Process for converting olefins in waste plastic pyrolysis oil into alkene products

Abstract

The present disclosure relates to a process for converting olefins from waste plastic pyrolysis oil into at least alkene products. The process includes contacting waste plastic pyrolysis oil 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 part of the olefins or products derived therefrom in the waste plastic pyrolysis oil 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 / 353,322, filed on June 17, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] The present disclosure relates to chemical processing. In particular, the present disclosure relates to a process for converting olefins in pyrolysis oils, such as waste plastic pyrolysis oil, into smaller desired hydrocarbon products.

Background Art

[0003] Hydrocarbons 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 (generally also called ethylene, propylene, and butylene, respectively). Various production processes for these lower hydrocarbons have been developed, including petroleum cracking and various synthetic processes. The pyrolysis of waste plastics can be used to recycle waste plastics. The pyrolysis of waste plastics can form pyrolysis oil. The pyrolysis oil can be used as a feedstock for producing more desirable hydrocarbons. However, first, additional treatment is required to remove olefin compounds in the pyrolysis oil. Conventional efforts to remove olefins from pyrolysis oil include hydrotreating. These processes are energy - inefficient and require high operating temperatures. There is a need for a new method for treating waste plastic pyrolysis oil.

Summary of the Invention

[0004] Embodiments of the present disclosure address these and other needs by providing a process for converting olefins in waste plastic pyrolysis oil into smaller alkene products. The processes described herein may enable two or more catalyst components within a reactor to perform multiple different chemical reactions, such as a combination of metathesis and isomerization to produce alkene products from, for example, waste plastic pyrolysis oil and alkene reactants.

[0005] According to one or more other aspects of the present disclosure, a process for converting olefins in waste plastic pyrolysis oil into alkene products of at least chemical formula C m H 2m The process includes contacting waste plastic pyrolysis oil with two or more catalyst components within a reactor, the reactor including an alkene reactant of 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 olefins in the waste plastic pyrolysis oil, or products derived therefrom, undergoes a metathesis reaction and an isomerization reaction to produce an effluent including alkene products of at least chemical formula C m H 2m

[0006] Additional features and advantages are described in the following "Detailed Description of the Invention," some of which 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 "Claims" included herein.

[0007] It should be understood that both the foregoing general description and the following detailed description are intended to explain various embodiments and provide an overview or framework for understanding the nature and characteristics of the claimed subject matter.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Figure 3

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Figure 5

DETAILED DESCRIPTION OF THE INVENTION

[0009] Some conventional processes for converting olefins in pyrolysis oil are energy-intensive and inefficient processes, for example, using hydrotreating to form aliphatics and then cracking this to form lighter products, which can increase the capital cost of operation and increase the CO2 footprint. In contrast, the processes disclosed herein enable the tandem catalysis of olefins in waste plastic pyrolysis oil to directly form alkene products by contacting the waste plastic pyrolysis oil with mutually compatible catalyst components. The catalytic cracking of heavier olefins under mild reaction conditions provides an advantageous and sustainable alternative for the production of hydrocarbon feedstocks, monomers, or other useful chemicals.

[0010] Here, detailed reference is made to embodiments of a process for converting olefins in waste plastic pyrolysis oil into alkene products within a reactor. As used herein, "waste plastic pyrolysis oil" refers to a mixture of products derived from the pyrolysis of waste plastics. The pyrolysis process of waste plastics can produce a mixture of liquid oil, gas, wax, and char. The liquid oil is called pyrolysis oil, but in the embodiments described herein, "pyrolysis oil" refers to a liquid oil that may include any of the products from the pyrolysis process such as wax. In an embodiment, the pyrolysis oil includes a mixture of at least paraffin, olefin, naphthene, and aromatic. In an embodiment, the waste plastic pyrolysis oil can be subjected to treatments such as, but not limited to, purification before use in the reactor. For example, in an embodiment, the waste plastic pyrolysis oil can be purified by various techniques including, but not limited to, filtration before the waste plastic pyrolysis oil contacts two or more catalyst compositions within the reactor. In an embodiment, the waste plastic pyrolysis oil can be purified by any method known in the art, such as passing it through a column containing silica, alumina, or a combination thereof. In an embodiment, one or more additives can optionally be included in the pyrolysis oil.

[0011] In an embodiment, the waste plastic pyrolysis oil can contain olefins in an amount of 20 weight percent (wt%) to 100 wt% based on the total weight of the waste plastic pyrolysis oil. For example, the waste plastic pyrolysis oil can contain olefins in an amount of 20 wt% to 90 wt%, 20 wt% to 80 wt%, 20 wt% to 70 wt%, 20 wt% to 60 wt%, 20 wt% to 50 wt%, 20 wt% to 40 wt%, 30 wt% to 100 wt%, 30 wt% to 90 wt%, 30 wt% to 80 wt%, 30 wt% to 70 wt%, 30 wt% to 60 wt%, 30 wt% to 50 wt%, 40 wt% to 100 wt%, 40 wt% to 90 wt%, 40 wt% to 80 wt%, 40 wt% to 70 wt%, 40 wt% to 60 wt%, 50 wt% to 80 wt%, 50 wt% to 70 wt%, 50 wt% to 60 wt%, 60 wt% to 80 wt%, or 60 wt% to 70 wt%.

[0012] In an embodiment, the waste plastic pyrolysis oil can contain monoolefins in an amount of 20 weight percent (wt%) to 100 wt% based on the total weight of the waste plastic pyrolysis oil. For example, the waste plastic pyrolysis oil can contain olefins in an amount of 20 wt% to 90 wt%, 20 wt% to 80 wt%, 20 wt% to 70 wt%, 20 wt% to 60 wt%, 20 wt% to 50 wt%, 20 wt% to 40 wt%, 30 wt% to 100 wt%, 30 wt% to 90 wt%, 30 wt% to 80 wt%, 30 wt% to 70 wt%, 30 wt% to 60 wt%, 30 wt% to 50 wt%, 40 wt% to 100 wt%, 40 wt% to 90 wt%, 40 wt% to 80 wt%, 40 wt% to 70 wt%, 40 wt% to 60 wt%, 50 wt% to 80 wt%, 50 wt% to 70 wt%, 50 wt% to 60 wt%, 60 wt% to 80 wt%, or 60 wt% to 70 wt%.

[0013] In an embodiment, the waste plastic pyrolysis oil can contain diolefins in an amount of 0 weight percent (wt%) to 10 wt% based on the total weight of the waste plastic pyrolysis oil. For example, the waste plastic pyrolysis oil can contain diolefins in an amount of 0 wt% to 10 wt%, 0 wt% to 5 wt%, 1 wt% to 10 wt%, 1 wt% to 5 wt%, or 5 wt% to 10 wt%.

[0014] In an embodiment, the waste plastic pyrolysis oil can contain paraffins in an amount of 20 weight percent (wt%) to 60 wt% based on the total weight of the waste plastic pyrolysis oil. For example, the waste plastic pyrolysis oil can contain paraffins in an amount of 20 wt% to 50 wt%, 20 wt% to 40 wt%, 30 wt% to 60 wt%, 30 wt% to 50 wt%, 40 wt% to 60 wt%, or 40 wt% to 50 wt%.

[0015] In an embodiment, the waste plastic pyrolysis oil can contain naphthene in an amount of 10 wt% to 30 wt% based on the total weight of the waste plastic pyrolysis oil. For example, the waste plastic pyrolysis oil can contain naphthene in an amount of 10 wt% to 25 wt%, 10 wt% to 20 wt%, 10 wt% to 15 wt%, 15 wt% to 30 wt%, 15 wt% to 25 wt%, 15 wt% to 20 wt%, or 20 wt% to 30 wt%.

[0016] In an embodiment, the waste plastic pyrolysis oil can contain aromatic compounds in an amount of 5 wt% to 15 wt% based on the total weight of the waste plastic pyrolysis oil. For example, the waste plastic pyrolysis oil can contain naphthene in an amount of 5 wt% to 12 wt%, 5 wt% to 10 wt%, 10 wt% to 15 wt%, or 10 wt% to 12 wt%.

[0017] In an embodiment, the waste plastic pyrolysis oil can contain Cl, Si, O, and N in an amount of less than 2 wt%, less than 1 wt%, less than 0.8 wt%, or less than 0.6 wt%.

[0018] In an embodiment, the waste plastic pyrolysis oil can have a density of 3 to 3 0.95 g / cm 3 For example, in an embodiment, the waste plastic pyrolysis oil can have a density of 3 0.64 g / cm 3 to 3 0.90 g / cm 3 to 3 0.85 g / cm 3 to 3 0.80 g / cm 3 to 3 0.75 g / cm 3 to 3 0.95 g / cm 3 to 3 0.90 g / cm 3 to 3 0.85 g / cm, 0.75 g / cm 3 ~0.80 g / cm 3 , 0.80 g / cm 3 ~0.90 g / cm 3 , or 0.80 g / cm 3 ~0.95 g / cm 3 and can have a density of. In an embodiment, the waste plastic pyrolysis oil can have a viscosity of 0.5 centipoise (cp) to 1000 cp.

[0019] In an embodiment, the reactor contains an alkene reactant. In an embodiment, the alkene reactant has the chemical formula C n H 2n , where n is an integer from 2 to 20. For example, the alkene reactant can have the chemical formula C n H 2n , where 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.

[0020] In an embodiment, the waste plastic pyrolysis oil can be brought into contact with two or more catalyst components in a reactor. In an embodiment, the waste plastic pyrolysis oil can be brought into contact 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 the present disclosure and the catalyst compositions prepared using the catalyst components can be utilized to promote various reactions such as dehydrogenation, metathesis, isomerization, or combinations thereof, but are not limited thereto. In an embodiment, 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.

[0021] In an embodiment, the catalyst component can include a metathesis catalyst component and an isomerization catalyst component. In an embodiment, the catalyst component can include a dehydrogenation catalyst component, a metathesis catalyst component, and an isomerization catalyst component. Without being bound by a particular theory, the metathesis catalyst can cleave the carbon chain of the olefin in the waste plastic pyrolysis oil in the presence of an alkene reactant to produce two products each having terminal unsaturation, and further metathesis of the terminal unsaturation intermediate product by the alkene reactant may be unproductive for further cleaving the carbon chain. The isomerization catalyst component can convert terminal unsaturation to internal unsaturation, and it is considered that the isomerization product can be further decomposed into two products in the presence of the metathesis catalyst component and the alkene reactant. The product derived from the olefin in the waste plastic pyrolysis oil that contacts both the metathesis catalyst component and the isomerization catalyst component in the presence of the alkene reactant continues to circulate between the metathesis reaction and the isomerization reaction, with the chemical formula C m H 2mSmaller alkene products such as compounds of can be produced, where m is an integer from 3 to 20 and is considered to be, for example, propylene. In an embodiment, increasing the reaction time enables additional metathesis and isomerization reaction cycles, so the reaction time can be increased to produce an effluent containing smaller alkene products. In an embodiment, when the alkene reactant contains ethylene, the metathesis catalyst component can cause ethenolysis of waste plastic pyrolysis oil or products derived therefrom.

[0022] In an embodiment, the metathesis catalyst component combined with an alkene reactant such as ethylene can function to cleave the olefin chain into two species. In an embodiment, the metathesis catalyst component can decompose alkene products derived from waste plastic pyrolysis oil. 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 combinations thereof. In an embodiment, the metathesis catalyst component can be selected from the group consisting of rhenium, ruthenium, tungsten, molybdenum, vanadium, or combinations thereof.

[0023] In an embodiment, the isomerization catalyst component may be operable to move the unsaturation on the olefin or on the product derived therefrom from one position on the skeleton to a different position. For example, in an embodiment, the isomerization catalyst component can move the unsaturation at the terminal position of the olefin 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.

[0024] In an embodiment, the dehydrogenation catalyst component may be operable to cause additional unsaturation in the olefin or the product derived therefrom. Without being bound by any particular theory, it is believed that the additional unsaturation caused by the dehydrogenation catalyst component can accelerate the occurrence of metathesis and / or isomerization reactions of the olefin or the product derived therefrom. In an embodiment, the dehydrogenation catalyst component can cause the olefin or the 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.

[0025] 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 may include a metathesis catalyst component and an isomerization catalyst component. In an embodiment, the catalyst composition may include a dehydrogenation catalyst component and an isomerization catalyst component. In an embodiment, the catalyst composition may include a metathesis catalyst component and an isomerization catalyst component. In an embodiment, the catalyst composition may include a dehydrogenation catalyst component and a metathesis catalyst component. In an embodiment, the catalyst composition may include a dehydrogenation catalyst component, a metathesis catalyst component, and an isomerization catalyst component. In an embodiment, the catalyst composition may include a dehydrogenation catalyst component, a metathesis catalyst component, or an isomerization catalyst component. In an embodiment, the reactor may include a first catalyst composition containing a metathesis catalyst component. In an embodiment, the reactor may include a second catalyst composition containing an isomerization catalyst component.

[0026] In an embodiment, the catalyst composition is represented by a 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 IUPAC Groups 5 to 10 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 IUPAC Groups 5 to 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 first catalyst composition. In an embodiment, the first catalyst composition can include any one of the elements selected from IUPAC Groups 5 to 10 in an amount 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% 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 IUPAC Groups 5 to 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.

[0027] 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 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% 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% 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.

[0028] It should be understood that according to an embodiment, the catalyst composition can be made by a method that results in the 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.

[0029] In an embodiment, the reactor can be any reactor useful for causing a catalytic reaction by contacting waste plastic pyrolysis oil with two or more catalyst components in the presence of an alkene reactant. Non-limiting examples of suitable reactors can include 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 contact 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 treatment of reactants, such as treatment of the alkene reactant, waste plastic pyrolysis oil, and / or catalyst components. In an embodiment, the 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.

[0030] In an embodiment, the pressure of the alkene reactant in the reactor, such as in the reaction zone during contact, 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 the alkene reactant used can be quantified by the pressure of the alkene reactant in the reactor. In other embodiments, the amount of the alkene reactant can be quantified by the space velocity of the alkene reactant.

[0031] In an embodiment, the temperature of the reactor, such as the reaction zone during contact, can be 500 °C or lower. For example, the temperature of the reactor during contact can be 450 °C or lower, 400 °C or lower, 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 500 °C, 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 low reactor temperature such as 500 °C or lower, 450 °C or lower, 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.

[0032] In an embodiment, the contact causes at least a portion of the olefins in the waste plastic pyrolysis oil to undergo a catalytic reaction to produce an effluent. In an embodiment, the effluent can contain at least an alkene product of the chemical formula C m H 2m The alkene product can be a compound of the chemical formula C m H 2m wherein m is an integer from 3 to 20. For example, the alkene product is of the chemical formula C m H 2mIt can be a compound of formula (I), wherein 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 embodiments, the alkene product can include propylene, butene, pentene, or combinations thereof. In embodiments, the alkene product can be selected from the group consisting of propylene, butene, pentene, and combinations thereof. In embodiments, the alkene product can consist essentially of or consist of propylene, butene, pentene, or combinations thereof. In embodiments, the alkene product can consist essentially of or consist of propylene. In embodiments, at least a portion of the alkene product can be separated from the effluent to produce a reformed effluent.

[0033] In embodiments, 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 the alkene product.

Examples

[0034] The various aspects of the present disclosure are further clarified by the following examples. These examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0035] Example 1. Purification of Waste Plastic Pyrolysis Oil

[0036] In Example 1, the waste plastic pyrolysis oil was purified using various filtration methods. The waste plastic pyrolysis oil was placed under a nitrogen atmosphere by bubbling nitrogen through the pyrolysis oil for 15 minutes. In addition, some samples were treated by passing 20 mL of the pyrolysis oil through a frit filter with a short plug of silica gel (about 40 g) and basic alumina (about 40 g), or by placing it on F-200 alumina beads (about 2 g). The purification methods for each example are shown in Table 1. The measured groups of paraffin, olefin, naphthene, and aromatic in the pyrolysis oil are shown in Table 2.

[0037]

Table 1

[0038]

Table 2

[0039] Example 2. Isomerization of Pyrolysis Oil by an Alkene Zipper

[0040] In Example 2, four oven-dried vials were each filled with acetonitrile(cyclopentadienyl)[2-(di-i-propylphosphino)-4-(t-butyl)-1-methyl-1H-imidazole]ruthenium(II) hexafluorophosphate (10 mg), C6D6 (0.5 mL), one of the pyrolysis oil samples of Examples 1A, 1B, 1C, and 1D (100 mg), and a stirring bar, corresponding to Examples 2A, 2B, 2C, and 2D, respectively, from Strem Chemicals, Inc. as an Alkene Zipper. The mixture was gently stirred and heated to 200 °C. Then, the first portion of the mixture was extracted with CDCl3 after 10 minutes, and the second portion was extracted after 24 hours. The resulting solution was 1 analyzed by 1H NMR spectroscopy (Figure 1). The conversion rate (%) to internal isomers as a function of the purification technique is shown in Table 3.

[0041]

Table 3

[0042] Example 3. Isomerization of Pyrolysis Oil by γ-Alumina

[0043] In Example 3, γ-alumina (20 g) was calcined in dry air at 500 °C for 5 hours at a heating rate of 10 °C / min, cooled to room temperature, and then transferred to a nitrogen-filled glove box. Four vials dried in an oven were each charged with γ-alumina (200 mg), one of the pyrolysis oil samples of Examples 1A, 1B, 1C, and 1D (400 mg) corresponding to Examples 3A, 3B, 3C, and 3D, respectively, and a stir bar. The mixture was gently stirred and heated at 200 °C for 16 hours. Then, the mixture was extracted with CDCl3, and the resulting solution was 1 analyzed by 1H NMR spectroscopy. Table 4 shows the conversion rate (%) to internal isomers as a function of the purification technique.

[0044] [Table 4]

[0045] Example 4. Tandem Isomerization and Ethanolysis of Waste Plastic Pyrolysis Oil

[0046] In Example 4, pyrolysis oil (84 g) was passed through a frit filter filled with silica gel (23 g). Nitrogen was bubbled through the resulting oil for 18 minutes to place the obtained oil under a nitrogen atmosphere. The oil was placed in a nitrogen-filled glove box and treated with activated 3A molecular sieve (6 g) overnight to obtain purified pyrolysis oil. In the nitrogen-filled glove box, purified pyrolysis oil (10 mL), triisopropylbenzene (TIPB, 0.5 mL), and toluene (100 mL) were charged into a 600 mL Parr reactor (Series 4560, mini bench top reactor). After mixing, an aliquot was taken and the initial pyrolysis oil / TIPB ratio was determined by gas chromatography (Agilent 7890A). The reactor was closed, removed from the glove box, and heated to 65 °C. When the temperature stabilized, Alkene Zipper (35 mg, in 5 mL toluene) was injected into the reactants and stirred under a nitrogen atmosphere for 0.5 hour.

[0047] Next, bis[1-[2,6-diethylphenyl]-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene][3-phenyl-1H-inden-1-ylidene]Ru[II]Cl2, (50 mg, in 5 mL toluene), commercially available as UltraCat from [Strem Chemicals, Inc.], was added. The reactor was pressurized with ethylene (500 psi), isolated from additional ethylene, and stirred for 17 hours. A gas sample was collected from the headspace at 65 °C using a cylinder and Tedlar bag. The sample was analyzed by gas chromatography using [Agilent 490 Micro GC] to confirm the formation of propylene (0.5 g). The reactor was cooled (<15 °C), and as shown in Figures 3 - 4 and Table 5, the reactor pressure was released to confirm the decrease in the total molecular weight of the pyrolysis oil, and a solution aliquot was analyzed using an Agilent 7890A GC.

[0048]

Table 5

[0049] Example 5. Tandem Isomerization and Metathesis of Waste Plastic Pyrolysis Oil and 1-Butene Using UltraNitroCat and Alkene Zipper Catalysts

[0050] In Example 5, a 600 mL Parr reactor (Series 4560, Mini Bench Top Reactor) was charged, inside a nitrogen-filled glove box, with purified pyrolysis oil (Example 5A, 4.0 mL), triisopropylbenzene (TIPB, 0.5 mL), and methylcyclohexane (20 mL). Acetonitrile(cyclopentadienyl)[2-(di-i-propylphosphino)-4-(t-butyl)-1-methyl-1H-imidazole]ruthenium(II) hexafluorophosphate (44 mg, in 5 mL of MCH), commercially available as Alkene Zipper Catalyst from [Strem Chemicals, Inc.], and (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II) (50 mg, in 5 mL of methylcyclohexane), commercially available as UltraNitroCat from [Strem Chemicals, Inc.] were added to the reactor. Cold (-35 °C) 1-butene (2.57 g, 0.046 mol) was added, the reactor was closed, removed from the glove box, heated to 65 °C, and stirred at 500 rpm for 16 h. The reactor was cooled (to about 10 °C), and a gas sample was taken from the headspace using a cylinder and Tedlar bag. The sample was analyzed by gas chromatography using [Agilent 490 Micro GC], and the formation of ethylene (50 mol %), propylene (31 mol %), and butenes (19 mol %) in the headspace was confirmed. A 0.5 mL aliquot (Example 5B) was removed from the Parr reactor and placed into a standard GC vial. Additional UltraNitroCat from [Strem Chemicals, Inc.] (50 mg in 5 mL of methylcyclohexane) was added to the reactor, the reactor was closed, heated to 65 °C, and stirred at 500 rpm for an additional 16 h. The reactor was cooled (to about 10 °C), and a gas sample was taken from the headspace using a cylinder and Tedlar bag. The sample was analyzed by gas chromatography using [Agilent 490 Micro GC], and the formation of ethylene (34 mol %), propylene (35 mol %), and butene (32 mol %) in the headspace was confirmed.A 0.5 mL aliquot (Example 5C) was removed from the Parr reactor and placed into a standard GC vial. The composition of the GC vial sample was analyzed as is on a GC-VUV instrument using automated PIONA class and multi-parameter analysis by the modified ASTM D8071A method and reported in Tables 6 - 8.

[0051]

Table 6

[0052]

Table 7

[0053]

Table 8

[0054]

Table 9

[0055] Example 6. Tandem Isomerization and Metathesis of Waste Plastic Pyrolysis Oil Using Grubbs Catalyst® M204 and Alkene Zipper Catalyst

[0056] In Example 6, a 600 mL Parr reactor (Series 4560, Mini Bench Top Reactor) was charged inside a nitrogen-filled glove box with purified pyrolysis oil (Example 5A, 4.0 mL), triisopropylbenzene (TIPB, 0.5 mL), and methylcyclohexane (20 mL). Acetonitrile(cyclopentadienyl)[2-(di-i-propylphosphino)-4-(t-butyl)-1-methyl-1H-imidazole]ruthenium(II) hexafluorophosphate (44 mg, in 5 mL of MCH), commercially available as an Alkene Zipper catalyst from [Strem Chemicals, Inc.], and benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlorotricyclohexylphosphine ruthenium (50 mg, in 5 mL of methylcyclohexane), commercially available as Grubbs Catalyst® M204 from [Sigma Aldrich, Inc.] were added to the reactor. Cold (-35 °C) 1-butene (2.57 g, 0.046 mol) was added, the reactor was closed, removed from the glove box, heated to 65 °C, and stirred at 500 rpm for 16 h. The reactor was cooled (to about 10 °C) and no headspace sample was taken due to insufficient pressure. A 0.5 mL aliquot (Example 6B) was removed from the Parr reactor and placed into a standard GC vial. The composition of the GC vial sample was analyzed as-is on a GC-VUV instrument using automated PIONA class and multi-parameter analysis by the modified ASTM D8071A method and reported in Tables 10 and 11.

[0057]

Table 10

[0058]

Table 11

[0059] Example 7. Reduction of Cobalt Oxide-Molybdenum Oxide on Alumina with Hydrogen at 500 °C

[0060] In Example 7, cobalt oxide - molybdenum oxide on alumina (CoO / MoO3 / Al2O3, 3.5% CoO, 14% MoO3) (20 g), commercially available from Strem Chemicals, Inc., was reduced in a quartz tube at 500 °C (heating rate of about 10 °C) for 5 hours using a 5% H2 / N2 gas mixture with a Carbolite VST12 / 400 Vertical Split Tube Furnace. The sample was cooled under nitrogen, sealed, and placed in a nitrogen - filled glove box.

[0061] Example 8. Tandem Isomerization and Metathesis of Waste Plastic Pyrolysis Oil with MoO3CoO - Al2O3

[0062] In Example 8, a 600 mL Parr reactor (Series 4560, mini - bench top reactor) was filled in a glove box filled with nitrogen gas with waste plastic pyrolysis oil (4.0 mL), triisopropylbenzene (TIPB, 0.5 mL), and methylcyclohexane (20 mL). Example 7 (4 g) commercially available from Strem Chemicals, Inc. was added to the reactor. Cold (-35 °C) 1 - butene (2.57 g, 0.046 mol) was added, the reactor was closed, removed from the glove box, heated to 65 °C, and stirred at 500 rpm for 16 hours. The reactor was cooled (to about 10 °C), and gas samples were collected from the headspace using a cylinder and Tedlar bag. The samples were analyzed by gas chromatography using [Agilent 490 Micro GC], and the formation of ethylene (52 mol%), propylene (32 mol%), and butene (15 mol%) in the headspace was confirmed. A 0.5 mL aliquot (Example 8A) was removed from the Parr reactor and placed in a standard GC vial. The composition of the GC vial sample was analyzed directly on a GC - VUV instrument using automated PIONA class and multi - parameter analysis by the modified ASTM D8071A method and reported in Tables 12 and 13.

[0063] [Table 12]

[0064]

Table 13

[0065] 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 listing of a series of features of a structure and should be interpreted 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" can 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 interpreted as a subset of non-limiting transitional phrases such as "comprising" and "including", and thus any use of a non-limiting phrase to introduce a listing of a series of elements, components, materials, or steps should be interpreted as also disclosing a listing 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 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 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".

[0066] 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 in a non-exclusive manner. The recited elements, components, or steps may be present, used, or combined with other elements, components, or steps that are not explicitly recited.

[0067] It should be understood that any two quantitative values assigned to a characteristic can form the range of that characteristic, and all combinations of ranges formed from all the recited quantitative values of a given characteristic 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 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

1. Olefins in waste plastic pyrolysis oil are at least chemical formula C ｍ H ２ｍ A process for converting to an alkene product, wherein the process includes contacting the waste plastic pyrolysis oil 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 the olefins in the waste plastic pyrolysis oil, or products derived therefrom, undergo 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.

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.

3. The process according to claim 1, wherein the temperature of the reactor during contact is 500°C or less.

4. The process according to claim 1, wherein the alkene reactant comprises ethylene, propylene, butene, pentene, or a combination thereof.

5. The process according to prior claim 1, wherein the alkene product comprises propylene, butene, pentene, or a combination thereof.

6. The aforementioned waste plastic pyrolysis oil is 0.64 g / cm³ ３ ~0.95 g / cm ３ The process according to claim 1, having a density of the following:

7. The process according to claim 1, wherein the waste plastic pyrolysis oil contains 20% by weight (wt%) to 100% by weight of olefins.

8. The process according to claim 1, wherein the waste plastic pyrolysis oil is purified before contact.

9. 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).

10. The process according to claim 1, wherein the metathesis catalyst component includes rhenium, ruthenium, tungsten, molybdenum, vanadium, or a combination thereof.

11. The process according to claim 1, wherein the isomerization catalyst component comprises an element selected from Groups 5 to 10 of the International Union of Pure and Applied Chemistry (IUPAC).

12. The process according to claim 1, wherein the isomerization catalyst component includes alumina, silica, iridium, palladium, ruthenium, or a combination thereof.

13. The process according to claim 1, wherein the process comprises contacting the waste plastic pyrolysis oil 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.

14. The process according to claim 13, wherein the dehydrogenation catalyst component comprises an element selected from Groups 5 to 10 of the International Union of Pure and Applied Chemistry (IUPAC).

15. The process according to any one of claims 1 to 14, further comprising separating at least a portion of the alkene product from the effluent.

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