, fuels and various downstream chemicals. Such hydrocarbons include olefins, such as ethene, propene and butene (also commonly referred to as ethylene, propylene and butylene, respectively). A variety of methods have been developed for the production of these lower hydrocarbons, including petroleum cracking and various synthesis methods. Polyethylene (PE) is the most widely used plastic in the world and can be made into a variety of products. However, it is desirable to recycle polyethylene into smaller monomers such as propylene. Conventional efforts for chemically recycling polyethylene typically use pyrolysis and high temperature thermal degradation. These methods are highly energy intensive and are subject to low selectivity of the desired product and greenhouse gases (e.g., CO 2 , CH 4 ) caused by. Summary of the invention

[0006] Embodiments of the present disclosure address these and other needs by providing methods for converting polyethylene into olefin products. The methods described herein can enable two or more catalyst components in a reactor to perform a variety of different chemical reactions, such as a combination of metathesis and isomerization for producing olefin products, for example, from unsaturated polyethylene and olefin reactants.

[0007] According to one or more other aspects of the present disclosure, a method for converting unsaturated polyethylene into at least one m H 2m A method for producing an olefin product, the method comprising contacting an unsaturated polyethylene with two or more catalyst components in a reactor, the reactor comprising a catalyst having a chemical formula of C n H 2nThe two or more catalyst components comprise a metathesis catalyst component and an isomerization catalyst component. The contacting causes at least a portion of the unsaturated polyethylene or a product derived therefrom to undergo a metathesis reaction and an isomerization reaction to produce at least one of the chemical formula C m H 2m The effluent is an olefin product.

[0008] Additional features and advantages will be set forth in the following Detailed Description, and in part will become apparent to those skilled in the art from that description or may be learned by practicing the embodiments described herein, including the following Detailed Description and claims.

[0009] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments, and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 schematically depicts a reactor according to one or more embodiments of the present disclosure;

[0011] For description Figure 1 For purposes of simplified schematics and description, many valves, temperature sensors, electronic controllers, etc. that may be employed in certain chemical processing operations and are well known to those of ordinary skill in the art are not included. In addition, accompanying components that are typically included in typical chemical processing operations, carrier gas supply systems, pumps, compressors, furnaces, or other subsystems are not depicted. It should be understood that these components are within the spirit and scope of the disclosed embodiments of the present invention. However, operating components (such as those described in the present disclosure) may be added to the embodiments described in the present disclosure. DETAILED DESCRIPTION

[0012] Some conventional methods for converting polyethylene into smaller products may use separate catalysts separated in separate catalyst zones, such as by loading each of the separate catalysts into separate reactors, which may increase the initial capital cost of the reaction system. In contrast, the methods disclosed herein can achieve tandem catalysis of polyethylene by contacting polyethylene with mutually compatible catalyst components to produce desired olefin products. Catalytic depolymerization of polyethylene under mild reaction conditions provides an advantageous and sustainable alternative for producing hydrocarbon feedstocks, monomers or other usable chemicals.

[0013] Reference will now be made in detail to an embodiment of a process for converting unsaturated polyethylene into olefin products in a reactor. As used herein, "unsaturated polyethylene" refers to a polyethylene comprising the formula C x H2x wherein x is an integer of at least 10 and wherein at least one carbon-carbon double bond is present. In an embodiment, the unsaturated polyethylene may include a branched polyethylene. In an embodiment, the unsaturated polyethylene may include a linear low density polyethylene (LLDPE), a low density polyethylene (LDPE), or a combination thereof. In an embodiment, the unsaturated polyethylene comprises C x H 2x , wherein x is an integer greater than or equal to 10, greater than or equal to 12, or even greater than or equal to 15. In an embodiment, the unsaturated polyethylene may have a number average molecular weight (M) of 150 g / mol to 1,000,000 g / mol. n ). In embodiments, the unsaturated polyethylene may be a waste stream of a hydrocarbon processing system or a product derived therefrom.

[0014] In embodiments, the reactor comprises an olefin reactant. In embodiments, the olefin reactant has the formula C n H 2n , wherein n is an integer from 2 to 20. For example, the olefin reactant may have the 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 olefin reactant may include ethylene, propylene, butene, pentene or a combination thereof. In an embodiment, the olefin reactant may be selected from the group consisting of ethylene, propylene, butene, pentene and a combination thereof. In an embodiment, the olefin reactant may include ethylene. In an embodiment, the olefin reactant may be substantially composed of ethylene or composed of ethylene. In an embodiment, the olefin reactant may include ethylene and butene. In an embodiment, the olefin reactant may be substantially composed of ethylene and butene or composed of ethylene and butene.

[0015] In an embodiment, the unsaturated polyethylene may be contacted with two or more catalyst components in a reactor. In other embodiments, the unsaturated polyethylene may be contacted with three or more catalyst components in a reactor. As used herein, "catalyst component" refers to any substance that increases the rate of a specific chemical reaction. Catalyst components and catalyst compositions made with the catalyst components described in the present disclosure can be used to promote various reactions, such as but not limited to dehydrogenation, metathesis, isomerization, or a combination of these. In an embodiment, the catalyst composition may include at least one catalyst component or at least two catalyst components. As used herein, "catalyst composition" refers to solid particles comprising at least one catalyst component. The catalyst composition may also include a catalyst support material.

[0016] In embodiments, catalyst component may include metathesis catalyst component, isomerization catalyst component and optionally dehydrogenation catalyst component.Do not wish to be bound by any particular theory, it is believed that in the presence of olefin reactant, metathesis catalyst can break the carbon chain of unsaturated polyethylene to produce two products with terminal unsaturates respectively, and the further metathesis of terminal unsaturated polyethylene intermediate product and olefin reactant may be unhelpful for further breaking the carbon chain.It is believed that isomerization catalyst component can convert terminal unsaturates into internal unsaturates, and isomerized product can be further decomposed into two products in the presence of metathesis catalyst component and olefin reactant.This circulation can continue until desired product or product group is produced from this process.In addition, it is believed that dehydrogenation catalyst can introduce additional unsaturates in the carbon chain of unsaturated polyethylene or the product derived therefrom, and this can increase the depolymerization of unsaturated polyethylene.

[0017] In an embodiment, a metathesis catalyst component in combination with an olefin reactant such as ethylene can be operated to break an unsaturated polyethylene chain into two species. In an embodiment, a metathesis catalyst component can break an olefin product derived from unsaturated polyethylene. In an embodiment, a metathesis catalyst component may include one or more elements selected from the 5th to 10th groups of the International Union of Pure and Applied Chemistry (IUPAC). In an embodiment, a metathesis catalyst component may include rhenium, ruthenium, tungsten, molybdenum, vanadium, or a combination thereof. In an embodiment, a metathesis catalyst component may be selected from the group consisting of rhenium, ruthenium, tungsten, molybdenum, vanadium, and a combination thereof. In an embodiment, a metathesis catalyst component may include methyltrioxorhenium (MTO).

[0018] In an embodiment, the isomerization catalyst component is operable to move the unsaturated on the unsaturated polyethylene or the unsaturated on the product derived therefrom from one position on the main chain to a different position. For example, in an embodiment, the isomerization catalyst component can move the unsaturated in the terminal position of the unsaturated polyethylene to an internal position. In an embodiment, the isomerization catalyst component may include one or more elements selected from the 5th to 10th groups of the International Union of Pure and Applied Chemistry (IUPAC). In an embodiment, the isomerization catalyst component may include alumina, silica, iridium, palladium, ruthenium, or a combination thereof. In an embodiment, the isomerization catalyst component may be selected from the group consisting of alumina, silica, iridium, palladium, ruthenium, and a combination thereof. In an embodiment, the isomerization catalyst component may include modified alumina, modified silica, or a combination thereof. For example, in an embodiment, the isomerization catalyst component may include, but is not limited to, chlorinated alumina, γ-alumina, chlorinated silica, or a combination thereof. In an embodiment, the isomerization catalyst component may include [tert-butyl-POCOP]Ir[C 2 H 4 ].

[0019] In an embodiment, the dehydrogenation catalyst component may cause the unsaturated polyethylene or a product derived therefrom to have additional unsaturations along the polyethylene backbone. In an embodiment, the dehydrogenation catalyst component may cause the unsaturated polyethylene or a product derived therefrom to undergo transfer dehydrogenation. In an embodiment, the dehydrogenation catalyst component may 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 may 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 a combination thereof.

[0020] In embodiments, the reactor may include one or more catalyst compositions comprising two or more catalyst components. For example, in embodiments, the catalyst composition may include a metathesis catalyst component and an isomerization catalyst component. In embodiments, the catalyst composition may include a dehydrogenation catalyst component and an isomerization catalyst component. In embodiments, the catalyst composition may include a metathesis catalyst component and an isomerization catalyst component. In embodiments, the catalyst composition may include a dehydrogenation catalyst component and a metathesis catalyst component. In embodiments, the catalyst composition may include a dehydrogenation catalyst component and a metathesis catalyst component. In embodiments, the catalyst composition may include a dehydrogenation catalyst component, a metathesis catalyst component, and an isomerization catalyst component. In embodiments, the catalyst composition may include a dehydrogenation catalyst component, a metathesis catalyst component, or an isomerization catalyst component. In embodiments, the reactor may include a first catalyst composition comprising a metathesis catalyst component and an isomerization catalyst component. For example, in embodiments, the reactor may include a first catalyst component, wherein the first catalyst component is MTO on alumina. In embodiments, the reactor may include a second catalyst composition comprising an additional metathesis catalyst component and / or an isomerization catalyst component. In embodiments, the reactor may include a second catalyst composition comprising a dehydrogenation catalyst component and an isomerization catalyst component. For example, in embodiments, the reactor may comprise a second catalyst component, wherein the second catalyst component may comprise platinum on alumina or platinum on silica. In embodiments, a first catalyst composition comprising MTO on alumina and a second catalyst composition may contact the unsaturated polyethylene in the reactor.

[0021] In an embodiment, the catalytic composition is specified by a certain weight percentage of one or more elements selected from the International Union of Pure and Applied Chemistry (IUPAC) Groups 5-10. In an embodiment, the first catalyst composition may include less than or equal to 15 weight % of any one of the elements selected from IUPAC Groups 5-10, based on the total weight of the first catalyst composition. For example, in an embodiment, the first catalyst composition may include less than or equal to 12 weight %, less than or equal to 10 weight %, less than or equal to 8 weight %, less than or equal to 6 weight %, less than or equal to 4 weight %, or even less than or equal to 2 weight % of any one of the elements selected from IUPAC Groups 5-10, based on the total weight of the first catalyst composition. In an embodiment, the first catalyst composition may include greater than 1 weight %, greater than 2 weight %, greater than 3 weight %, greater than 4 weight %, greater than 5 weight %, greater than 6 weight %, greater than 7 weight %, greater than 8 weight %, or even greater than 9 weight % of any one of the elements selected from IUPAC Groups 5-10, based on the total weight of the first catalyst composition. In an embodiment, the first catalyst composition may comprise any one element selected from IUPAC Groups 5-10 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.

[0022] In an embodiment, the second catalyst composition may include less than or equal to 15 wt % of any one of the elements selected from IUPAC Groups 5-10, based on the total weight of the second catalyst composition. For example, in an embodiment, the second catalyst composition may include less than or equal to 12 wt %, less than or equal to 10 wt %, less than or equal to 8 wt %, less than or equal to 6 wt %, less than or equal to 4 wt %, or even less than or equal to 2 wt % of any one of the elements selected from IUPAC Groups 5-10, based on the total weight of the second catalyst composition. In an embodiment, the second catalyst composition may include greater than 1 wt %, greater than 2 wt %, greater than 3 wt %, greater than 4 wt %, greater than 5 wt %, greater than 6 wt %, greater than 7 wt %, greater than 8 wt %, or even greater than 9 wt % of any one of the elements selected from IUPAC Groups 5-10, based on the total weight of the second catalyst composition. In an embodiment, the second catalyst composition may comprise any one element selected from IUPAC Groups 5-10 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 second catalyst composition.

[0023] It should be understood that, depending on the embodiment, the catalyst composition can be prepared by a process that produces the desired composition. Some non-limiting examples include incipient wetness impregnation or vapor deposition of a metal precursor (organic or inorganic in nature) followed by controlled decomposition thereof.

[0024] In embodiments, contacting the unsaturated polyethylene with two or more catalyst components in a reactor containing an olefin reactant may cause at least a portion of the unsaturated polyethylene or a product derived therefrom to undergo metathesis and isomerization reactions to produce at least one of the following: m H 2mThe effluent of the olefin product. For example, in an embodiment, the unsaturated polyethylene can contact the metathesis catalyst component in the presence of the olefin reactant to break the unsaturated polyethylene to form two products, wherein each product comprises terminal unsaturated polyethylene. The terminal unsaturated polyethylene can contact the isomerization catalyst component to cause the unsaturated in the terminal unsaturated polyethylene to move from the terminal position to the internal position to form an internal unsaturated polyethylene. Without wishing to be bound by any particular theory, it is believed that the internal unsaturated polyethylene can undergo further metathesis reaction by contacting the metathesis catalyst component in the presence of the olefin reactant. It is believed that the product derived from the unsaturated polyethylene contacting the metathesis catalyst component and the isomerization catalyst component in the presence of the olefin reactant can continue to circulate between the metathesis and isomerization reactions to produce smaller olefin products, such as the chemical formula C m H 2m wherein m is an integer from 3 to 20, such as propylene. In an embodiment, the reaction time may be increased to produce an effluent comprising smaller olefin products, as the increased reaction time will allow for additional metathesis and isomerization reaction cycles.

[0025] In an embodiment, the reactor can be any reactor that can be used to contact two or more catalyst components in the presence of olefin reactants with polyethylene and to carry out the 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 reaction 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 may include a reaction zone, in which contact and catalytic reaction may occur. In an embodiment, two or more catalyst components may be in the same reaction zone. In other embodiments, the reactor may include two or more reaction zones. In an embodiment, the reactor may include additional processing of reactants, such as processing of olefin reactants, unsaturated polyethylene and / or catalyst components. In an embodiment, the effluent containing one or more products from the catalytic reaction may be further processed, such as separating one or more products from the effluent. For example, in an embodiment, propylene may be separated from the effluent.

[0026] In embodiments, the pressure of the olefin reactant in the reactor (such as in the reaction zone) during contact can be 0 pounds per square inch gauge (psig) to 3000psig. For example, the pressure of the olefin reactant can be 0psig to 3000psig, 0psig to 2000psig, 0psig to 1000psig, 0psig to 900psig, 0psig to 800psig, 0psig to 700psig, 0psig to 600psig, 0psig to 500psig or 100psig to 3000psig. In some embodiments, the amount of the olefin reactant used can be quantified by the pressure of the olefin reactant in the reactor. In other embodiments, the amount of the olefin reactant can be quantified by the space velocity of the olefin reactant.

[0027] In embodiments, the temperature of the reactor (such as in the reaction zone) during contacting may be less than or equal to 400°C. For example, the temperature of the reactor during contacting may be less than or equal to 350°C, less than or equal to 300°C, less than or equal to 250°C, or even less than or equal to 200°C. In embodiments, the temperature of the reactor during contacting may be 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 wishing to be bound by any particular theory, it is believed that reduced reactor temperatures (such as less than or equal to 400°C, less than or equal to 350°C, less than or equal to 300°C, or less than or equal to 250°C) may reduce the formation of undesirable byproducts during contacting. Furthermore, the reduced operating temperature of the reactor can reduce the energy required for the process, which can also reduce the economic cost of operation.

[0028] In an embodiment, the contacting causes at least a portion of the unsaturated polyethylene to undergo a catalytic reaction to produce an effluent. In an embodiment, the effluent may include hydrocarbons having an average molecular weight of 40 g / mol to 1000 g / mol. In an embodiment, the effluent may include at least a m H 2m In an embodiment, the olefin product is an olefin product of the formula C m H 2m wherein m is an integer from 3 to 20. For example, the olefin product may be a compound of formula C m H 2mThe compound wherein m is an integer of 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 olefin product may include propylene, butenes, pentenes or a combination thereof. In an embodiment, the olefin product may be selected from the group consisting of propylene, butenes, pentenes and a combination thereof. In an embodiment, the olefin product may be substantially composed of propylene, butenes, pentenes or a combination thereof or may be composed of propylene, butenes, pentenes or a combination thereof. In an embodiment, the olefin product may be substantially composed of propylene or may be composed of propylene.

[0029] In embodiments, the effluent may comprise 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% olefin product.

[0030] Example

[0031] Various aspects of the present disclosure will be further illustrated by the following examples. The examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure. The materials used in these examples are provided in Table 1 below. In Examples 1-7, catalysts according to the present disclosure were prepared.

[0032] Table 1

[0033]

[0034]

[0035] Example 1.4 wt% CH 3 R 3 / Cl-Al 2 O 3 Preparation of catalyst composition

[0036] The catalyst composition of Example 1 was synthesized using the following protocol: 4 wt. CH 3 R 3 / Cl-Al 2 O 3 : γ-Al 2 O 3 (Strem Chemicals) was calcined at 550 °C for 4 h in air and then heated under dynamic vacuum (10 -4 The partially dehydrated and dehydroxylated alumina was heated in CCl 4 The chlorination was carried out at 300 °C for 1 h in a fixed bed reactor in a saturated Ar flow (Air Gas Company, UHP, 10 mL / min). CCl 4 Distillation. The obtained Cl-Al 2 O 3The mixture was evacuated at 450 °C overnight and vacuum sublimated at room temperature (about 10 -4 Torr) with CH 3 R 3 (MTO, Sigma-Aldrich) was modified to obtain a material containing 4 wt% MTO and 4 wt% Cl based on the total weight of the material. The solid was periodically shaken vigorously to promote uniform deposition of MTO. 2 O 3 After that, the catalyst was evacuated at room temperature for 30 min to remove physically adsorbed materials, and the catalyst was stored under N 2 Fill the glove box to prevent inactivation in air.

[0037] Example 2. Re 2 O 7 / γ-Al 2 O 3 Preparation of catalyst composition

[0038] The catalyst composition Re of Example 5 was synthesized using the following protocol 2 O 7 / γ-Al 2 O 3 : By incipient wetness impregnation of γ-Al with ammonium perrhenate 2 O 3 (Strem Chemical Company) Preparation of Re 2 O 7 / γ-Al 2 O 3 To obtain a material containing 10 wt% Re. Before impregnation, the γ-Al 2 O 3 Calcination was performed at 550 °C for 4 h within 2 h. After impregnation, the dried material was activated by calcination at 650 °C for 8 h in oxygen at 5 °C / min. The calcined catalyst was stored in N 2 The filled glove box was kept until use to avoid inactivation in air.

[0039] Comparative Example A. 4 wt% CH 3 R 3 / Cl-Al 2 O 3 Preparation of catalyst composition

[0040] The catalyst composition of Comparative Example 1 was synthesized using the following protocol: 4 wt. CH 3 R 3 / α-Al 2 O 3 :α-Al 2 O 3 (Sigma-Aldrich) was calcined at 550 °C for 4 h in air and then heated under dynamic vacuum (10 -4 The dehydrated α-Al 2 O 3 Vacuum sublimation at room temperature (about 10 -4 Torr) with CH 3R 3 (MTO, Sigma-Aldrich) to obtain a material containing 4 wt% MTO based on the total weight of the material. The solid was periodically shaken vigorously to promote uniform deposition of MTO. 2 O 3 After that, the catalyst was evacuated at room temperature for 30 min to remove physically adsorbed materials, and the catalyst was stored under N 2 Fill the glove box to prevent inactivation in air.

[0041] Comparative Example B. γ-Al 2 O 3 Preparation of catalyst composition

[0042] The catalyst composition of Comparative Example B was prepared as follows: γ-Al 2 O 3 (Strem Chemicals) was calcined at 550 °C for 4 h in air and then heated under dynamic vacuum (10 -4 The mixture was stirred at 450°C with evacuation at 200 torr overnight.

[0043] Example 3. Ru[PPh 3 ] 3 Preparation of [CO][Cl]H catalyst composition

[0044] The catalyst composition of Example 3 Ru[PPh 3 ] 3 [CO][Cl]H was synthesized according to the following literature: Prasanna, N.; Synthesis, Spectral and Electrochemical Studies of Ruthenium(II) / (III) Complexes of Alicyclic B-Ketamines, Indian J. Chem. 2001, 40, 426-429.

[0045] Example 4. Re / Al 2 O 3 Preparation of catalyst composition

[0046] The catalytic composition of Example 4, 10 wt% Re / Al 2 O 3 :1024mgγ-Al 2 O 3 Place in a round bottom flask with a stirring bar and heat to 110°C using a hot oil bath and dry for 24 hours. Add 163 mg of ammonium perrhenate to 5 mL of deionized water to form a mixture, and add the mixture to the dried γ-Al 2 O 3The slurry was stirred at 80°C overnight. The resulting solid was calcined in a furnace under a flow of dry air for 8 hours. The furnace ramp rate was 5°C / min until 650°C. The catalyst was cooled to room temperature under a flow of helium and transferred to an Ar-filled glove box for storage to obtain a catalyst composition comprising 10 wt% Re based on the total weight of the catalyst composition.

[0047] Example 5.7 wt% CH 3 R 3 / Cl-Al 2 O 3 Preparation of catalyst composition

[0048] The catalyst composition of Example 5 was synthesized using the following protocol, 7 wt% CH 3 R 3 / Cl-Al 2 O 3 : Sublimation of MTO to 816 mg Al in 5 hours 2 O 3 / Cl (4 wt%), using liquid N 2 The trap kept it at -78 °C. After the MTO was completely sublimated, the mixture was stirred for 0.5 h and allowed to warm to room temperature under static vacuum. The solid was then placed under dynamic vacuum for another 0.5 h. The material was inertly transferred to an Ar-filled glove box for storage.

[0049] Example 6. PtRe / SiO 2 Preparation of catalyst composition

[0050] The catalytic composition PtRe / SiO of Example 6 was prepared using the following protocol 2 : PtRe / SiO was prepared by incipient wetness impregnation of silica powder with ammonium perrhenate to obtain a material containing 1 wt%-5 wt% Re. 2 After impregnation, the material was calcined at 500°C. Pt was deposited on the material by incipient wetness impregnation with platinum acetylacetonate in toluene to obtain a material containing 1 wt% to 5 wt% Pt. The resulting solid was dried in air at 120°C for 4 h, after which the temperature was increased to 210°C for 4 h. The material was heated to 400°C. 2 The reduced catalyst was stored in N 2 atmosphere until use to avoid re-oxidation in air. 2 The catalyst was calcined at 500 °C for 4 h and then heated with H 2 The reduction was carried out at 280 °C for 2 h. The heating rate was 2 °C / min. After the reduction, the catalyst was evacuated at room temperature for 30 min to remove the physically adsorbed H 2 , and stored in N 2 Fill the glove box to prevent inactivation in air.

[0051] Example 7. tBu POCOP]Ir[C 2 H 4 Preparation of Catalytic Compositions

[0052] The catalytic composition of Example 7 [ tBu POCOP]Ir[C 2 H 4 ] was prepared according to "Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation-Olefin Metathesis" Science 2006, 312, 257-261. 6 H 3 -2,6-[OP(t-Bu) 2 ] 2 ]Ir[H][Cl] and NaO-t-Bu were weighed into an oven-dried Schlenk flask at a molar ratio of 1:1.2, respectively. The solid was then placed under an argon stream. 40 mL of toluene was added to the flask via a syringe, and the resulting suspension was stirred at room temperature for 10 minutes. Ethylene was bubbled through the solution for 1-2 hours. The solution was cannulated filtered through a diatomaceous earth pad, the volatiles were evaporated under vacuum, and the resulting red solid was dried overnight under vacuum to obtain a 60% yield of the product.

[0053] Example 8. Preparation of olefin-terminated polyethylene

[0054] In Example 8, olefin-terminated polyethylene was prepared as follows: a 300 ml Parr HP 5500 small 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. In an Ar-filled glove box, 2.8 mg (5 μmol) of {κ2-P, O-2-[bis(2-methoxyphenyl)phosphino]benzenesulfonate} nickel (II)-methylpyridine was weighed into a dry 7 mL glass vial and dissolved in 1 mL of toluene. The catalytic solution was inertly transferred to the Parr reactor using a gas-tight syringe. Ethylene (35 bar) was charged into the reactor, and the polymerization reaction was carried out for 60 minutes. The reactor was then vented and cooled to room temperature. The resulting polymer solution was precipitated in excess methanol (500 mL) and collected via vacuum filtration. The material was vacuum dried at 43 ° C. Because the product polymer contains a single unsaturated bond per polymer chain, the number of olefin protons (terminal and internal) was used to determine the -CH 2-- Normalization with protons provides an estimate of the polymer molecular weight (M N ). 1 HNMR (Toluene-d 8 ), alkyl-CH- 2 :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).

[0055] In Examples 9-11, the catalytic process according to the present disclosure was carried out in a batch reactor. The gas fraction products (C 1 -C 6 ) in the sample. The signal coefficient depends on the carbon number of each hydrocarbon species. The injector and detector temperature was 200°C. The temperature ramp program was as follows: 90°C (hold for 3 minutes), 10°C / min ramp to 150°C (hold for 20 minutes). Helium was used as the carrier gas. H 2 , C 2 H 4 and C 2 H 6 Quantification was performed on 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 TCD signal was confirmed to be positive for H using a standard gas mixture. 2 , C 2 H 4 and C 2 H 6 The response factor was obtained as the slope of the fitted line. The column, injector and detector temperatures were 130°C. The TCD current was 70 mA and the carrier gas pressure was 300 kPa (N 2 ). Liquid product (>C 5 ) were analyzed on an Agilent 6890N network gas chromatograph equipped with a DB-5 column and a FID detector. 1 H NMR spectra were recorded at 600 MHz on a Varian Unity Inova AS600 spectrometer in 1,1,2,2-tetrachloroethane-d 2 The samples were collected and analyzed using MestReNova (v11.0.1, Mestrelab Research SL). Chemical shifts (δ, ppm) were calibrated using the residual proton signal of the solvent and referenced to tetramethylsilane (TMS).

[0056] Example 9. Catalytic conversion of unsaturated polyethylene in a batch reactor

[0057] In Example 9, the unsaturated polyethylene (M n =1300 g / mol) was reacted with ethylene according to Table 2 in a 10 mL batch reactor (Parr reactor, series 2550) over one of the following catalyst compositions: Comparative Example A or Example 1.2 In a filled glove box, the catalyst composition, unsaturated polyethylene and unsaturated polyethylene are loaded into a reactor equipped with a pressure gauge and a K-type thermocouple. Ethylene (99.999%, Air Gas Company) is passed through a moisture / oxygen trap (Chromatography Company) before use. Before ethylene is introduced into the reactor, the residual air in the gas line is purged for three 5-minute cycles. Reactor heating is started and the reaction time is tracked after reaching the desired temperature of 130°C. After a reaction time of 3 hours, the reactor is cooled in flowing air. Before exhausting the remaining head space in the fume hood, an aliquot of the gas is taken from the reactor head space for GC analysis. The remaining solids and liquids are transferred to a fine glass filter (4.0μm-5.5μm) and filtered by heating with hot (50°C) CHCl 3 The insoluble material was removed by filtration and washing. The soluble hydrocarbons were recovered by evaporating the solvent under reduced pressure (0.1 torr). The insoluble material was recovered from the filter, including the insoluble hydrocarbons in the hot CHCl 3 The solid was analyzed by GPC. The results of the product formed in Example 9 are shown in Table 3.

[0058] Table 2

[0059]

[0060] Table 3

[0061]

[0062] Example 10. Catalytic conversion of unsaturated polyethylene to olefins in a batch reactor at different reaction times hydrocarbon

[0063] In Example 10, the unsaturated polyethylene (M n =1300 g / mol) was reacted with ethylene in a batch reactor according to Table 4 over one of the following catalyst compositions: Example 1 or Example 2 (Examples 10-1 and 10-2: 10 mL Parr reactor, series 2550; Example 10-3; Comparative Examples 10A and 10B: 25 mL Parr reactor, series 4590). 2In a filled glove box, the catalyst composition and unsaturated polyethylene are loaded into a reactor equipped with a pressure gauge and a K-type thermocouple. Ethylene (99.999%, Air Gas Company) is passed through a moisture / oxygen trap (Chromatography Company) before use. Before introducing ethylene into the reactor, the residual air in the gas line is purged for three 5-minute cycles. Reactor heating is started. According to Table 4, the reaction time is tracked after reaching the specified temperature. After the specified reaction time, the reactor is cooled in flowing air. Before exhausting the remaining head space in the fume hood, an aliquot of the gas is taken from the reactor head space for GC analysis. The remaining solids and liquids are transferred to a fine glass filter (4.0μm-5.5μm) and filtered through a hot (50°C) CHCl 3 The insoluble material was removed by filtration and washing. The soluble hydrocarbons were recovered by evaporating the solvent under reduced pressure (0.1 torr). The insoluble material was recovered from the filter, including the insoluble hydrocarbons in the hot CHCl 3 The solid was analyzed by GPC. The results of the product formed in Example 10 are shown in Table 5.

[0064] Table 4

[0065]

[0066] Table 5

[0067]

[0068] Example 11.1-Catalytic Conversion of Octadecene in a Batch Reactor over Catalyst Composition Example 1

[0069] In Example 11, 1-octadecene was reacted with ethylene according to Table 6 over the catalyst composition of Example 1 and in a batch reactor (Parr reactor, Series 2550). The 1-octadecene was degassed using three freeze-pump-thaw cycles and then transferred to N 2 Then use molecular sieve Dry the liquid. 2In a glove box filled with 1-octadecene, the catalyst composition of Example 1 and 1-octadecene were loaded into a Parr reactor (10 mL, 2550 series) equipped with a pressure gauge and a K-type thermocouple. Ethylene (99.999%, Air Gas Company) was passed through a moisture / oxygen trap (Chromatography Company) before use. Before ethylene was introduced into the reactor, the residual air in the gas line was purged for three cycles. After pressurization with ethylene, it was heated to a specified temperature. After the specified reaction time, the reactor was cooled in flowing air. An aliquot of gas and liquid was taken out from the reactor head space and gas chromatography was performed with a flame ionization detector (GC-FID). The remaining solid and liquid were transferred to a fine glass filter (4.0 μm-5.5 μm) and filtered by 5 mL of CS 2 The solution is washed and filtered to remove insoluble materials, such as coke. After filtering, the filtrate solution is analyzed by GC-FID. The 1H NMR spectrum of the reaction product is measured. The peak characteristics of internal olefins and terminal olefins are integrated. The ratio of internal olefins to terminal olefins is calculated. The results are shown in Table 7.

[0070] Table 6

[0071]

[0072] Table 7

[0073]

[0074] In Example 12, a stirred tank reactor was used, such as Figure 1As shown. A 20mL glass reaction sleeve (ID = 19.56mm, OD = 22.15mm) is placed in a 40mL stainless steel stirred tank reactor (ID = 22.16mm, OD = 40mm), and the reactor is placed in an aluminum heating jacket. The temperature of the heating jacket is controlled by a hot plate and a thermocouple (IKA C-MAG HS7 digital). The reactor has two inlets, one for liquid substrates and the second for gaseous substrates. Liquid substrates are delivered to the device using a Hamilton gas-tight syringe (5mL) and a Kd Scientific Legato 100 syringe pump. The gaseous substrate is supplied by a pressurized tank, and its flow rate is set by an Alcat mass flow controller (MCS series). The outlet flows to an Equilibar back pressure regulator, which is used to control the reaction pressure. Attached downstream of the regulator is an Agilent 6850 gas chromatograph (GC). GC is equipped with a 6-port VICI-Valco gas sampling valve. A continuous ethylene flow is used as an internal standard for quantitative olefin formation rate. Stainless steel tubing and fittings were purchased from McMaster-Carr and Swagelok. The GC was equipped with a FID and a Petrocol DH capillary GC column (100 mm×0.25 mm×0.5 μm film thickness). The column was maintained at 45 PSI and the gas sample was split at 50:1. The column conditions and product elution times are shown in Tables 8 and 9, respectively.

[0075] Table 8

[0076] Oven slope ℃ / min Next ℃ Keep min initial 50 8 Ramp1 15 100 1 Ramp2 15 150 15.00

[0077] Table 9

[0078] Hydrocarbon substances Elution time min Ethylene 8.2 Propylene 8.3 Butene 8.8–9.0 Pentene 10.1–9.5 Hexene 12.2–14.1 Heptene 15.1-17.0 Octene 19.0-20.1 Nonene 22.0-24.1 Decene 25.4-26.3

[0079] In Example 12, an olefin-terminated polyethylene prepared as in Example 8 was reacted with ethylene and a catalyst composition as described herein in a stirred tank reactor using various reaction conditions. The maximum propylene formation rate (R) detected while the catalyst was running was measured. C3,max ), the unit is millimole / hour (mmol h -1 ). Measure the maximum propylene selectivity (S C3,max ) and butene selectivity (S C4,max The formation rates of propylene and butene were normalized by the cumulative olefin formation rate for a given reaction time. The average propylene selectivity (S C3,avg ) and the average butene selectivity (S C4,avg) is evaluated at each sampling point during the continuous reaction process of each substance. The polyethylene conversion rate (in weight percent) is also calculated by calculating the mass of polyethylene consumed per olefin produced according to Formula 1:

[0080]

[0081] Where i represents the number of carbon units in the olefin, MW i represents the molecular weight of substance "i", n ci- is the number of moles of substance "i" formed during the experiment, and m PE,o- is the initial loading of polyethylene, assuming that each olefin molecule formed contains two carbons from ethylene. The results are summarized in Table 10.

[0082] Example 12. Catalytic conversion of olefin-terminated polyethylene to form olefins in a stirred tank reactor

[0083] Example 12-1 is carried out as follows: In an Ar-filled glove box, 157 mg of olefin-terminated polyethylene is loaded into a stirred tank reactor. The reactor is taken out of the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. The Ar atmosphere in the reactor is evacuated for at least 15 minutes using a continuous ethylene flow fed at 5 mL / min. A catalyst solution is prepared in an Ar-filled glove box by mixing 5 mL of toluene with 53.0 mg of Ultracat in a 20 mL scintillation bottle. The solution is stirred for 3 to 5 minutes and then transferred to a 5 mL syringe, which is capped with a needle and a septum for inert delivery via a syringe pump. Within 9 hours, the catalyst solution (0.01 mL / min) is co-fed with ethylene gas (2.2 mL / min) to a reactor heated to and maintained at 85 ° C and 5.4 atm. In order to monitor the reaction progress, a sample (0.25 mL) of the gas effluent is analyzed via GC every 34.2 minutes for a reaction duration of 9 hours.

[0084] Example 12-2 was carried out according to Example 12-1, but before heating, 100 mg of Example 6 was loaded into the stirred tank reactor together with PE, and the reaction temperature was 100° C. In addition, Example 12-2 used 250 mg of PE instead of 157 mg, and 51.0 mg of UltraCat instead of 53 mg.

[0085] Example 12-3 was carried out according to Example 12-2, but 19.4 mg of Example 3 was loaded into the stirred tank reactor together with PE instead of Example 6 before heating.

[0086] Example 12-4 is carried out as follows: In an Ar-filled glove box, 250 mg of olefin-terminated polyethylene is loaded into a stirred tank reactor. The reactor is taken out of the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. The Ar atmosphere in the reactor is evacuated for at least 15 minutes using a continuous ethylene flow fed at 5 mL / min. A catalyst solution is prepared in an Ar-filled glove box by mixing 5 mL of toluene with 50.0 mg Ultracat and 20 mg of Example 3 in a 20 mL scintillation bottle. The solution is stirred for 3 to 5 minutes and then transferred to a 5 mL syringe, which is capped with a needle and a septum for inert delivery via a syringe pump. Within 8 hours, the catalyst solution (0.01 mL / min) is co-fed with ethylene gas (2.2 mL / min) to a reactor heated to and maintained at 100 ° C and 5.4 atm. In order to monitor the reaction progress, a sample (0.25 mL) of the gas effluent is analyzed via GC every 34.2 minutes for a reaction duration of 8 hours.

[0087] Example 12-5 was carried out according to Example 12-4, but the reaction pressure was 1 atm instead of 5.4 atm.

[0088] Embodiment 12-6 is carried out according to embodiment 12-4, but reaction temperature is 70 ℃, pressure is 1.0atm, and time is 9 hours.In addition, after 9 hours reaction, the mixture is cooled and left to stand for two days.The second catalyst feed of the same concentration is prepared in the glove box filled with Ar.Subsequently, catalyst solution (0.01mL / min) and ethylene gas (2.2mL / min) are co-fed into the reactor, and the reactor is heated to and maintained at 70 ℃ and 1atm for another 8 hours.In order to monitor the progress of the reaction, for the reaction duration of 8 hours, a sample (0.25mL) of the gas effluent is analyzed via GC every 34.2 minutes.

[0089] Example 12-7 was carried out according to Example 12-5, but the mass of Example 3 used to prepare the catalyst solution was 103 mg instead of 20 mg.

[0090] Example 12-8 was performed as follows: 253 mg of the olefin-terminated polyethylene of Example 8 was loaded into a stirred tank reactor in an Ar-filled glove box. Next, the reactor was removed from the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. The Ar atmosphere in the reactor was evacuated for at least 15 minutes using a continuous ethylene flow fed at 5 mL / min. 5 mL of toluene, 50.0 mg of UltraCat, and 42.0 mg of [Pd I [μ-Br] t Bu 3 P] 2-(Strem Chemical Company) mixed, in the glove box filled with Ar, prepare catalyst solution.The solution was stirred for 3 to 5 minutes, then transferred to a 5mL syringe, which was capped with a needle and septum for inert delivery via a syringe pump.In 9 hours, the catalyst solution (0.01mL / min) was co-fed with ethylene gas (10.1mL / min) to a reactor heated to and maintained at 70°C and 1atm.In order to monitor the reaction progress, for a reaction duration of 9 hours, a sample (0.25mL) of gas effluent was analyzed via GC every 34.2 minutes.

[0091] Example 12-9 was carried out according to Example 12-8, but 61 mg of Alkene Zipper (Strem Chemical Company) was used instead of [Pd I [μ-Br] t Bu 3 P] 2 Prepare the catalyst solution.

[0092] Example 12-10 is carried out as follows: In an Ar-filled glove box, 253 mg of the olefin-terminated polyethylene of Example 8 and 202 mg of Example 5 are loaded into a stirred tank reactor. Next, the reactor is taken out of the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. The Ar atmosphere in the reactor is evacuated for at least 15 minutes using a continuous ethylene flow fed at 5 mL / min. Over 20 hours, ethylene gas (10.1 mL / min) is continuously flowed into the reactor, and the reactor is heated to and maintained at 100 ° C and 1 atm for 20 hours. In order to monitor the reaction progress, for a reaction duration of 20 hours, a sample (0.25 mL) of the gas effluent is analyzed via GC every 34.2 minutes.

[0093] Example 12-11 was carried out according to Example 12-10, but in addition to Example 5, 14.5 mg of [Pd I [μ-Br] t Bu 3 P] 2- (Strem) was loaded into a stirred tank reactor. The reaction was run for 10.5 hours instead of 20 hours.

[0094] Example 12-12 was carried out according to 12-11, but 51 mg of Example 6 was loaded into the stirred tank reactor instead of [Pd I [μ-Br] t Bu 3 P] 2 149 mg UltraCat was used instead of 202 mg. The reaction was run for 8 hours instead of 10.5 hours.

[0095] Example 12-13 was carried out according to 12-12, but 24.6 mg of Example 7 was charged to the stirred tank reactor instead of Example 6. 156 mg UltraCat was used instead of 149 mg. The reaction was carried out for 19.5 hours instead of 8 hours.

[0096] Examples 12-14 were carried out as follows: In 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 MeOH dissolved in toluene (2 M) were added. 3 Al is loaded into stirred tank reactor. Next, the reactor is taken out from the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. The Ar atmosphere in the reactor is evacuated for at least 15 minutes using a continuous ethylene stream fed with 5mL / min. Within 10 hours, ethylene gas (2.2mL / min) is continuously flowed into the reactor heated to and maintained at 170°C and 6.8atm. In order to monitor the reaction progress, for a 10-hour reaction duration, a sample (0.25mL) of gas effluent is analyzed via GC every 34.2 minutes.

[0097] Examples 12-15 were carried out according to Examples 12-14, but 3 mg of Example 7 were loaded into the stirred tank reactor instead of Example 6. The reaction temperature was 150°C instead of 170°C.

[0098] Table 10

[0099]

[0100]

[0101] Example 13. Catalytic conversion of olefin-terminated polyethylene to form olefins in a stirred tank reactor at low temperature

[0102] Example 13-1 was performed as follows: In an Ar-filled glove box, 250 mg of olefin-terminated polyethylene was loaded into a stirred tank reactor with 2 mL of toluene. Next, the reactor was removed from the glove box, placed in an aluminum heating jacket, and connected to an ethylene delivery source. The Ar atmosphere in the reactor was evacuated for at least 10 minutes using a continuous ethylene flow fed at 5 mL / min. 3 mL of toluene, 50.0 mg of UltraCat, and 9.5 mg of [Pd I [μ-Br] t Bu 3 P] 2Mix, prepare catalyst solution in the glove box filled with Ar.The solution is stirred for 5 to 10 minutes, then transferred to a 5mL syringe, which is capped with a needle and a septum for inert delivery via a syringe pump.In 5 hours, the catalyst solution (0.01mL / min) and ethylene gas (5.0mL / min) are co-fed into a reactor heated to and maintained at 35°C and 2atm.In order to monitor the reaction progress, for a reaction duration of 9 hours, a sample (0.25mL) of gas effluent is analyzed via GC every 10 minutes.

[0103] Example 13-2 was performed as follows: In an Ar-filled glove box, 250 mg of olefin-terminated polyethylene was loaded into a stirred tank reactor with 1 mL of toluene. Next, the reactor was taken out of the glove box, placed in an aluminum heating jacket, and heated to 70 ° C for 30 minutes. Next, the reactor was connected to ethylene and nitrogen delivery sources. The Ar atmosphere in the reactor was evacuated for at least 5 minutes using continuous ethylene and nitrogen flows each fed at 5 mL / min. The 20 mL scintillation vial was mixed with 2 mL of toluene and 30 mg of C 31 H 38 Cl 2 N 2 ORu and 2 mL toluene with 16 mg [Pd I [μ-Br] t Bu 3 P] 2 Two catalyst solutions were prepared in an Ar-filled glove box. The solutions were stirred for at least 15 min and then transferred to two separate 5 mL syringes capped with needles and septa for inert delivery via syringe pumps. [Pd I [μ-Br] t Bu 3 P] 2 The catalyst solution is fed into the reactor, followed by C 31 H 38 Cl 2 N 2 The ORu solution was fed for 5 hours (0.01 mL / min) and co-fed with ethylene gas (5.0 mL / min) and nitrogen (5.0 mL / min) into a reactor heated to and maintained at 35°C and 1 atm. To monitor the progress of the reaction, samples (0.25 mL) of the gas effluent were analyzed via GC every 10 minutes for a reaction duration of 9 hours.

[0104] Table 11

[0105]

[0106] A The maximum propylene formation rate detected when the catalyst is running B This value describes the maximum selectivity evaluated when the catalyst is running. The propylene formation rate is normalized by the cumulative olefin formation rate for a given reaction time. C This value is the average value of the selectivity evaluated at each sampling point during the continuous reaction process of a given substance D The PE conversion is calculated by calculating the mass of PE consumed per olefin produced (see equation 1)

[0107] Example 14. Catalytic Conversion of Unsaturated Polyethylene Using Propylene as Olefin Reactant in a Batch Reactor

[0108] In Example 14, the unsaturated polyethylene (M n =1300 g / mol, dispersion = 11) were reacted with different amounts of propylene according to Table 12 over the catalyst composition of Example 1 in a 10 mL batch reactor (Parr reactor, series 2550) for different amounts of time. 2 In a filled glove box, the catalyst composition and unsaturated polyethylene are loaded into a reactor equipped with a pressure gauge and a K-type thermocouple. Propylene (99.8%, Praxair) is passed through a moisture / oxygen trap (Chromatography) before use. Before propylene is introduced into the reactor, the gas line is thoroughly evacuated to remove residual air. Reactor heating is started, and the reaction time is tracked after reaching the desired temperature of 130°C. After a reaction time of 1 or 5 hours, the reactor is cooled in flowing air. Before exhausting the remaining head space in the fume hood, an aliquot of the gas is taken out from the reactor head space for GC analysis. At 110°C, the remaining solid is transferred to a 20mL vial containing xylene to dissolve the product from the catalyst. The xylene solution is mixed with 180mL of room temperature methanol to precipitate the extraction product, and the extraction product is separated from methanol by vacuum filtration. Comparative Example 14-4 is prepared similarly to Example 14-1, but saturated polyethylene is used instead of unsaturated polyethylene. The product is analyzed by GPC. The results of the product formed in Example 14 are shown in Table 33.

[0109] Table 12

[0110]

[0111] Table 13

[0112]

[0113] Example 15. Catalyst composition for the preparation of unsaturated polyethylene in a batch reactor Catalytic conversion in Example 1

[0114] In Example 15, the unsaturated polyethylene (M n =1300 g / mol, dispersion = 11) According to Table 14 and ethylene in MTO / Cl-Al2 O 3 and Cl-Al 2 O 3 The mixture was reacted in a 10 mL batch reactor (Parr reactor, series 2550). 2 In a filled glove box, the catalyst composition mixture, unsaturated polyethylene and unsaturated polyethylene are loaded into a reactor equipped with a pressure gauge and a K-type thermocouple. Ethylene (99.999%, Air Gas Company) is passed through a moisture / oxygen trap (Chromatography Company) before use. Before ethylene is introduced into the reactor, the residual air in the gas line is purged for three 5-minute cycles. Start the reactor heating and track the reaction time after reaching the desired temperature of 130°C. After a reaction time of 3 hours, the reactor is cooled in flowing air. Before exhausting the remaining head space in the fume hood, an aliquot of the gas is taken from the reactor head space for GC analysis. The remaining solid is transferred to a 20mL vial containing xylene at 110°C to dissolve the product from the catalyst. The xylene solution is mixed with 180mL of room temperature methanol to precipitate the extraction product, which is separated from methanol by vacuum filtration. The product is analyzed by GPC. The results of the product formed in Example 15 are shown in Table 15. Table 3

[0115] Table 14

[0116]

[0117] Table 15

[0118] Example Propylene produced (mg) 2-Butene produced (mg) 15-1 41 7.3 15-2 26 4.8 15-3 12 2.3 15-4 19 1.7

[0119] Example 16.1-Catalytic Conversion of Octadecene in a Batch Reactor over Catalyst Composition Example 1

[0120] In Example 16, 1-octadecene was reacted with ethylene in MTO / Cl-Al according to Table 16. 2 O 3 and Cl-Al 2 O 3 The mixture was reacted in a batch reactor (Parr reactor, series 2550). 1-Octadecene was degassed using three freeze-pump-thaw cycles and then transferred to N 2 Then use molecular sieve Dry the liquid. 2In a glove box filled with 1-octadecene, the catalyst composition of Example 1 and 1-octadecene were loaded into a Parr reactor (10 mL, 2550 series) equipped with a pressure gauge and a K-type thermocouple. Ethylene (99.999%, Air Gas Company) was passed through a moisture / oxygen trap (Chromatography Company) before use. Before ethylene was introduced into the reactor, the residual air in the gas line was purged for three cycles. After pressurization with ethylene, it was heated to a specified temperature. After the specified reaction time, the reactor was cooled in flowing air. An aliquot of gas and liquid was taken out from the reactor head space and gas chromatography was performed with a flame ionization detector (GC-FID). The remaining solid and liquid were transferred to a fine glass filter (4.0 μm-5.5 μm) and filtered by 5 mL of CS 2 The solution was washed and filtered to remove insoluble materials such as coke. After filtration, the filtrate solution was analyzed by GC-FID. The results of the product formed in Example 16 are shown in Table 17. Table 3

[0121] Table 7.

[0122]

[0123]

[0124] Table 17

[0125]

[0126] Example 17. Reaction of olefins other than ethylene in a batch reactor over catalyst composition Example 1 Catalytic conversion of 1-octadecene by

[0127] In Example 17, 1-octadecene was reacted with propylene or 2-butene according to Table 18 in a batch reactor (Parr reactor, series 2550) over the catalyst composition of Example 1. The 1-octadecene was degassed using three freeze-pump-thaw cycles and then transferred to N 2 Then use molecular sieve Dry the liquid. 2In a filled glove box, the catalyst composition of Example 1 and 1-octadecene are loaded into a Parr reactor (10 mL, 2550 series) equipped with a pressure gauge and a K-type thermocouple. Propylene (99.8%, Praxair) is passed through a moisture / oxygen trap (Chromatography) before use. 2-Butene (>99%, Sigma Aldrich) is used as is. Before the olefin reactant is introduced into the reactor, the gas line is evacuated to remove residual air. After pressurization with the olefin reactant, it is heated to a specified temperature. After the specified reaction time, the reactor is cooled in flowing air. An aliquot of gas and liquid is taken out from the reactor head space, and gas chromatography is performed with a flame ionization detector (GC-FID). The remaining solid and liquid are transferred to a fine glass filter (4.0 μm-5.5 μm), and by using 5 mL CS 2 The solution was washed and filtered to remove insoluble materials, such as coke. After filtering, the filtrate solution was analyzed by GC-FID. The results are shown in Table 19.

[0128] Table 18

[0129]

[0130]

[0131] Table 19

[0132]

[0133] Example 18. Catalytic Conversion of 1-Pentene in a Batch Reactor over Catalyst Composition Example 1

[0134] In Example 18, 1-pentene was reacted with ethylene in MTO / Cl-Al according to Table 6. 2 O 3 and Cl-Al 2 O 3 The mixture was reacted in a batch reactor. 1-Pentene (Aldrich, 98.5%) was degassed using three freeze-pump-thaw cycles and vacuum distilled (ca. 10 -4 and transfer to N 2 The glove box was filled with liquids stored over molecular sieves (Aldrich, Vacuum activated at 300°C overnight). In a glove box, 1-pentene (1 mL) was sealed in a 1 mL Schlenk flask equipped with a Teflon stopper. The flask was partially filled with molecular sieves (Aldrich, The gas ball of 1-pentene (Pyrex, UN1964, batch number 304325039305) was filled with 900 mbar ethylene (Prax, UN1964, batch number 304325039305) containing 2 mol% propane as internal standard at 300°C. The catalyst composition of Example 1 was loaded into a 120 mL Pyrex reactor in an Ar-filled glove box. The reactor, ethylene gas ball and pentene flask were attached to the 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 the ethylene ball was sealed again (to prevent cross contamination), the 1-pentene storage flask was opened to produce a mixture of pentene and ethylene (after the reaction, the ethylene present in the 1-pentene flask was removed via a freeze-pump-thaw cycle). The mixture of 1-pentene and ethylene (23 mol C 2 / mol C 5 ) into the evacuated reactor, generating a reactor pressure of 170 mbar. By allowing a portion of the headspace gas to enter the evacuated section of the vacuum line equipped with a rubber septum, aliquots of the headspace gas were removed at timed intervals with a gas-tight syringe. The reaction progress was monitored by GC-FID (Shimadzu GC-2010, equipped with a Supelco Alumina Sulfateplot column, 30m×0.32mm) using propane present in ethylene as an internal standard. The column temperature was kept constant at 90°C. After the reaction, the reaction mixture was concentrated using room temperature CHCl 3 The non-volatile products were recovered by extraction from the catalyst. The extracted products were analyzed by GC-MS using a Shimadzu GC2010 gas chromatograph equipped with an Agilent DB-1 capillary column (dimethylpolysiloxane, 30m×0.25mm×0.25μm) coupled to a QP2010 mass spectrometer. The injector and detector temperatures were 250°C. The temperature ramp program was: 40°C (held for 3 minutes), 25°C per minute ramped to 250°C (held for 10 minutes). The results are shown in Table 21.

[0135] Table 20

[0136]

[0137] Table 21

[0138]

[0139] It should be noted that one or more of the following claims utilize the term "where" or "in which" as a transitional phrase. For purposes of defining the present technology, it should be noted that this term is introduced in the claims as an open transitional phrase that is used to introduce a recitation of a series of characteristics of a structure and should be interpreted in a manner similar to the more commonly used open preamble term "comprising". For purposes of defining the present technology, the transitional phrase "consisting of" may be introduced in a claim as a closed preamble term that limits the scope of the claim to the listed components or steps and any naturally occurring impurities. For purposes of defining the present technology, the transitional phrase "consisting essentially of" may be introduced in a claim to limit the scope of one or more claim items to the stated elements, components, materials, or method steps and any non-stated elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter. The transition phrases "consisting of" and "consisting essentially of" may be interpreted as a subset of open transition phrases, such as "comprising" and "including", such that any use of an open phrase to introduce a statement of a list of elements, components, materials, or steps should be interpreted as also disclosing the statement of the list of elements, components, materials, or steps using the closed terms "consisting of" and "consisting essentially of". For example, a statement that a composition "comprising" components A, B, and C should be interpreted 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 may be considered to include open embodiments that conform to the transition phrases "comprising" or "comprising" as well as closed or partially closed embodiments that conform to the transition phrases "consisting of" and "consisting essentially of".

[0140] As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly indicates otherwise. The verb "comprise" and its cognate forms should be interpreted as referring to elements, components, or steps in a non-exclusive manner. The referenced elements, components, or steps may exist, be utilized, or be combined with other elements, components, or steps that are not explicitly referenced.

[0141] It should be understood that any two quantitative values ​​assigned to a characteristic may constitute the range of the characteristic, and all combinations of ranges formed by all said quantitative values ​​of a given characteristic are considered in the present disclosure. The subject matter of the present disclosure has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of one or more embodiments does not necessarily imply that a component or feature is necessary for a particular embodiment or any other embodiment. Further, it will be apparent to those skilled in the art that various modifications and changes may be made to the described embodiments without departing from the essence and scope of the claimed subject matter.

Claims

1. A method for converting unsaturated polyethylene into at least one m H 2m A method for producing an olefin product, the method comprising contacting the unsaturated polyethylene with two or more catalyst components in a reactor, the reactor comprising a catalyst having a chemical formula of C n H 2n of an olefin reactant; in: m is an integer from 3 to 20; n is an integer from 2 to 20; The two or more catalyst components comprise a metathesis catalyst component and an isomerization catalyst component; and The contacting causes at least a portion of the unsaturated polyethylene or a product derived therefrom to undergo metathesis and isomerization to produce at least a portion of the unsaturated polyethylene having the formula C m H 2m of the olefin product effluent.

2. The process of any one of the preceding claims, wherein the pressure of the olefin reactant in the reactor during the contacting is from 0 pounds per square inch gauge (psig) to 3000 psig.

3. The process according to any one of the preceding claims, wherein the temperature of the reactor during the contacting is less than or equal to 400°C.

4. The process of any one of the preceding claims, wherein the olefin reactant comprises ethylene, propylene, butenes, pentenes, or combinations thereof.

5. The process of any one of the preceding claims, wherein the olefin product comprises propylene, butenes, pentenes, or combinations thereof.

6. The process according to any one of the preceding claims, wherein the metathesis catalyst component comprises an element selected from International Union of Pure and Applied Chemistry (IUPAC) Groups 5-10.

7. The process of any one of the preceding claims, wherein the metathesis catalyst component comprises rhenium, ruthenium, tungsten, molybdenum, vanadium, or a combination thereof.

8. The process according to any one of the preceding claims, wherein the metathesis catalyst component comprises methyltrioxorhenium (MTO).

9. The process according to any one of the preceding claims, wherein the isomerization catalyst component comprises an element selected from IUPAC Groups 5-10.

10. The process of any one of the preceding claims, wherein the isomerization catalyst component comprises alumina, silica, iridium, palladium, ruthenium, or combinations thereof.

11. The process of any one of the preceding claims, wherein a first catalyst composition comprises the metathesis catalyst component and the isomerization catalyst component, and wherein the first catalyst composition comprises MTO on alumina.

12. The process of any one of the preceding claims, wherein a first catalyst composition comprising MTO on alumina and a second catalyst composition comprising ruthenium, palladium, platinum, or a combination thereof contact the unsaturated polyethylene in the reactor.

13. The method of any one of the preceding claims, wherein the method comprises contacting the unsaturated polyethylene with three or more catalyst components, and wherein the three or more catalyst components comprise a metathesis catalyst component, an isomerization catalyst component, and a dehydrogenation catalyst component.

14. The process of claim 13, wherein the dehydrogenation catalyst component comprises an element selected from IUPAC Groups 5-10.

15. The process of claim 13 or claim 14, wherein the dehydrogenation catalyst component comprises platinum, iridium, ruthenium, rhenium, or a combination thereof.

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