Plastic waste pyrolysis for production of light gaseous hydrocarbons and integration with ethylene cracker

Abstract

Processes for the manufacture of various chemicals, e.g., recycled ethylene, recycled ethylene polymers and copolymers, and other recycled products, using pyrolysis gas as a feedstock or co-feedstock. In these processes, pyrolysis reactor conditions can be selected to increase or optimize production of pyrolysis gas over pyrolysis oil, and pyrolysis gas that would normally be used as fuel or combustion material can be fed downstream of the steam cracker furnace for the purpose of economic use to form recycled chemicals. Operating parameters of the pyrolysis unit can be adjusted to increase or decrease the proportion of pyrolysis gas relative to pyrolysis liquids depending on the relative economic value of pyrolysis gas and pyrolysis liquids.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 175,978, filed April 16, 2021, which is incorporated herein by reference in its entirety.

[0003] The technical field of this disclosure

[0004] This disclosure relates to the production of chemicals and plastics using pyrolysis products from the pyrolysis of plastic waste as feedstock or as co-feedstock with petroleum-based fuel feedstock or fossil fuel feedstock.

[0005] Background Art of This Disclosure

[0006] The global environmental impact associated with waste plastic products is enormous, and the incentives for recycling plastic waste are ubiquitous. Recycling raw materials through pyrolysis of plastic waste is a potentially attractive alternative to traditional melt-and-recycle methods. Pyrolysis breaks down the polymer components into hydrocarbon components, which can then be recycled as feedstock or co-feedstock in refineries or chemical plants and converted into fuels or chemicals.

[0007] One beneficial use of pyrolysis products is in the production of ethylene, known as "recycled" ethylene, which can then be used to produce other recycled products, such as polyethylene. Typically, the desired pyrolysis products are liquid mixtures, but a preferred feedstock for ethylene and polyethylene production is a mixture of light hydrocarbon gases. However, it can be advantageous if the pyrolysis system can produce a high proportion of pyrolysis gaseous hydrocarbons relative to the pyrolysis oil or liquid hydrocarbons, thereby facilitating integration of the pyrolysis process with ethylene or polyethylene plants or with natural gas or ethylene pipelines. Therefore, improved processes and systems for producing pyrolysis gases and pyrolysis oils, and for using pyrolysis gases and pyrolysis oils as feedstocks or co-feedstocks, would be useful.

[0008] Summary of the Invention disclosed herein

[0009] This disclosure provides novel processes and methods for producing, for example, recycled ethylene, polyethylene, and other recycled products using pyrolysis gas and / or pyrolysis oil as feedstocks or co-feedstocks. Traditionally, pyrolysis reactors are typically optimized for pyrolysis oil production rather than pyrolysis gas, and the resulting pyrolysis gas can be used as fuel for a heating furnace. However, pyrolysis gas is underutilized in this role, and various economic advantages can be achieved by operating the pyrolysis unit under conditions that increase the proportion of pyrolysis gas relative to pyrolysis liquid in the pyrolysis unit effluent. Furthermore, the ability to adjust the operating conditions of the pyrolysis unit based on the relative economic value of the pyrolysis gas as feedstock relative to the pyrolysis oil provides additional economic advantages as described herein.

[0010] Generally, plastic waste pyrolysis focuses on producing pyrolysis oil, which can be fed into a steam cracker, where it is converted into ethylene, and subsequently fed into a polyethylene reactor to produce recycled polymer. These processes typically use pyrolysis conditions designed to maximize the production of liquid pyrolysis oil rather than gaseous pyrolysis products. However, most ethylene-producing steam crackers are designed to operate with light, gaseous feedstocks, and their capacity to feed liquid pyrolysis oil into the steam cracker without interrupting the process is limited.

[0011] Therefore, in one aspect, this disclosure provides for the pyrolysis of waste plastics under conditions that allow for a higher production of C5 and lighter gaseous hydrocarbon products relative to the proportion of lighter gases produced in conventional pyrolysis operations. These gaseous products can then be fed, for example, into a steam cracker furnace or mixed with steam cracker effluent, which is subsequently purified and fed into a polymerization reactor.

[0012] In one aspect, a pyrolysis process is also provided that can convert plastic waste into C5 and lighter hydrocarbon pyrolysis gases, which can be mixed with effluent from a steam cracker, purified or separated, and subsequently fed to a downstream reactor, such as a polymerization reactor. In another aspect, any light saturated fractions (such as ethane or propane) generated during purification / separation can be recycled back to the steam cracker.

[0013] On the other hand, a pyrolysis process is provided that converts plastic waste into C5 and lighter hydrocarbon pyrolysis gases, which undergo a condensation step to separate the heavier (C4-C5) products from the lighter (C2-C3) products in the pyrolysis gas stream. The lighter (C2-C3) gases can then be combined with effluent from a steam cracker and undergo a separation process downstream of the steam cracker furnace, subsequently feeding ethylene and / or propylene to a downstream reactor or a type of process, such as a polymerization reactor. If desired, the light saturated hydrocarbons can be recycled back to the steam cracker. In this case, the heavier (C4-C5) products to be condensed from the pyrolysis gas stream can be fed as feed or co-feed to the steam cracker.

[0014] According to another aspect, a process is provided that can convert plastic waste into C5 and lighter hydrocarbon pyrolysis gases and pyrolysis oils, wherein the C5 and lighter hydrocarbon gas streams, with or without condensable components, can be fed downstream of a fluidized catalytic cracker (FCC) to an FCC reactor effluent purification or separation unit.

[0015] On the other hand, this disclosure provides a process for producing pyrolysis gas hydrocarbons to pyrolysis oil hydrocarbons with a higher ratio than conventional processes. Depending on various aspects, the relative ratio of pyrolysis gas to pyrolysis oil can be adjusted according to their respective market prices, which can improve the economic feasibility of using the pyrolysis products for the production of chemicals and fuels.

[0016] In a further aspect, the polymers and chemicals disclosed herein can be certified as circular polymers and chemicals in accordance with the International Sustainability and Carbon Certification (ISCC) regulations. Furthermore, methods are provided for certifying polymers and chemicals as circular polymers and chemicals at any point along a complex chemical reaction pathway (even when far from the point of introduction of pyrolysis oil). The ability to trace the polymer or chemical content of the original pyrolysis gas co-feedstock allows for ISCC certification.

[0017] Therefore, among other things, this disclosure describes the following aspects I-VI.

[0018] I. In one aspect, this disclosure provides a process for recycling plastic waste, the process comprising:

[0019] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0020] (b) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0021] (c) Providing a separation unit feed to the separation unit, the separation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the steam cracker furnace effluent; and

[0022] (d) Separate the feed to the separation unit to provide a recycled product comprising ethylene effluent, propylene effluent and light (C2-C3) saturated hydrocarbon effluent.

[0023] II. In another aspect, a process for recycling plastic waste is provided, the process comprising:

[0024] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0025] (b) The pyrolysis gas is supplied to the condensation unit to form a first condenser effluent having a higher proportion of C4-C5 hydrocarbons than the pyrolysis gas and a second condenser effluent having a higher proportion of C2-C3 hydrocarbons than the pyrolysis gas;

[0026] (c) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent, the steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0027] (d) Providing a separation unit feed to the separation unit, the separation unit feed comprising at least a portion of the effluent from the second condenser and at least a portion of the effluent from the steam cracker furnace; and

[0028] (e) Separate the feed to the separation unit to provide a recycled product comprising ethylene effluent, propylene effluent and light (C2-C3) saturated hydrocarbon effluent.

[0029] III. A process for recycling plastic waste according to any one of aspects I and II set forth above is also provided, wherein the process may further include the following steps:

[0030] (a') is the market price of the pyrolysis oil formed under the first set of pyrolysis conditions, which is equivalent to the market price of the reference liquid product.

[0031] (b') Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gases formed under the first set of pyrolysis conditions; and

[0032] (c')(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0033] IV. In a further aspect, a process for recycling plastic waste is provided, the process comprising:

[0034] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0035] (b) Assign a market price equivalent to the market price of the reference liquid product to the pyrolysis oil formed under the first set of pyrolysis conditions;

[0036] (c) Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gases formed under the first set of pyrolysis conditions; and

[0037] (d)(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0038] V. In a further aspect, this disclosure describes a process for recycling plastic waste, the process comprising:

[0039] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0040] (b) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0041] (c) Feeding the separation unit to the separation unit, the separation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the steam cracker furnace effluent;

[0042] (d) is the market price of the pyrolysis oil formed under the first set of pyrolysis conditions, which is equivalent to the market price of the reference liquid product.

[0043] (e) Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gas formed under the first set of pyrolysis conditions; and

[0044] (f)(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0045] VI. According to another aspect, a process for recycling plastic waste is provided, the process comprising:

[0046] (a) Pyrolyzing plastic waste in a pyrolysis unit to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil, and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 fractions having C2-C3 fractions and C4-C5 fractions, and lighter (C5 and C4-C5 fractions). C≤5 )hydrocarbon;

[0047] (b) A heavy hydrocarbon feed stream is fed into a fluidized catalytic cracking (FCC) reactor to produce an FCC effluent containing naphtha (C6-C4). 10 Hydrocarbons) and C5 and lighter (C ≤5 )hydrocarbon;

[0048] (c) Providing a fractionation unit feed to the fractionation unit, the fractionation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the FCC effluent; and

[0049] (d) Separating the feed from the fractionation unit to provide a recycled product, the recycled product comprising: C5 and lighter (C5) compounds. ≤5 The first fraction of hydrocarbons and the effluent containing heavy hydrocarbons (C 6+ The second fraction of hydrocarbon effluent.

[0050] Although pyrolysis reactors are traditionally optimized for pyrolysis oil production rather than pyrolysis gas, by operating the pyrolysis unit under conditions chosen to increase, optimize, or maximize the ratio of pyrolysis gas to pyrolysis liquid in the pyrolysis unit effluent, one or more of the following advantages of utilizing pyrolysis gas more advantageously than existing methods can be achieved. On the one hand, for example, when ethylene effluent produced according to aspect I or II above is fed to a polymerization reactor to form recycled polyethylene, the amount of recycled polyethylene produced can be, for example, about 10% to about 25% higher than that produced in a corresponding process using only liquid pyrolysis effluent feedstock, as quantified by the percentage (%) of gas production from the pyrolysis unit per unit weight of plastic feed. In a further aspect, the carbon footprint of any independently selected recycled product can be reduced by about 15% to about 40% compared to the carbon footprint of the corresponding non-recycled product produced in the absence of pyrolysis gas and pyrolysis oil. According to another aspect, plastic waste can be pyrolyzed in an amount of up to about 10% by weight, sufficient to replace the raw material required from the separation unit located downstream of the steam cracker furnace to produce the same amounts of ethylene effluent, propylene effluent, and light (C2-C3) saturated hydrocarbon effluent. A further aspect proposes that plastic waste can be pyrolyzed in an amount sufficient to provide feed to the separation unit.

[0051] These and other embodiments and aspects of the processes, methods, systems and compositions are described more fully in the detailed description, the listed aspects and claims, and in additional disclosures such as the embodiments provided herein. Brief description of the attached diagram

[0053] Figure 1 The diagram illustrates a process for recycling plastic waste according to aspect I, showing an exemplary process flow diagram of the feed and product. Figure 1 In this process, the pyrolysis gas is routed from the downstream pyrolysis unit of the steam cracker, so that the separation unit feed receives both the steam cracker furnace effluent and the pyrolysis gas as feed.

[0054] Figure 2 The illustration depicts another process for recycling plastic waste according to aspect II, showing an exemplary process flow diagram of feed and product. Figure 2 In the process, the pyrolysis gas is separated, and the light fraction (C2-C3 hydrocarbons) is transported downstream of the steam cracker furnace along a route, so that the separation unit feed receives both the steam cracker furnace effluent and the light fraction of the pyrolysis gas as feed. Detailed Implementation

[0055] General description

[0056] This disclosure provides processes and methods for producing a variety of chemicals (e.g., recycled ethylene, polyethylene, and other recycled products) using pyrolysis gases as feedstocks or co-feedstocks. In these processes, pyrolysis reactor conditions can be adjusted to increase or optimize the production rate of pyrolysis gas relative to pyrolysis oil. Furthermore, operating parameters of the pyrolysis unit can be selected or adjusted to increase or decrease the proportion of pyrolysis gas to pyrolysis liquid in the pyrolysis unit effluent based on the relative economic value of the pyrolysis gas compared to the pyrolysis oil, which can improve the economic feasibility of using the pyrolysis products to produce chemicals and fuels.

[0057] definition

[0058] To more clearly define the terms used herein, the following definitions are provided, and unless otherwise specified or required by context, these definitions apply throughout this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may apply, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition is applied ambiguous or invalid. If any definition or usage provided in any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0059] Transitional terms or phrases relating to claims, the transitional term "comprising / including," synonymous with "comprising," "containing," or "characterized in," is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consisting substantially of" limits the scope of the claim to the specified materials or steps, and those that do not materially affect the essential and novel characteristics(s) of the claimed invention. Claims "consisting substantially of" fall between closed claims drafted in "consisting of" format and fully open claims drafted in "comprising." Unless stated to the contrary, the description of a compound or composition as "consisting substantially of" should not be construed as "comprising," but rather is intended to describe the listed components, including materials that do not materially alter the composition or method to which the term is applied. For example, a raw material consisting substantially of material A may include impurities typically present in commercially produced or commercially available samples of the listed compounds or compositions. When a claim includes different features and / or feature categories (e.g., method steps, raw material features, and / or product features, and other possibilities), transitional terms such as include, substantially consist of, and consist of apply only to the feature category used, and it is possible to have different transitional terms or phrases used in the claim with different features. For example, a method may include several listed steps (and other unlisted steps), but is prepared using a catalyst composition consisting of specific steps, but utilizes a catalyst composition containing listed components and other unlisted components. While compositions and methods are described with regard to "comprising" various components or steps, the compositions and methods may also be "substantially consist of" various components and steps or "consist of" various components and steps.

[0060] Unless otherwise expressly indicated, the terms “a”, “an”, and “the” are intended to include multiple alternatives, such as at least one alternative. For example, unless otherwise specified, the disclosure of “organoaluminum compound” means to cover one organoaluminum compound, or a mixture or combination of more than one organoaluminum compound.

[0061] This document uses the terms “configured for” or “adapted to” and similar language to reflect the specific enumerated structures or procedures used in olefin polymerization systems or processes. For example, unless otherwise specified, a particular structure “configured for” means “configured for use in an olefin polymerization reactor system” and is therefore designed, shaped, arranged, constructed and / or tailored to achieve olefin polymerization, as will be understood by those skilled in the art.

[0062] For any particular compound disclosed herein, unless otherwise indicated, the general structure or name presented is also intended to cover all structural isomers, conformational isomers, and stereoisomers that can be produced by a particular set of substituents. Therefore, unless explicitly indicated otherwise, general references to a compound include all structural isomers; for example, general references to pentane include n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while general references to butyl include n-butyl, sec-butyl, isobutyl, and tert-butyl. Additionally, when the context permits or requires, references to the general structure or name cover all enantiomers, diastereomers, and other optical isomers (whether enantiomers or racemic forms), as well as mixtures of stereoisomers. For any particular formula or name provided, any general formula or name provided also covers all conformational isomers, regio isomers, and stereoisomers that can be produced by a particular set of substituents.

[0063] Unless otherwise specified, in accordance with appropriate chemical practice, any carbon-containing group without a specified number of carbon atoms may have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms, or any range or combination of these values. For example, unless otherwise specified or unless the context requires otherwise, any carbon-containing group may have 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms, etc. On the one hand, the context may require additional scope or limitations; for example, when the carbon-containing group of the subject is aryl or alkenyl, the lower limit for carbon in these subject groups is six carbon atoms and two carbon atoms, respectively. Furthermore, other identifiers or qualifying terms may be used to indicate the presence or absence of specific substituents, specific regional chemistry and / or stereochemistry, or the presence or absence of branched basic structures or the main chain, etc.

[0064] This document discloses various numerical ranges. When an applicant discloses or claims protection for any type of range, unless otherwise specified, the applicant intends to individually disclose or claim protection for every possible number that such range can reasonably cover, including the endpoints of the range and any subranges and combinations thereof covered therein. For example, by disclosing temperatures from 70°C to 80°C, the applicant intends to individually list 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, and 80°C, including any subranges and combinations thereof covered therein, and these methods of describing such ranges are interchangeable. Furthermore, all numerical endpoints of the ranges disclosed herein are approximate unless excluded by attached conditions. As a representative example, if the applicant states that one or more steps in the process disclosed herein can be performed at temperatures ranging from 10°C to 75°C, then this range should be interpreted as covering temperatures ranging from “about” 10°C to “about” 75°C.

[0065] Values ​​or ranges herein may be expressed as “about,” “about” a specific value, and / or “about” another specific value. When such values ​​or ranges are expressed, other disclosed embodiments include the specific values ​​listed from one specific value and / or to another specific value. Similarly, when a value is expressed as an approximation using the antecedent “about,” it should be understood that the specific value forms another embodiment. It will be further understood that numerous values ​​are disclosed herein, and each value is also disclosed herein as “about” the specific value, in addition to the value itself. On the other hand, the use of the term “about” implies ±15% of the stated value, ±10% of the stated value, ±5% of the stated value, or ±3% of the stated value.

[0066] Therefore, if the applicant chooses to claim protection for less than the full extent of the disclosure for any reason, such as considering references that the applicant might not have been aware of at the time of filing, the applicant reserves the right to specify or exclude any individual member of any such group of values ​​or ranges (including any subranges or combinations of subranges within the group) that can be claimed based on the scope or in any similar manner. Furthermore, if the applicant chooses to claim protection for less than the full extent of the disclosure for any reason, such as considering references or prior disclosures that the applicant might not have been aware of at the time of filing, the applicant reserves the right to specify or exclude any individual substituent, analogue, compound, ligand, structure, or group thereof, or any member of the claimed group.

[0067] The term “substituted” is intended, when used to describe a group (e.g., when referring to a substituted analogue of a particular group), to describe any non-hydrogen portion that formally replaces hydrogen in the group, and is intended to be non-limiting. A group or groups may also be referred to herein as “unsubstituted”, or by equivalent terms such as “non-substituted,” which refers to the original group in which the non-hydrogen portion does not replace hydrogen in the group. Unless otherwise specified, as will be understood by those skilled in the art, “substituted” is intended to be non-limiting and includes both inorganic and organic substituents.

[0068] "Aliphatic" compounds are a class of acyclic or cyclic saturated or unsaturated carbon compounds (excluding aromatic compounds), such as non-aromatic organic compounds. An "aliphatic group" is a generalized group formed by removing one or more hydrogen atoms (as required by the specific group) from the carbon atoms of an aliphatic compound. Aliphatic compounds, and therefore aliphatic groups, can contain organic functional groups and / or atoms other than carbon and hydrogen.

[0069] Whenever used in this specification and claims, the term "ene" refers to an alkene having at least one carbon-carbon double bond. Unless otherwise expressly indicated, the term "ene" includes aliphatic or aromatic, cyclic or acyclic, and / or straight-chain and branched alkenes. Unless expressly indicated, the term "ene" itself does not indicate the presence or absence of heteroatoms and / or other carbon-carbon double bonds. Other identifiers may be used to indicate the presence or absence of specific groups within the alkene. Alkenes can also be further identified by the position of the carbon-carbon double bond. Alkenes having more than one such multiple bond are dienes, trienes, etc., and can be further identified by the position of the carbon-carbon double bond.

[0070] The term "olefin" is used herein according to the definition specified by IUPAC: an acyclic and cyclic hydrocarbon having one or more carbon-carbon double bonds in addition to a formal carbon-carbon double bond in an aromatic compound. The class "olefin" includes alkenes and cycloalkenes, as well as corresponding polyenes. Ethylene, propylene, 1-butene, 2-butene, 1-hexene, etc., are non-limiting examples of olefins. As used in this specification and claims, the term "α-olefin" refers to an olefin having a double bond between the first and second carbon atoms of the longest continuous chain of carbon atoms. Unless otherwise expressly stated, the term "α-olefin" includes both straight-chain and branched α-olefins.

[0071] "Aromatic group" refers to a generalized group formed by removing one or more hydrogen atoms (as required by the specific group and at least one of which is an aromatic ring carbon atom) from an aromatic compound. Therefore, as used herein, "aromatic group" refers to a group derived by removing one or more hydrogen atoms from an aromatic compound, i.e., a compound containing a cyclic conjugated hydrocarbon following Hückel's (4n+2) rule and containing (4n+2) π electrons, where n is an integer from 1 to about 5. Unless otherwise specified, aromatic compounds and therefore "aromatic groups" can be monocyclic or polycyclic. Aromatic compounds include "aromatic hydrocarbons" (hydrocarbon aromatic compounds) and "heteroarenes," also known as "hetarenes" (heteroarenes formally derived from aromatic hydrocarbons by replacing one or more methine (–C=) carbon atoms with trivalent or divalent heteroatoms in a manner that preserves the continuous π electron system characteristic of the aromatic system and the number of out-of-plane π electrons corresponding to Hückel's (4n+2) rule). Although aromatic compounds and heteroaromatic compounds are mutually exclusive members of the group of aromatic compounds, compounds having both an aromatic group and a heteroaromatic group are generally considered heteroaromatic compounds. Unless otherwise specified, aromatic compounds, aromatics, and heteroaromatics can be monocyclic or polycyclic. Examples of aromatics include, but are not limited to, benzene, naphthalene, and toluene. Examples of heteroaromatics include, but are not limited to, furan, pyridine, and methylpyridine. As disclosed herein, the term "substituted" may be used to describe an aromatic group in which any non-hydrogen moiety formally substitutes for a hydrogen in the group, and is intended to be non-limiting.

[0072] As used herein, the term "polymer" generally includes olefin homopolymers, copolymers, terpolymers, etc. Copolymers are derived from an olefin monomer and one olefin comonomer, while terpolymers are derived from an olefin monomer and two olefin comonomers. Therefore, "polymer" encompasses copolymers, terpolymers, etc., derived from any olefin monomer and comonomer disclosed herein. Similarly, ethylene polymers will include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, etc. As an example, an olefin copolymer of an ethylene copolymer may be derived from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, then the resulting polymer can be classified as an ethylene / 1-hexene copolymer.

[0073] In a similar manner, the term "polymerization" encompasses homopolymerization, copolymerization, ternary polymerization, and so on. Thus, a copolymerization process may involve contacting an olefin monomer (e.g., ethylene) and an olefin comonomer (e.g., 1-hexene) to produce a copolymer.

[0074] The term "cracker" is used herein to refer to either a steam cracking unit or a fluidized catalytic cracking (FCC) unit. Therefore, unless otherwise specified, a steam cracking unit includes a steam cracker to which pyrolysis products can be fed, an upstream pretreatment unit, and a downstream separation unit. An FCC includes a fluidized catalytic cracking reactor, an upstream pretreatment unit, and a downstream separation unit. Pyrolysis oil is typically fed to the FCC pretreatment unit, although it can also be fed directly to the FCC reactor.

[0075] This article uses the terms “reforming,” “reforming unit,” or “reforming cell,” and also the terms “Aromax” or “…”. Units. Although both reforming and Aromax units produce aromatic compounds, the catalysts used in these units differ. However, the methods and processes disclosed herein can be used with either reforming or Aromax units, and for the purposes of this disclosure, it should be considered that when one type of unit is specified, the other type of unit may also be used and considered disclosed. Reforming catalysts are alumina-based and contain metals such as platinum. Aromax catalysts are zeolite-based catalysts and also contain platinum or other Group VIII or 1B metals (Groups 8-11 metals) and halides such as chlorides, fluorides, etc. Both processes feed naphtha from a fluidized catalytic cracking (FCC) unit. However, since the sulfur hydrotreating unit is located directly upstream of the Aromax unit, it is also possible to bypass the FCC unit and feed pyrolysis oil directly to the sulfur hydrotreating unit.

[0076] When “natural gas” feed is mentioned in this disclosure, it is intended to refer to natural gas liquids (NGL) feed. Therefore, the petroleum / fossil fuel feed to the steam cracker / steam blast furnace can be light hydrocarbons, primarily a saturated feed in the C2-C5 range (after methane removal), and the steam cracker primarily feeds a mixture of C2-C3. The natural gas liquids (NGL) facility separates methane, and in some cases, separates purified C2-C3 feed. Alternatively, the steam cracker may also feed naphtha (C6-C5). 10 Furthermore, the steam cracker that feeds naphtha can also be mixed with the naphtha feed in the pyrolysis oil.

[0077] Although any methods, apparatus, and materials similar to or equivalent to those described herein may be used in the practice or testing of this invention, typical methods, apparatus, and materials are described herein.

[0078] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, constructs and methods described in the publications that can be used in conjunction with the inventions described herein. The publications discussed throughout are provided solely for their disclosure prior to the filing date of this application. Nothing herein should be construed as an admission that the inventor has no right to any prior disclosure by virtue of a prior invention.

[0079] Plastic waste pyrolysis for the production of light gaseous hydrocarbons and the integration of the pyrolysis unit with an ethylene cracker. Regarding aspect I of this disclosure, a process for recycling plastic waste (including the production of chemicals or polymers from plastic waste) is provided, the process comprising:

[0080] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent containing pyrolysis gas and pyrolysis oil in known ratios, wherein the pyrolysis gas contains C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0081] (b) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0082] (c) Providing a separation unit feed to the separation unit, the separation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the steam cracker furnace effluent; and

[0083] (d) Separate the feed to the separation unit to provide a recycled product comprising ethylene effluent, propylene effluent and light (C2-C3) saturated hydrocarbon effluent.

[0084] In this respect, the pyrolysis gas is routed downstream of the steam cracker to the separation unit, and ethylene, propylene, light (C2-C3) saturated hydrocarbons, and other effluents can subsequently be routed from the separation unit. The pyrolysis gas and steam cracker effluent can be combined to form the desired separation unit feed, or the pyrolysis gas and steam cracker effluent can be supplied to the separation unit separately. In either case, the separation unit feed may include at least a portion of the pyrolysis gas and at least a portion of the steam cracker effluent. If desired, the pyrolysis gas can be compressed before being supplied to the separation unit as separation unit feed.

[0085] According to aspect II of this disclosure, a process is provided for recycling plastic waste (including producing chemicals or polymers from plastic waste), the process comprising:

[0086] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent containing pyrolysis gases and pyrolysis oil, wherein the pyrolysis gases contain C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0087] (b) The pyrolysis gas is supplied to the condensation unit to form a first condenser effluent having a higher proportion of C4-C5 hydrocarbons than the pyrolysis gas and a second condenser effluent having a higher proportion of C2-C3 hydrocarbons than the pyrolysis gas;

[0088] (c) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent, the steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0089] (d) Providing a separation unit feed to the separation unit, the separation unit feed comprising at least a portion of the effluent from the second condenser and at least a portion of the effluent from the steam cracker furnace; and

[0090] (e) Separate the feed to the separation unit to provide a recycled product comprising ethylene effluent, propylene effluent and light (C2-C3) saturated hydrocarbon effluent.

[0091] In this respect, the second condenser effluent and the steam cracker furnace effluent can be combined to form a separate unit feed prior to step (d). This respect may further include the step of feeding at least a portion of the first condenser effluent to the steam cracker furnace. If desired, the first condenser effluent and the first feed stream can be combined before being fed to the steam cracker furnace, or they can be provided to the steam cracker furnace separately.

[0092] Once the feed to the separation unit is separated to provide a recycled product comprising ethylene effluent, propylene effluent, and light (C2-C3) saturated hydrocarbon effluent according to aspect I or aspect II, the light saturated hydrocarbon effluent, or a portion thereof, can be recycled to the steam cracker for further ethylene production. The light saturated hydrocarbon effluent, or a portion thereof, can be treated to remove contaminants before being recycled to the steam cracker.

[0093] The feed stream leading to the steam cracker furnace that produces the steam cracker furnace effluent is described herein as a first feed stream, which may contain liquefied petroleum gas (LPG), natural gas liquefaction (NGL), light (C2-C5) hydrocarbons, or naphtha (C6-C5) oil. 10Additionally, the feed stream to the steam cracker furnace may also include pyrolysis oil or a portion thereof that can be fed from the pyrolysis unit to the steam cracker furnace. For example, in one aspect, the steam cracker feed (first feed stream) may include naphtha (C6-C...). 10 (or any other first feed stream component or combination thereof, together with the pyrolysis oil or a portion thereof produced in the pyrolysis unit.)

[0094] In one aspect of the disclosed process for recycling plastic waste, the first feed stream leading to the steam cracker may contain alkanes or alkanes together with olefins. In this aspect, at least a portion of the olefins may be removed from the first feed stream before it is fed into the steam cracker furnace. For example, the olefins may be removed from the first feed stream by contacting it with sulfolane or by other methods as understood by those skilled in the art.

[0095] On the other hand, pyrolysis oil from the pyrolysis unit can be recycled back to the refining unit as feedstock or co-feedstock. For example, pyrolysis oil can be recycled back to the crude oil refining unit to produce recycled naphtha or recycled natural gas liquids (NGL).

[0096] To utilize the pyrolysis gas from the pyrolysis unit as disclosed herein, it is advantageous to co-locate the pyrolysis unit with the steam cracker furnace. Alternatively, it is advantageous to co-locate the pyrolysis unit with the aforementioned separation unit, or alternatively, co-locate the pyrolysis unit with both the steam cracker furnace and the separation unit as described above. Describing these units as co-located indicates that the pyrolysis unit is positioned sufficiently close to the steam cracker furnace or the separation unit, such that the pyrolysis unit, the steam cracker furnace, and / or the separation unit are co-located within the same plot space of the same operating crew. For example, the pyrolysis unit may be positioned sufficiently close to the steam cracker furnace or the separation unit, or both, such that the C2-C3 fraction of the pyrolysis gas or the second condenser effluent can be supplied to the steam cracker furnace without additional compression or piping. In one aspect, the C2-C3 fraction of the pyrolysis gas or the second condenser effluent can be transported to the steam cracker furnace via piping without compression. On the other hand, regardless of whether the pyrolysis unit, the steam cracker furnace, and / or the separation unit are located together, the C2-C3 fraction of the pyrolysis gas or the effluent from the second condenser can be compressed and transported to the steam cracker furnace via pipeline.

[0097] Figure 1 The diagram illustrates an exemplary process flow route for recycling plastic waste, such as the process according to aspect I. Figure 1The diagram illustrates a pyrolysis unit 10, which may include a pyrolysis furnace or reactor and may accept various types of plastic waste as pyrolysis unit feed 15. The pyrolysis unit feed 15 is pyrolyzed in the pyrolysis unit 10 to form a pyrolysis unit effluent 20, which is subsequently separated at 25, thus providing pyrolysis gas 30 and pyrolysis oil 35. The pyrolysis gas may, for example, contain C1 to C5 hydrocarbons, including ethylene, propylene, and butene (EPB).

[0098] Figure 1 The process also illustrates a first feed stream 40, which is fed into a steam cracker furnace 45 to produce a steam cracker effluent 50, which may contain, for example, olefins (such as ethylene and propylene) and light (C2-C3) saturated hydrocarbons. The steam cracker effluent 50 is fed into a separation unit 55 located downstream of the steam cracker furnace 45, and pyrolysis gas 30 is routed downstream of the steam cracker furnace 45. Therefore, the separation unit 55 receives both the steam cracker effluent 50 and the pyrolysis gas 30 as feed. The pyrolysis gas 30 may be fed directly into the separation unit 55 or combined with the steam cracker effluent 50 before being fed into the separation unit 55, as shown in the figure.

[0099] The feed to the separation unit 55 can then be separated to form various effluents from the separation unit 55, such as olefin effluent 60. For example, olefin effluent 60 can be ethylene effluent, which can then be fed to the polymerization reactor 65 to form polyethylene 70. The separation unit 55, located downstream of the steam cracker furnace 45, can also provide light (C2-C3) saturated hydrocarbon effluent 75, which can be recycled back to the steam cracker furnace 45 if desired.

[0100] according to Figure 1 The produced pyrolysis oil 35 can be transported along a route to other uses, such as refinery 80, or, if needed, pyrolysis oil 35 can be used as feed or co-feed to steam cracker 45.

[0101] Figure 2 The illustration depicts another process for recycling plastic waste according to aspect II, showing an exemplary process flow diagram of feed and product. Figure 2The diagram shows a pyrolysis unit 100, which may include a pyrolysis furnace or reactor and can accept various plastic waste products as pyrolysis unit feed 105. The pyrolysis unit feed 105 is pyrolyzed in the pyrolysis unit 100 to form pyrolysis unit effluent 110, which is then separated at 115 to provide pyrolysis gas 120 and pyrolysis oil 125. The pyrolysis gas may, for example, contain C1 to C5 hydrocarbons, including ethylene, propylene, and butene (EPB). The pyrolysis gas 120 is then routed to a condensation unit 130, which can form a first condenser effluent 135 having a higher proportion of C4-C5 hydrocarbons than the pyrolysis gas and a second condenser effluent 140 having a higher proportion of C2-C3 hydrocarbons than the pyrolysis gas.

[0102] Figure 2 The process also illustrates a first feed stream 145, which is fed into a steam cracker furnace 150 to produce a steam cracker effluent 155, which may contain, for example, olefins (such as ethylene and propylene) and light (C2-C3) saturated hydrocarbons. The steam cracker effluent 155 is then fed into a separation unit 160 located downstream of the steam cracker furnace 150, and a second condenser effluent 140 is routed downstream of the steam cracker furnace 150. Thus, the separation unit 160 receives both the steam cracker effluent 155 and a lighter fraction of the pyrolysis gas as feedstock, the lighter fraction being the second condenser effluent 140 having a higher concentration of C2-C3 hydrocarbons than the pyrolysis gas. The second condenser effluent 140 can be fed directly to the separation unit 160, or combined with the steam cracker furnace effluent 155 before being fed to the separation unit 160, as shown in the figure. The first condenser effluent 135, having a higher proportion of C4-C5 hydrocarbons than the pyrolysis gas 120, can be routed to the steam cracker furnace 150. The first condenser effluent 135 can be fed directly to the steam cracker furnace 150, or, if necessary, combined with the first feed stream before being fed to the steam cracker furnace 150.

[0103] The feed to the separation unit, which contains both steam cracker furnace effluent 155 and second condenser effluent 140, can then be separated to form various effluents from separation unit 160, such as olefin effluent 165. For example, olefin effluent 165 could be ethylene effluent, which can subsequently be fed to polymerization reactor 170 to form polyethylene 175. Separation unit 160, located downstream of steam cracker furnace 150, can also provide light (C2-C3) saturated hydrocarbon effluent 180, which can be recycled back to steam cracker furnace 150 if desired. Figure 2The produced pyrolysis oil 125 can be transported to other uses, such as refinery 185, or, if needed, pyrolysis oil 125 can be used as feed or co-feed for steam cracker 150.

[0104] exist Figure 1 and Figure 2 In the implementation plan, the described process for recycling plastic waste may further include the following step: using an economic decision tree to adjust the operation of the pyrolysis unit from a first set of conditions to a new second set of conditions that increases or decreases the proportion of pyrolysis gas relative to pyrolysis oil in the pyrolysis unit effluent. This economic decision-making process is based on the relative market price of the products produced under the first set of conditions and whether the second set of conditions should be selected to increase or decrease the proportion of pyrolysis gas relative to pyrolysis oil, as disclosed below.

[0105] Economic analysis applied to the pyrolysis of plastic waste. This disclosure also provides a process for recycling plastic waste, the process involving determining and setting or adjusting operating parameters of a pyrolysis unit to increase the production of pyrolysis gases or pyrolysis oils or liquids. Specifically, it has been found that various economic advantages can be achieved by operating the pyrolysis unit under conditions selected to increase the proportion of pyrolysis gases relative to pyrolysis liquids in the pyrolysis unit effluent.

[0106] According to aspect III of this disclosure, a process for recycling plastic waste is provided according to any one of aspect I or aspect II, wherein aspect III further includes the following steps:

[0107] (a') is the market price of the pyrolysis oil formed under the first set of pyrolysis conditions, which is equivalent to the market price of the reference liquid product.

[0108] (b') Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gases formed under the first set of pyrolysis conditions; and

[0109] (c')(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0110] Different methods can be used to value pyrolysis gas products and pyrolysis oil products. For example, the market price of a combination of ethylene, propylene, and butene (EPB) products in the pyrolysis gas can be compared with the assigned market price of the pyrolysis oil, each formed under the first set of pyrolysis conditions. Assigning market prices to pyrolysis oil can be accomplished in various ways, such as assigning a market price to each fraction of the pyrolysis oil equal to the market price of its equivalent reference liquid product.

[0111] Economic analysis of plastic waste pyrolysis is not required only when carried out according to aspects I and II. For example, this disclosure also provides a process for recycling plastic waste according to aspect IV, wherein the process includes the following steps:

[0112] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent containing pyrolysis gas and pyrolysis oil in known ratios, wherein the pyrolysis gas contains C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0113] (b) Assign a market price equivalent to the market price of the reference liquid product to the pyrolysis oil formed under the first set of pyrolysis conditions;

[0114] (c) Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gases formed under the first set of pyrolysis conditions; and

[0115] (d)(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0116] The methods for evaluating pyrolysis gas products and pyrolysis oil products that can be used in other aspects can also be used in this aspect or in the implementation plan.

[0117] In another aspect of this disclosure, economic analysis and the resulting response to the economic analysis can be applied to the pyrolysis of plastic waste separate from aspects I and II according to aspect V, which provides a process for recycling plastic waste, wherein the process includes the following steps:

[0118] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent containing pyrolysis gas and pyrolysis oil in known ratios, wherein the pyrolysis gas contains C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0119] (b) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0120] (c) Feeding the separation unit to the separation unit, the separation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the steam cracker furnace effluent;

[0121] (d) is the market price of the pyrolysis oil formed under the first set of pyrolysis conditions, which is equivalent to the market price of the reference liquid product.

[0122] (e) Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gas formed under the first set of pyrolysis conditions; and

[0123] (f)(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0124] Methods for evaluating pyrolysis gas products and pyrolysis oil products that can be used in other aspects may also be used in this aspect or in the implementation plan.

[0125] As described above, different assignment methods can be used to determine the market price or valuation of pyrolysis gas products and pyrolysis oil products. For example, the pyrolysis gas can be valued by determining the market price of the valuable components of the pyrolysis gas (e.g., a combination of ethylene, propylene, and butene (EPB) in the pyrolysis gas). This value can then be compared with the assigned market price of the pyrolysis oil formed under the same pyrolysis conditions used to form the pyrolysis gas. On one hand, the disclosed process can further include the step of tracking the market price of the combined EPB and referencing the market price of the liquid products in real time.

[0126] There are various ways to assign a market price to pyrolysis oil. For example, a market price can be assigned to each fraction of the pyrolysis oil that is equal to the market price of the equivalent reference liquid product of each fraction. In this respect, the market price assigned to the pyrolysis oil can be a weighted average of the equivalent reference liquid product of each fraction, which is a function of the amount of each fraction obtained from the pyrolysis oil. For example, the fractions of the pyrolysis oil can include any combination of fractions selected from diesel, gasoline, naphtha, kerosene, gas oil, and wax.

[0127] On the other hand, when assigning a market price to pyrolysis oil, the reference liquid product may include gasoline, diesel, or a gasoline-diesel blend. For example, the reference liquid product may include a blend of gasoline and diesel having about 95% to 5% gasoline and about 5% to 95% diesel. That is, if desired, the reference liquid product can be adjusted according to the properties of the pyrolysis oil (such as the properties and quantity of the fractions obtained from the pyrolysis oil). On the other hand, the reference liquid product may include a blend of gasoline and diesel having about 90% to 50% gasoline and about 10% to 50% diesel. Alternatively, the reference liquid product may include a blend of gasoline and diesel having about 70% gasoline and about 30% diesel.

[0128] When the relative market prices of pyrolysis gas and pyrolysis oil formed under the first set of pyrolysis conditions are determined, these prices can be compared to determine whether the market conditions can provide higher overall margins by increasing the relative amount of pyrolysis gas or pyrolysis oil in the pyrolysis unit effluent. Once determined, a second set of pyrolysis conditions can be applied that increases either the ratio of pyrolysis gas to pyrolysis oil or the ratio of pyrolysis oil to pyrolysis gas in the pyrolysis unit effluent. On the one hand, the second set of pyrolysis conditions increases the ratio of pyrolysis gas to pyrolysis oil in the pyrolysis reactor effluent. On the other hand, the second set of pyrolysis conditions increases the ratio of pyrolysis oil to pyrolysis gas in the pyrolysis reactor effluent.

[0129] According to one aspect, after applying the second set of pyrolysis conditions, a pyrolysis reactor effluent containing about 60% to about 85% wt% pyrolysis gas and about 40% to about 15% wt% pyrolysis liquid can be obtained. Alternatively, after applying the second set of pyrolysis conditions, a pyrolysis reactor effluent containing about 75% to about 83% wt% pyrolysis gas and about 25% to about 17% wt% pyrolysis liquid can be formed.

[0130] Furthermore, applying the second set of pyrolysis conditions can increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor. The pyrolysis oil produced under the second set of pyrolysis conditions has a higher content of aromatic compounds than that produced under the second set of pyrolysis conditions. Applying the second set of pyrolysis conditions can also increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor. The pyrolysis oil produced under the second set of pyrolysis conditions has a lower wax content than that produced under the second set of pyrolysis conditions.

[0131] In each of these processes for recycling plastic waste that use pyrolysis gas, pyrolysis oil, or both, the weight or fraction of the recycled products attributable to the pyrolysis gas or plastic waste can be determined by mass balance, examples of which are provided herein. The disclosed processes may further include the step of certifying the pyrolysis oil, pyrolysis gas, or any subsequent products generated using the pyrolysis oil or pyrolysis gas as recycled, based on the weight or fraction of the recycled products attributable to the plastic waste as determined by mass balance and free attribution methods, in accordance with International Sustainability and Carbon Certification (ISCC) standards.

[0132] Pyrolysis unit operation, pyrolysis gas, and pyrolysis oil. Conventional pyrolysis reactors have been operated to favor the production of pyrolysis oil for chemical and refining processes, while the less desirable pyrolysis gas is often used as fuel. The applicant has discovered that various economic advantages can be achieved by operating the pyrolysis unit under conditions selected to increase the proportion of pyrolysis gas relative to pyrolysis oil in the pyrolysis unit effluent. This disclosure also provides for adjusting the operating conditions of the pyrolysis unit according to the relative economic value of the pyrolysis gas as feed compared to the pyrolysis oil, to provide additional economic advantages.

[0133] Those skilled in the art will understand the conventional pyrolysis unit operations that favor the production of pyrolysis oil. On one hand, the pyrolysis unit can be operated under conditions selected to increase, optimize, or maximize the ratio of pyrolysis gas to pyrolysis liquid (also known as pyrolysis oil) in the pyrolysis unit effluent. For example, pyrolysis temperature, the use and selection of catalysts, etc., can be used to increase the relative proportion of pyrolysis gas to pyrolysis oil. Those skilled in the art will understand that pyrolysis parameters can be adjusted to increase the yield of gaseous products in the pyrolysis unit. For example, publications such as (1) The Chemistry and Kinetics of Polyethylene Pyrolysis: A Process to Produce Fuels and Chemicals (ChemSusChem 2020, 13, 1764-1774) by GWHuber et al. and (2) J. Chem. 2013, 1-5 by SMFakhrHoseini and M. Dastanian describe the effects of pyrolysis conditions (including temperature, reactor type, residence time, catalyst, etc.) on the product yield distribution of many polymer materials, each of which is incorporated herein by reference.

[0134] In the implementation scheme, the pyrolysis unit can be operated under conditions selected to increase, optimize, or maximize the ratio of the C2-C3 fraction to the C4-C5 fraction of the pyrolysis gas. The conditions for operating the pyrolysis unit can also be selected to increase, optimize, or maximize the ratio of ethylene to other olefins or saturated hydrocarbons in the pyrolysis gas. In the implementation scheme, the conditions can also be selected to increase, optimize, or maximize the ratio of C5 and lighter (C4-C5) fractions in the pyrolysis gas. ≤5 Hydrocarbons relative to C6 and any heavier (C6) hydrocarbons ≥6 The pyrolysis unit is operated under conditions of hydrocarbon ratio.

[0135] In one implementation, plastic waste can be processed in the pyrolysis unit at a temperature of approximately 450°C to approximately 800°C. Alternatively, plastic waste can be processed in the pyrolysis unit at a temperature of approximately 600°C to approximately 800°C. These temperatures provide a higher ratio of pyrolysis gas to pyrolysis oil compared to conventional operating temperatures. On one hand, the pyrolysis unit can be operated such that plastic waste is processed by pyrolysis at the following temperatures: about 450°C, about 460°C, about 470°C, about 480°C, about 490°C, about 500°C, about 510°C, about 520°C, about 530°C, about 540°C, about 550°C, about 560°C, about 570°C, about 580°C, about 590°C, about 600°C, about 610°C, about 620°C, about 630°C, about 640°C, about 650°C, about 660°C, about 670°C, about 680°C, about 690°C, about 700°C, about 710°C, about 720°C, about 730°C, about 740°C, about 750°C, about 760°C, about 770°C, about 780°C, about 790°C, or about 800°C, or any range between these temperatures. The fact that pyrolysis can be carried out at different temperatures in different zones of the pyrolysis reactor is also taken into consideration, as those skilled in the art will understand. In embodiments, for example, temperature ramps between operating temperatures are considered when adjusting the operating conditions of the pyrolysis unit to increase or decrease the ratio of pyrolysis gas to pyrolysis oil.

[0136] On the other hand, plastic waste can be processed in a pyrolysis unit under catalytic conditions in the presence of a catalyst. For example, plastic waste can be processed in a pyrolysis unit under catalytic conditions using a catalyst, including alumina, aluminosilicates (e.g., zeolites or silica-alumina), silica-alumina-phosphates, transition metal oxides (e.g., titanium oxide, zirconium oxide, hafnium oxide, or niobium oxide), polyoxometalates, heteropolyoxometalates, polystyrene sulfonate resins, sulfonated carbon, solid phosphoric acid, or niobic acid, or combinations thereof. It is also possible to process plastic waste in a pyrolysis unit under non-catalytic conditions in the absence of a catalyst.

[0137] On the one hand, the pyrolysis unit can be operated continuously in the same manner as the steam cracker, separation unit, and other operations, allowing for a continuous supply of pyrolysis gas. For example, when the pyrolysis furnace temperature varies in a ramp-like manner between different operating temperatures, causing an increase or decrease in the ratio of pyrolysis gas to pyrolysis oil, the unit can continue to supply pyrolysis gas and pyrolysis oil throughout any temperature ramp. On the other hand, the pyrolysis gas, or a portion thereof, can be continuously supplied downstream of the steam cracker according to aspects I and II. On the other hand, the pyrolysis unit can be operated intermittently, for example, when the operating conditions of the pyrolysis unit are adjusted by changing the catalyst.

[0138] On the other hand, pyrolysis gas can be generated by pyrolyzing plastic waste under conditions that provide pyrolysis gas containing about 15 wt% to about 40 wt% ethylene. Alternatively, the pyrolysis gas may contain about 18 wt% to about 38 wt% ethylene or about 20 wt% to about 35 wt% ethylene. In this respect, the pyrolysis unit can be operated under conditions that provide pyrolysis gas containing ethylene at concentrations of about 15 wt%, about 18 wt%, about 20 wt%, about 23 wt%, about 25 wt%, about 28 wt%, about 30 wt%, about 33 wt%, about 35 wt%, about 38 wt%, or about 40 wt% (inclusive of any range between these values).

[0139] According to one aspect, pyrolysis gas can be generated by pyrolyzing plastic waste under conditions that provide pyrolysis gas containing about 25 wt% to about 60 wt% of C2 hydrocarbons (ethane and ethylene). Alternatively, the pyrolysis gas may contain about 30 wt% to about 55 wt% of C2 hydrocarbons or about 35 wt% to about 50 wt% of C2 hydrocarbons. In this aspect, the pyrolysis unit can be operated under conditions that provide pyrolysis gas containing C2 hydrocarbons of concentrations of about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, or about 60 wt% (inclusive of any range between these values) of ethylene.

[0140] In another aspect, pyrolysis gas can be generated by pyrolyzing plastic waste under conditions that provide pyrolysis gas containing about 15 wt% to about 35 wt% propylene. Alternatively, the pyrolysis gas may contain about 17 wt% to about 32 wt% propylene or about 20 wt% to about 30 wt% propylene. In this aspect, the pyrolysis unit can be operated under conditions that provide pyrolysis gas containing propylene at concentrations of about 15 wt%, about 17 wt%, about 20 wt%, about 22 wt%, about 25 wt%, about 27 wt%, about 30 wt%, about 32 wt%, or about 35 wt% propylene (inclusive of any range between these values).

[0141] In a further aspect of this disclosure, pyrolysis gas can be generated by pyrolyzing plastic waste under conditions that provide pyrolysis gas comprising from about 17 wt% to about 45 wt% of C3 hydrocarbons (propane and propylene). Alternatively, the pyrolysis gas may comprise from about 20 wt% to about 42 wt% of C3 hydrocarbons or from about 22 wt% to about 40 wt% of C3 hydrocarbons. In this aspect, the pyrolysis unit can be operated under conditions that provide pyrolysis gas comprising C3 hydrocarbons at concentrations of about 17 wt%, about 20 wt%, about 22 wt%, about 25 wt%, about 27 wt%, about 30 wt%, about 32 wt%, about 35 wt%, about 37 wt%, about 40 wt%, about 42 wt%, or about 45 wt% (inclusive of any range between these values).

[0142] In implementations, the pyrolysis gas can be purified before being fed into the separation unit. Regardless of the concentrations of the various components of the pyrolysis gas, any process disclosed herein may further include steps for real-time tracking of fuel costs and the total value of the recycled products.

[0143] The pyrolysis gases and pyrolysis oils disclosed herein (sometimes abbreviated as pyrolysis gases (pygas) and pyrolysis oils (pyoil), respectively) can be derived from the pyrolysis of a wide range of plastic wastes. For example, the pyrolysis gases and pyrolysis oils can be derived from the pyrolysis of any type of polyolefin, such as polyethylene and polypropylene polymers and copolymers, polystyrene, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyamide, polycarbonate, polyurethane, polyester, their copolymers, their filled polymers, their composites, natural or synthetic rubber, tires, or any combination thereof. For example, plastic waste can contain polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET), polyamide, polycarbonate, polyurethane, or polyester.

[0144] In some processes, it may be desirable for pyrolysis gases and pyrolysis oils to have relatively low concentrations of chloride ions, which can be achieved, for example, by selecting plastic waste with low concentrations of chlorinated polymers (such as PVC). Alternatively, the use of pyrolysis gases or pyrolysis oils with relatively low concentrations of chloride ions can also be achieved, for example, by purifying them before using them as feedstocks or co-feedstocks.

[0145] For example, on one hand, the plastic waste may contain chlorinated polymers, at least a portion of which has been removed from the plastic waste before it is pyrolyzed in the pyrolysis unit. On the other hand, the plastic waste may contain chlorinated polymers, and at least a portion of the chloride-containing pyrolysis products has been removed from the pyrolysis gas or pyrolysis oil before being fed to the downstream unit.

[0146] In the implementation scheme, the pyrolysis gas or pyrolysis oil may contain a range of non-hydrocarbon contaminants. For example, the pyrolysis gas or pyrolysis oil may contain non-hydrocarbon contaminants that include or are selected from inorganic acids, organic acids, binary compounds of Group 15 elements and hydrogen, binary compounds of Group 16 elements and hydrogen, organic compounds containing Group 15 elements, or organic compounds containing Group 16 elements. Examples of non-hydrocarbon contaminants that may be present in the pyrolysis gas or pyrolysis oil include, but are not limited to, HCl, HBr, phosphine, arsine, antimony, alcohols, organic acids, nitrogen oxides, chloroform, C1-C3 hydrocarbon chlorides, or C1-C3 hydrocarbon fluorides.

[0147] Before feeding the pyrolysis gas to the separation unit as in aspect I, or to the condensation unit as in aspect II, the pyrolysis gas may be pretreated with a caustic alkali or amine, which helps to remove acidic components. The pyrolysis gas may also be pretreated with metal oxides, such as in a metal oxide catalyst bed, before feeding it to the separation unit as in aspect I or to the condensation unit as in aspect II. For example, the metal oxide catalyst bed may include or may be selected from zinc oxide, calcium oxide, or iron oxide, or various combinations of metal oxides. In some embodiments, the pyrolysis gas may be pretreated with molecular sieves or promoted or activated alumina before being fed to the separation unit, condensation unit, or any downstream unit.

[0148] Subsequent processing of effluents from the pyrolysis unit and the separation unit. Once plastic waste has been pyrolyzed and processed as disclosed herein, a range of recycled products can be provided, and multiple subsequent processing steps can be performed to generate other recycled chemicals or recycled polymers, as well as to recycle certain effluents. For example, according to the processes described in Aspects I and II above, ethylene, propylene, and light (C2-C3) saturated hydrocarbons can be formed, separated, and used in downstream processes.

[0149] For example, the process disclosed herein may further include the following steps: feeding ethylene effluent or at least a portion of ethylene effluent to one or more downstream processing units to provide a recycled product comprising or selected from: ethylene homopolymer, ethylene-α-olefin copolymer, ethylene-ionomer copolymer, ethylene-propylene elastomer, n-α-olefin (C4-C4) 30 +), chlorosulfonated polyethylene, vinyl chloride, ethylene oxide, ethylbenzene, acetaldehyde, vinyl acetate, or polyvinyl acetate. Recycled ethylene effluent or a portion thereof can be fed as feed to the polymerization reactor and converted into any type of recycled polyethylene or other recycled products derived from ethylene, such as ethylbenzene. Each of these recycled products can then be processed to provide additional recycled chemicals and polymers, some examples of which are described below.

[0150] On one hand, for example, when one or more downstream processing units provide recycled vinyl chloride, the recycled vinyl chloride can be fed to one or more subsequent processing units to provide a recycled product selected from: polyvinyl chloride homopolymer, polyvinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, 1,1,2-trichloroethane, vinylidene chloride, or polyvinylidene chloride.

[0151] When the one or more downstream processing units provide recycled ethylene oxide, in a further aspect, the recycled ethylene oxide can be fed to one or more subsequent processing units to provide a recycled product selected from: ethylene glycol, poly(ethylene terephthalate), polyethylene glycol-polyalkylene glycol copolymer, ethoxylated phenol, ethoxylated amine, diethylene glycol, polyester, unsaturated polyester, polyester polyol, adipic acid, polyurethane resin, hydroxyethyl starch, hydroxyethyl gum, or hydroxyethyl cellulose.

[0152] In a further aspect, when the one or more downstream processing units provide recycled ethylbenzene, the recycled ethylbenzene can be fed to one or more subsequent processing units to provide a recycled product selected from: styrene, polystyrene, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene terpolymer, styrene-acrylonitrile copolymer, polyester resin, styrene-divinylbenzene resin, styrene-alkyd copolymer, or styrene-maleic anhydride copolymer.

[0153] According to another aspect, when the one or more downstream processing units provide recycled acetaldehyde, the recycled acetaldehyde can be fed to one or more subsequent processing units to provide a recycled product selected from pentaerythritol, alkyd resin or acetic acid.

[0154] In the case where the one or more downstream processing units provide recycled vinyl acetate, in one aspect, the recycled vinyl acetate can be fed to one or more subsequent processing units to provide a recycled product selected from: poly(vinyl acetate), poly(vinyl acetate) copolymer, ethylene-vinyl acetate copolymer, or vinyl chloride-vinyl acetate copolymer.

[0155] According to another aspect, when the one or more downstream processing units provide recycled poly(vinyl acetate), the recycled poly(vinyl acetate) can be fed to one or more subsequent processing units to provide a recycled product selected from poly(vinyl alcohol), poly(vinylbutyral) and poly(vinylformal).

[0156] In a further aspect, when the one or more downstream processing units provide recycled alpha olefins, the recycled alpha olefins can be fed to one or more subsequent processing units to provide recycled products selected from polyalpha olefins or poly(ethylene-co-alpha olefins). For example, the recycled alpha olefins may be recycled n-alpha olefins (C4-C... 30 +), and can circulate n-α-olefins (C4-C) 30 +) Feed to one or more subsequent processing units to provide a recycled product selected from poly(n-α olefin) or poly(ethylene-co-(n-α olefin)).

[0157] On the other hand, the one or more downstream processing units may provide recycled α-olefins, which include or are selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene, and these recycled α-olefins may be fed to one or more subsequent processing units to provide recycled products comprising or selected from the following: poly(ethylene-co-1-butene), poly(ethylene-co-1-pentene), poly(ethylene-co-1-hexene), poly(ethylene-co-1-heptene), poly(ethylene-co-1-octene), poly(ethylene-co-1-nonene), poly(ethylene-co-1-decene), poly(ethylene-co-1-dodecene), poly(ethylene-co-1-tetradecene), poly(ethylene-co-1-hexadecene), or poly(ethylene-co-1-octadecene).

[0158] Pyrolytic plastic waste can also be provided as recycled propylene effluent as disclosed above, and any number of subsequent processing steps can be performed to produce other recycled chemicals or recycled polymers from the recycled propylene. In one aspect, for example, the process disclosed herein may further include the step of feeding the propylene effluent or at least a portion thereof to one or more downstream processing units to provide a recycled product comprising or selected from: polypropylene homopolymer, polypropylene copolymer, acrylonitrile, propylene oxide, cumene, n-butyraldehyde, isobutyraldehyde, allyl chloride, acrylate, or isopropanol. For example, the propylene effluent or at least a portion thereof can be fed as feed to a polymerization reactor to form recycled polypropylene.

[0159] On the other hand, when the one or more downstream processing units provide recycled acrylonitrile, the recycled acrylonitrile can be fed to one or more subsequent processing units to provide a recycled product selected from: polyacrylonitrile, modified polyacrylonitrile copolymer, acrylonitrile butadiene styrene (ABS), styrene-acrylonitrile resin (SAN), nitrile elastomer, acrylonitrile copolymer, hexamethylenediamine, nylon 6,6, acrylamide, polyacrylamide homopolymer, or polyacrylamide copolymer.

[0160] According to one aspect, when the one or more downstream processing units provide recycled propylene oxide, the recycled propylene oxide can be fed to one or more subsequent processing units to provide a recycled product selected from propylene glycol, polyester, poly(propylene glycol) homopolymer, poly(propylene glycol) copolymer or polyurethane.

[0161] In a further aspect, when the one or more downstream processing units provide recycled n-butyraldehyde, the recycled n-butyraldehyde can be fed to one or more subsequent processing units to provide a recycled product selected from poly(vinyl butyral), n-butyric acid, n-butyric anhydride, or cellulose acetate butyrate.

[0162] On another front, when the one or more downstream processing units provide recycled isobutyraldehyde, the recycled isobutyraldehyde can be fed to one or more subsequent processing units to provide a recycled product selected from neopentyl glycol, polyester or polyurethane.

[0163] According to a further aspect, when the one or more downstream processing units provide recycled allyl chloride, the recycled allyl chloride can be fed to one or more subsequent processing units to provide a recycled product selected from epichlorohydrin or epoxy resin.

[0164] In another aspect, when the one or more downstream processing units provide recycled acrylate, the recycled acrylate can be fed to one or more subsequent processing units to provide a recycled product selected from acrylic homopolymers or copolymers.

[0165] In a further aspect, when the one or more downstream processing units provide recycled isopropanol, the recycled isopropanol can be fed to one or more subsequent processing units to provide a recycled product selected from: acetone, bisphenol A, epoxy resin, polycarbonate, polysulfone, methacrylic acid, poly(methyl methacrylate) homopolymer or poly(methyl methacrylate) copolymer.

[0166] In some implementations, pyrolyzed plastic waste can be processed as described to provide a variety of recycling products, such as ethylene, propylene, light (C2-C3) saturated hydrocarbons, and other products. For example, according to the processes of aspects I and II described above, ethylene, propylene, and light (C2-C3) saturated hydrocarbons can be formed and separated. However, additional products may also be generated in these processes and separated downstream. In both aspects I and II, C5 and lighter hydrocarbon pyrolysis gases or fractions thereof may be fed downstream of a steam cracker, mixed with the effluent from the steam cracker, then purified or separated, and subsequently fed to other subsequent processes or reactors. In these processes, the separation step can provide recycling products further comprising butene and butane effluents. The butene and butane effluents can be used in any number of downstream processes to produce other recycling chemicals or recycling polymers.

[0167] On one hand, for example, butene and butane effluents or a portion thereof may be fed to one or more downstream processing units to provide a recycled product comprising or selected from: recycled butadiene, maleic anhydride, butene oxide, 1-butene, mixed butene, isobutene or butane.

[0168] On one hand, when the one or more downstream processing units provide recycled butadiene, the recycled butadiene can be fed as feed to one or more subsequent processing units to provide recycled products selected from: recycled styrene, polybutadiene elastomers, polybutadiene resins, hexamethylenediamine, nylon, chloroprene, chloroprene rubber elastomers, 1,5-cyclooctadiene, ethylene-propylene terpolymer elastomers, 1,5,9-cyclododecanetriene, dodecanoic acid, nylon 6,12, quaana, lauryl lactam, nylon 12, OH-terminated polymers and copolymers, polyurethane elastomers, or 1,4-hexadiene.

[0169] On the other hand, it provides that when the one or more downstream processing units provide recycled maleic anhydride, the recycled maleic anhydride can be fed to one or more subsequent processing units to provide a recycled product selected from recycled polyester, alkyd resin or styrene-maleic anhydride copolymer.

[0170] On the other hand, it provides that when the one or more downstream processing units provide recycled butene oxide, the recycled butene oxide can be fed to one or more subsequent processing units to provide a recycled product selected from recycled poly(butene oxide) or polyurethane.

[0171] When the one or more downstream processing units provide recycled 1-butene, mixed butene and / or isobutene, in one aspect, the recycled 1-butene, mixed butene and / or isobutene can be fed to one or more subsequent processing units to provide a recycled product selected from recycled poly(1-butene), poly(butene), poly(isobutene) or butyl rubber.

[0172] In a further aspect, when the one or more downstream processing units provide recycled butane, the recycled butane can be fed to one or more subsequent processing units to provide a recycled product selected from recycled acetic acid.

[0173] As with any of the recycling products described herein, the weight or fraction of the recycling products attributable to pyrolysis gases or plastic waste can be determined by mass balance. In a further aspect, any one or more of these recycling products can be certified according to the International Sustainability and Carbon Certification (ISCC) standards, based on the weight or fraction of the recycling products attributable to pyrolysis gases or plastic waste as determined by mass balance and free attribution methods.

[0174] When ethylene effluent produced according to this disclosure (e.g., according to aspect I or aspect II) is fed into a polymerization reactor to form recycled polyethylene, the amount of recycled polyethylene produced may be, for example, about 10%, about 15%, about 20%, or about 25%, or any range therebetween, higher than the amount of recycled polyethylene produced in a corresponding process using only liquid pyrolysis effluent feedstock, such as by the percentage (%) of gas production from the pyrolysis unit per unit weight of plastic feed.

[0175] In a further aspect, the carbon footprint of any independently chosen cyclic product can be reduced by approximately 15%, approximately 20%, approximately 25%, approximately 30%, approximately 35%, or approximately 40% compared to the carbon footprint of the corresponding non-cyclic products generated in the absence of pyrolysis gases and pyrolysis oils.

[0176] According to another approach, plastic waste can be pyrolyzed in amounts sufficient to displace the raw materials required to produce the same quantities of ethylene effluent, propylene effluent, and light (C2-C3) saturated hydrocarbon effluent from a separation unit located downstream of a steam cracker furnace, at approximately 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%.

[0177] A further aspect provides that plastic waste can be pyrolyzed in amounts sufficient to provide feed to the separation unit, such as about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt%.

[0178] Plastic waste pyrolysis for the production of light gaseous hydrocarbons and the integration of the pyrolysis unit with a fluidized catalytic cracker. Regarding aspect VI of this disclosure, a process for recycling plastic waste (including the production of chemicals or polymers from plastic waste) is provided, the process comprising:

[0179] (a) Pyrolysis of plastic waste in a pyrolysis unit to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil, wherein the pyrolysis gas comprises C5 fractions having C2-C3 fractions and C4-C5 fractions, and lighter (C5 and C4-C5 fractions). C≤5 )hydrocarbon;

[0180] (b) A heavy hydrocarbon feed stream is fed into a fluidized catalytic cracking (FCC) reactor to produce an FCC effluent containing naphtha (C6-C4). 10 Hydrocarbons) and C5 and lighter (C ≤5 )hydrocarbon;

[0181] (c) Providing a fractionation unit feed to the fractionation unit, the fractionation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the FCC effluent; and

[0182] (d) Separating the feed from the fractionation unit to provide a recycled product, the recycled product comprising: C5 and lighter (C5) compounds. ≤5 The first fraction of hydrocarbons and the effluent containing heavy hydrocarbons (C 6+ The second fraction of hydrocarbon effluent.

[0183] In this respect, C5 and lighter hydrocarbon gas streams, with or without condensable components, can be fed downstream of the FCC to the reactor effluent purification / separation unit. Pyrolysis gases can be fed directly to the fractionation unit, or the FCC effluent and pyrolysis gases can be combined before being fed to the fractionation unit to form the fractionation unit feed.

[0184] Regarding the FCC reactor, in one aspect, a heavy hydrocarbon feed stream can be fed into a fluidized catalytic cracker (FCC) pre-processor to form a treated stream, which is then fed into the FCC reactor. For example, the treated stream may have a lower sulfur content, a lower aromatic compound content, or both, compared to the sulfur content and / or aromatic compound content in the pre-pretreatment heavy hydrocarbon feed stream.

[0185] Regarding the fractionation unit feed, in this respect, the fractionation unit feed may further include at least a portion of the pyrolysis oil in the pyrolysis unit effluent generated from pyrolysis plastic waste.

[0186] On the one hand, if necessary, the substance containing heavy matter (C) can be made... 6+ At least a portion of the second fractionation effluent of the hydrocarbon is recycled to the fluidized catalytic cracker (FCC) reactor.

[0187] When the feed to the fractionation unit is separated to provide a recycle product consisting of a first fraction effluent containing C5 and lighter hydrocarbons and a second fraction effluent containing heavier hydrocarbons, the heavy hydrocarbons (C5 and lighter hydrocarbons) can be separated. 6+ The second fraction of the hydrocarbon effluent or a portion thereof is fed into the reforming unit or Units, respectively, to provide respective reformate streams containing recycled aromatics or Product flow. On the one hand, reforming the product flow or... The product stream may further contain hydrogen and / or aliphatic hydrocarbons.

[0188] The reforming product stream or The recycled aromatic hydrocarbon products provided in the product stream are fed to one or more subsequent processing units to provide a variety of recycled products, examples of which include the following.

[0189] In some aspects, reforming product logistics or The product stream may include recycled benzene, and the recycled benzene is fed to one or more subsequent processing units to provide a recycled product selected from ethylbenzene, benzenesulfonic acid, chlorobenzene, cumene, cyclohexane, nitrobenzene, or maleic anhydride. Reforming product stream or The product stream may include recycled toluene, and the recycled toluene may be fed to one or more subsequent processing units to provide a recycled product selected from dinitrotoluene, toluene diisocyanate, or carbamate.

[0190] In other aspects, reforming product logistics or The product stream may include recycled o-xylene, and the recycled o-xylene may be fed to one or more subsequent processing units to provide a recycled product selected from phthalic anhydride, alkyd resins, polyester resins, polyester polyols, urethanes, or polyurethanes. Reforming product stream or The product stream may also include recycled m-xylene, which can be fed to one or more subsequent processing units to provide a recycled product selected from isophthalic acid, polyester, alkyd resins, polyamide resins, diphenyl isophthalate, or polybenzimidazole. Reforming product stream or The product stream may also include recycled p-xylene, and the recycled p-xylene may be fed to one or more subsequent processing units to provide recycled products selected from terephthalic acid, polyethylene terephthalate, or polybutylene terephthalate.

[0191] In each step of this process, the reforming product stream or... can be determined through quality balance. The fraction of aromatic hydrocarbons attributable to plastic waste or pyrolysis gases in the product stream. The fraction of benzene, toluene, o-xylene, m-xylene, p-xylene, or any recycled products attributable to plastic waste or pyrolysis gases generated in the one or more subsequent processing units can also be determined by mass balance. Alternatively, according to the International Sustainability and Carbon Certification (ISCC) standards, the benzene, toluene, o-xylene, m-xylene, p-xylene, or any recycled products attributable to plastic waste or pyrolysis gases generated in the one or more subsequent processing units can be certified as recycled based on the weight or fraction of recycled products attributable to plastic waste as determined by mass balance and free attribution methods.

[0192] Further relating to aspect VI and related aspects stated above, these processes may further include the following steps: [The text abruptly ends here, likely due to an incomplete sentence or missing information.] ≤5At least a portion of the first fractionation effluent of the hydrocarbons is fed into a steam cracker to form a steam cracker product stream comprising ethylene and light (C2-C3) saturated hydrocarbons. The steam cracker product stream can then be fed into a separation unit, where the feed can be separated to provide ethylene effluent, propylene effluent, and light (C2-C3) saturated hydrocarbon effluent. If desired, the light (C2-C3) saturated hydrocarbon effluent, or a portion thereof, can be recycled back to the steam cracker. The ethylene effluent, propylene effluent, or a portion thereof can be fed into a polymerization reactor to form recycled polyethylene or recycled polypropylene. In any of these processes, the fraction of products (such as recycled polyethylene or recycled polypropylene) attributable to plastic waste or pyrolysis gases is determined by mass balance, and these products can be certified as recycled according to the International Sustainability and Carbon Certification (ISCC) standards based on the weight or fraction of recycled products attributable to plastic waste, as determined by mass balance and free attribution methods.

[0193] This disclosure is further illustrated by the following embodiments, which should not be construed as limiting the scope of this disclosure in any way. Rather, it should be clearly understood that various other aspects, embodiments, modifications, and equivalents thereof will be apparent to those skilled in the art upon reading this description without departing from the spirit of the invention or the scope of the appended claims.

[0194] Example

[0195] General considerations

[0196] Certification calculations for the percentage of recycled products. The ISCC Sustainability Statement is issued for discrete mass quantities of products; therefore, certification is for a specific product weight. The conversion factor used in the certification calculations can vary considerably depending on the specific reactor, processing unit, and conditions, and the conversion factor is predetermined and therefore retrospective. The conversion factor can be re-determined based on certification requirements (e.g., in the absence of changes in processing conditions) and can be re-determined and adjusted annually. The certification calculation for the weight of recycled products is based on the assumption that a significant portion of the weight of the pyrolysis oil added to the cracker and mixed with petroleum-based or fossil fuel-based feedstocks is also reflected in the recycled products. Therefore, this calculation assumes that the conversion rate applies to both the pyrolysis oil portion of the feedstock and the petroleum-based or fossil fuel-based feedstock.

[0197] Therefore, this certification process uses a free attribution method to assign recycling product credits to each product stream, subtracting any waste streams (such as the combusted portion of the product stream). Furthermore, the free attribution method allows all credits generated by mixing the pyrolysis oil stream with petroleum-based or fossil fuel-based feedstocks to be allocated as needed to any or all processing unit (e.g., cracker) products from said stream, similarly reducing any waste streams. For example, the total recycling product credits for all recovered products can be considered as recycling ethylene, provided the pyrolysis oil is used to produce ethylene, propylene, fuel gas, and any other products recovered from the stream.

[0198] This free attribution method is reasonably based on the measured or calculated conversion factors of the various plants or units reflected in this disclosure, which may have conversion factors >0.90 (e.g., in the range of about 0.90 to about 0.998). Therefore, to determine the weight of the recycled ethylene produced, this conversion factor of about 1 is multiplied by the weight of the pyrolysis oil fed to the cracker. This free attribution principle also applies to polyethylene (PE) reactors and fluidized catalytic crackers (FCCs) with similarly high conversion factors. The application of this calculation method will be demonstrated in the following examples.

[0199] Example 1. Calculation for certifying ethylene production.

[0200] A feedstock containing 10% by weight of pyrolysis oil, mixed with petroleum-based or fossil fuel-based feedstock, is fed into the cracker. It has been previously calculated over discrete time periods that the cracker will convert the feedstock into a mixture of ethylene (60% by weight), propylene (25% by weight), and fuel gas (12% by weight), which constitutes 97% by weight of the recovered products, with the remaining 3% by weight being combusted. Therefore, in this embodiment, the cracker conversion factor is calculated to be 0.97 for the previous time period. Every 100 pounds of total feedstock contains 10 pounds of pyrolysis oil (10% by weight concentration), with the remainder being petroleum-based or fossil fuel-based feedstock. Therefore, the weight of the recycled products attributable to the pyrolysis oil can be calculated as 9.7 pounds (10 pounds × 0.97 conversion factor). The total amount of 9.7 pounds of recycled products is attributed to the recovered ethylene used for recycling. Therefore, the resulting recycled ethylene is certified as 9.7 pounds according to ISCC standards.

[0201] Example 2. Calculation for certification of ethylene homopolymer production volume

[0202] The ethylene containing recycled products produced according to Example 2 is fed into the polymerization reactor and converted into ethylene homopolymer. Therefore, it is calculated that 60 pounds of ethylene (100 pounds of feedstock × 60 wt%) contains 9.7 pounds of recycled ethylene. Previously, it was calculated that the polymerization reactor converts the ethylene feedstock into polyethylene (98 wt%) over discrete time periods, with the remaining 2 wt% being discarded; therefore, in this example, the calculated conversion factor for the polymerization reactor for the previous time period is 0.98.

[0203] The total polyethylene product obtained from 60 pounds of ethylene is 58.8 pounds (60 pounds of total ethylene × 0.98 conversion factor). Therefore, the weight of the recycled polyethylene product attributable to the pyrolysis oil can be calculated as 9.5 pounds (9.7 pounds of recycled ethylene × 0.98 conversion factor), and is certified as 9.5 pounds according to ISCC standards.

[0204] Example 3. Calculation for certification of ethylene copolymer production volume

[0205] Ethylene containing recycled products, produced according to Example 2, is fed into a polymerization reactor containing the non-recycled comonomer 1-hexene and converted into a poly(ethylene-co-1-hexene) copolymer. Therefore, it is calculated that 60 pounds of ethylene (100 pounds of feed × 60 wt%) contains 9.7 pounds of recycled ethylene. Previously, it was calculated over discrete time periods that the polymerization reactor converts the ethylene and 1-hexene feed into poly(ethylene-co-1-hexene) (98 wt%), with the remaining 2 wt% being discarded; therefore, in this example, the calculated conversion factor for the polymerization reactor is also 0.98 for the previous time period.

[0206] Therefore, the total poly(ethylene-co-1-hexene) product obtained from 60 pounds of ethylene is 58.8 pounds (60 pounds of total ethylene × 0.98 conversion factor). Therefore, the weight of the recycled poly(ethylene-co-1-hexene) product attributable to the pyrolysis oil can be calculated as 9.5 pounds (9.7 pounds of recycled poly(ethylene-co-1-hexene) × 0.98 conversion factor), and is certified as 9.5 pounds according to ISCC standards.

[0207] Example 4. Calculation for certification of ethylene copolymer production volume

[0208] Ethylene containing recycled products, produced according to Example 2, is fed into a polymerization reactor containing the recycled comonomer 1-hexene and converted into a poly(ethylene-co-1-hexene) copolymer. Therefore, 60 pounds of ethylene (100 pounds of feed × 60 wt%) is calculated to contain 9.7 pounds of recycled ethylene. In this example, the feed may contain 60 pounds of ethylene (9.7 pounds recycled) and 5 pounds of 1-hexene (of which 1 pound is certified as recycled), resulting in 10.7 pounds (9.7 pounds of recycled ethylene + 1 pound of recycled 1-hexene) of a total feed of 65 pounds, certified as recycled. Previously, it was calculated that the polymerization reactor converts the ethylene and 1-hexene feed into poly(ethylene-co-1-hexene) (98 wt%) over discrete time periods, with the remaining 2 wt% being discarded; therefore, in this example, the calculated conversion factor for the polymerization reactor is also 0.98 for the previous time period.

[0209] Therefore, the total poly(ethylene-co-1-hexene) product obtained from this 65 lb feed is 63.7 lb (65 lb total feed × 0.98 conversion factor). Thus, the weight of the recycled poly(ethylene-co-1-hexene) product attributable to the pyrolysis oil can be calculated as 10.49 lb [(9.7 lb recycled ethylene × 0.98 conversion factor) + (1 lb recycled 1-hexene × 0.98 conversion factor)], and is certified as 10.49 lb according to ISCC standards. This 10.49 lb recycled product can also be easily calculated using 10.7 lb recycled product from the 65 lb feed × 0.98 conversion factor.

[0210] Example 5. Calculation of Ethylbenzene Production Capacity

[0211] The principle illustrated above can be applied to other products, and the certification of a specific weight of the produced product as a recycled product can be calculated according to ISCC standards. In this embodiment, benzene containing recycled benzene is reacted with ethylene containing recycled ethylene in a catalytic reaction to produce ethylbenzene. Each hundred pounds of total feed contains 10 pounds of recycled benzene and 5 pounds of recycled ethylene. It has been previously calculated over discrete time periods that this reactor converts the benzene and ethylene feed into a mixture of ethylbenzene (95% by weight) plus 3% of other recovered products, with the remaining 2% by weight discarded. Therefore, in this embodiment, the calculated conversion factor for the reaction unit is 0.98 for the previous time period.

[0212] Therefore, the total ethylbenzene product obtained from 100 lbs of total feed is 95 lbs (100 lbs total feed × 95 wt%). Thus, the weight of recycled ethylbenzene attributable to recycled benzene and recycled ethylene can be calculated as 14.7 lbs [(10 lbs recycled benzene × 0.98 conversion factor) + (5 lbs recycled ethylene × 0.98 conversion factor)], and is certified as 14.7 lbs according to ISCC standards.

[0213] Therefore, these and other features or embodiments of this disclosure may be further included in the aspects of this disclosure set forth below.

[0214] This disclosure

[0215] Aspect 1. A process for recycling plastic waste, the process comprising:

[0216] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0217] (b) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0218] (c) Providing a separation unit feed to the separation unit, the separation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the steam cracker furnace effluent; and

[0219] (d) Separate the feed to the separation unit to provide a recycled product comprising ethylene effluent, propylene effluent and light (C2-C3) saturated hydrocarbon effluent.

[0220] Aspect 2. The process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas and the steam cracker effluent are combined to form the feed to the separation unit.

[0221] Aspect 3. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0222] The pyrolysis gas is compressed before at least a portion of it is fed into the separation unit.

[0223] Aspect 4. A process for recycling plastic waste, the process comprising:

[0224] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0225] (b) The pyrolysis gas is supplied to the condensation unit to form a first condenser effluent having a higher proportion of C4-C5 hydrocarbons than the pyrolysis gas and a second condenser effluent having a higher proportion of C2-C3 hydrocarbons than the pyrolysis gas;

[0226] (c) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent, the steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0227] (d) Providing a separation unit feed to the separation unit, the separation unit feed comprising at least a portion of the effluent from the second condenser and at least a portion of the effluent from the steam cracker furnace; and

[0228] (e) Separate the feed to the separation unit to provide a recycled product comprising ethylene effluent, propylene effluent and light (C2-C3) saturated hydrocarbon effluent.

[0229] Aspect 5. The process for recycling plastic waste according to aspect 4, wherein:

[0230] Prior to step (d), the effluent from the second condenser and the effluent from the steam cracker furnace are combined to form the feed for the separation unit.

[0231] Aspect 6. The process for recycling plastic waste according to any one of Aspects 4-5, said process further comprising the following steps:

[0232] At least a portion of the effluent from the first condenser is fed into the steam cracker furnace.

[0233] Aspect 7. A process for recycling plastic waste according to any one of Aspects 4-6, wherein:

[0234] Before being fed into the steam cracker, the first condenser effluent and the first feed stream are combined.

[0235] Aspect 8. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0236] (a') is the market price of the pyrolysis oil formed under the first set of pyrolysis conditions, which is equivalent to the market price of the reference liquid product.

[0237] (b') Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gases formed under the first set of pyrolysis conditions; and

[0238] (c')(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0239] Aspect 9. A process for recycling plastic waste, the process comprising:

[0240] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0241] (b) Assign a market price equivalent to the market price of the reference liquid product to the pyrolysis oil formed under the first set of pyrolysis conditions;

[0242] (c) Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gases formed under the first set of pyrolysis conditions; and

[0243] (d)(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0244] Aspect 10. A process for recycling plastic waste, the process comprising:

[0245] (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 and lighter (C1, C2, C3, C4 and C5) hydrocarbons, including ethylene, propylene and butene (EPB).

[0246] (b) A first feed stream is fed into a steam cracker furnace to produce a steam cracker furnace effluent comprising ethylene, propylene and light (C2-C3) saturated hydrocarbons;

[0247] (c) Feeding the separation unit to the separation unit, the separation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the steam cracker furnace effluent;

[0248] (d) is the market price of the pyrolysis oil formed under the first set of pyrolysis conditions, which is equivalent to the market price of the reference liquid product.

[0249] (e) Determine the market price of the combination of ethylene, propylene, and butene (EPB) in the pyrolysis gases formed under the first set of pyrolysis conditions; and

[0250] (f)(1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis reactor; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis reactor.

[0251] Aspect 11. A process for recycling plastic waste according to any one of Aspects 8-10, wherein assigning a market price to the pyrolysis oil includes assigning a market price to each fraction of the pyrolysis oil equal to the market price of an equivalent reference liquid product for each fraction.

[0252] Aspect 12. The process for recycling plastic waste according to aspect 11, wherein the market price of the pyrolysis oil includes a weighted average of equivalent reference liquid products for each fraction.

[0253] Aspect 13. A process for recycling plastic waste according to any one of Aspects 11-12, wherein the fraction of said pyrolysis oil comprises any combination of fractions selected from diesel, gasoline, naphtha, kerosene, gas oil and wax.

[0254] Aspect 14. A process for recycling plastic waste according to any one of Aspects 8-13, the process further comprising the step of tracking in real time the market price of the combined EPB and the market price of the reference liquid product.

[0255] Aspect 15. A process for recycling plastic waste according to any one of Aspects 8-14, wherein the reference liquid product comprises gasoline, diesel, or a blend of gasoline and diesel.

[0256] Aspect 16. A process for recycling plastic waste according to any one of Aspects 8-14, wherein the reference liquid product comprises a blend of gasoline and diesel having about 95% to 5% gasoline and about 5% to 95% diesel.

[0257] Aspect 17. A process for recycling plastic waste according to any one of Aspects 8-14, wherein the reference liquid product comprises a blend of gasoline and diesel having about 90% to 50% gasoline and about 10% to 50% diesel.

[0258] Aspect 18. A process for recycling plastic waste according to any one of Aspects 8-14, wherein the reference liquid product comprises a blend of gasoline and diesel having about 70% by weight gasoline and about 30% by weight diesel.

[0259] Aspect 19. A process for recycling plastic waste according to any one of Aspects 8-18, wherein the second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas relative to the pyrolysis oil in the effluent of the pyrolysis reactor.

[0260] Aspect 20. A process for recycling plastic waste according to any one of aspects 8-19, wherein the second set of pyrolysis conditions is applied to provide a pyrolysis reactor effluent having about 60% to about 85% pyrolysis gas and about 40% to about 15% pyrolysis liquid.

[0261] Aspect 21. A process for recycling plastic waste according to any one of aspects 8-19, wherein the second set of pyrolysis conditions is applied to provide a pyrolysis reactor effluent having about 75% to about 83% pyrolysis gas and about 25% to about 17% pyrolysis liquid.

[0262] Aspect 22. A process for recycling plastic waste according to any one of Aspects 8-21, wherein the second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas relative to the pyrolysis oil in the effluent of the pyrolysis reactor, and wherein the aromatic compound content of the pyrolysis oil produced under the second set of pyrolysis conditions is higher than that of the pyrolysis oil produced under the second set of pyrolysis conditions.

[0263] Aspect 23. A process for recycling plastic waste according to any one of Aspects 8-22, wherein the second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas relative to the pyrolysis oil in the effluent of the pyrolysis reactor, and wherein the wax content of the pyrolysis oil produced under the second set of pyrolysis conditions is lower than that produced under the second set of pyrolysis conditions.

[0264] Aspect 24. A process for recycling plastic waste according to any one of Aspects 8-18, wherein the second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil relative to the pyrolysis gas in the effluent of the pyrolysis reactor.

[0265] Aspect 25. The process for recycling plastic waste according to any one of Aspects 8-24, said process further comprising the following steps:

[0266] According to the International Sustainability and Carbon Certification (ISCC) standard, the pyrolysis oil, the pyrolysis gas, or any subsequent products generated using the pyrolysis oil or the pyrolysis gas are certified as circular based on the weight or fraction of the circular products attributable to the plastic waste, as determined by mass balance and free attribution methods.

[0267] Aspect 26. A process for recycling plastic waste according to any one of the preceding aspects, wherein the weight or fraction of the recycled products attributable to the pyrolysis gas or the plastic waste is determined by mass balance.

[0268] Aspect 27. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0269] According to the International Sustainable Development and Carbon Certification (ISCC) standard, any one or more of the recycled products from the separation unit are certified as recycled products based on the weight or fraction of the recycled products attributable to the pyrolysis gas or the plastic waste, as determined by mass balance and free attribution methods.

[0270] Aspect 28. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0271] At least a portion of the light (C2-C3) saturated hydrocarbon effluent is recycled back to the steam cracker.

[0272] Aspect 29. The process for recycling plastic waste according to aspect 28, wherein the light (C2-C3) saturated hydrocarbon effluent is treated to remove contaminants before at least a portion of the light saturated hydrocarbon effluent is recycled to the steam cracker.

[0273] Aspect 30. A process for recycling plastic waste according to any one of the preceding aspects, wherein the first feed stream comprises olefins and alkanes, and at least a portion of the olefins are removed from the first feed stream before the first feed stream is fed into the steam cracker furnace.

[0274] Aspect 31. The process for recycling plastic waste according to aspect 30, wherein the olefin is removed from the first feed stream by contacting the first feed stream with sulfolane.

[0275] Aspect 32. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis oil is recycled as a raw material or co-raw material to a refining unit.

[0276] Aspect 33. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis oil is recycled to a crude oil refining unit to produce recycled naphtha or recycled natural gas liquids (NGL).

[0277] Aspect 34. The process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit is co-located with the steam cracker furnace.

[0278] Aspect 35. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit is co-located with the separation unit.

[0279] Aspect 36. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit is located sufficiently close to the steam cracker furnace or the separation unit such that the pyrolysis unit, the steam cracker furnace and / or the separation unit are co-located within the same unit drawing space of the same operator.

[0280] Aspect 37. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit is located sufficiently close to the steam cracker furnace or the separation unit such that the C2-C3 fraction of the pyrolysis gas or the second condenser effluent can be supplied to the steam cracker furnace without additional compression or piping.

[0281] Aspect 38. A process for recycling plastic waste according to any one of the preceding aspects, wherein the C2-C3 fraction of the pyrolysis gas or the second condenser effluent is not compressed and is transported via pipeline to the steam cracker furnace.

[0282] Aspect 39. A process for recycling plastic waste according to any one of Aspects 1-37, wherein the C2-C3 fraction of the pyrolysis gas or the second condenser effluent is compressed and transported via pipeline to the steam cracker furnace.

[0283] Aspect 40. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0284] At least a portion of the pyrolysis oil from the pyrolysis unit is fed into the steam cracker furnace.

[0285] Aspect 41. A process for recycling plastic waste according to any one of the preceding aspects, wherein the first feed stream leading to the steam cracker furnace comprises liquefied petroleum gas (LPG), natural gas liquefaction (NGL), light (C2-C5) hydrocarbons, or naphtha (C6-C5) oil. 10 ).

[0286] Aspect 42. The process for recycling plastic waste according to any one of the preceding aspects, wherein the steam cracker feed comprises naphtha (C6-C) 10 ) and the pyrolysis oil.

[0287] Aspect 43. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0288] At least a portion of the ethylene effluent is fed to one or more downstream processing units to provide a recycled product selected from: such as n-α-olefins (C4-C5). 30+ α-olefins, ethylene homopolymers, ethylene-α-olefin copolymers, and ethylene-n-α-olefins (C4-C5) 30 +) copolymers, ethylene-propylene copolymers, ethylene-ionomer copolymers, chlorosulfonated polyethylene, vinyl chloride, ethylene oxide, ethylbenzene, acetaldehyde, vinyl acetate or polyvinyl acetate.

[0289] Aspect 44. The process for recycling plastic waste according to aspect 43, wherein:

[0290] The one or more downstream processing units provide recycled vinyl chloride, and

[0291] The recycled vinyl chloride is fed to one or more subsequent processing units to provide a recycled product selected from: polyvinyl chloride homopolymer, polyvinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, 1,1,2-trichloroethane, vinylidene chloride, or polyvinylidene chloride.

[0292] Aspect 45. The process for recycling plastic waste according to aspect 43, wherein:

[0293] The one or more downstream processing units provide recycled ethylene oxidation, and

[0294] The recycled ethylene oxide is fed to one or more subsequent processing units to provide a recycled product selected from: ethylene glycol, poly(ethylene terephthalate), polyethylene glycol-polyalkylene glycol copolymer, ethoxylated phenol, ethoxylated amine, diethylene glycol, polyester, unsaturated polyester, polyester polyol, adipic acid, polyurethane resin, hydroxyethyl starch, hydroxyethyl gum, or hydroxyethyl cellulose.

[0295] Aspect 46. The process for recycling plastic waste according to aspect 43, wherein:

[0296] The one or more downstream processing units provide recycled ethylbenzene, and

[0297] The recycled ethylbenzene is fed to one or more subsequent processing units to provide a recycled product selected from: styrene, polystyrene, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene terpolymer, styrene-acrylonitrile copolymer, polyester resin, styrene-divinylbenzene resin, styrene-alkyd copolymer, or styrene-maleic anhydride copolymer.

[0298] Aspect 47. The process for recycling plastic waste according to aspect 43, wherein:

[0299] The one or more downstream processing units provide recycled acetaldehyde, and

[0300] The recycled acetaldehyde is fed to one or more subsequent processing units to provide a recycled product selected from pentaerythritol, alkyd resin, or acetic acid.

[0301] Aspect 48. The process for recycling plastic waste according to aspect 43, wherein:

[0302] The one or more downstream processing units provide recycled vinyl acetate, and

[0303] The recycled vinyl acetate is fed to one or more subsequent processing units to provide a recycled product selected from: poly(vinyl acetate), poly(vinyl acetate) copolymer, ethylene-vinyl acetate copolymer, or vinyl chloride-vinyl acetate copolymer.

[0304] Aspect 49. The process for recycling plastic waste according to aspect 43, wherein:

[0305] The one or more downstream processing units provide recycled poly(vinyl acetate), and

[0306] The recycled poly(vinyl acetate) is fed to one or more subsequent processing units to provide a recycled product selected from poly(vinyl alcohol), poly(vinyl butyral), and poly(vinyl alcohol formaldehyde).

[0307] Aspect 50. The process for recycling plastic waste according to aspect 43, wherein:

[0308] The one or more downstream processing units provide recycled α-olefins, and

[0309] The recycled α-olefin is fed to one or more subsequent processing units to provide a recycled product selected from poly-α-olefins or poly(ethylene-co-α-olefins).

[0310] Aspect 51. The process for recycling plastic waste according to aspect 43, wherein:

[0311] The one or more downstream processing units provide recycled n-α olefins (C4-C5). 30 +), and

[0312] The cyclic α-olefin (C4-C) 30 +) Feed to one or more subsequent processing units to provide a recycled product selected from poly(n-α olefin) or poly(ethylene-co-(n-α olefin)).

[0313] Aspect 52. The process for recycling plastic waste according to aspect 43, wherein:

[0314] The cyclic α-olefin is selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene, and

[0315] The recycled products are selected from poly(ethylene-co-1-butene), poly(ethylene-co-1-pentene), poly(ethylene-co-1-hexene), poly(ethylene-co-1-heptene), poly(ethylene-1-octene), poly(ethylene-1-nonene), poly(ethylene-1-decene), poly(ethylene-1-dodecene), poly(ethylene-1-tetradecene), poly(ethylene-co-1-hexadecene), or poly(ethylene-co-1-octadecene).

[0316] Aspect 53. The process for recycling plastic waste according to any one of Aspects 1-52, said process further comprising the following steps:

[0317] At least a portion of the ethylene effluent is fed as feed to the polymerization reactor to form recycled polyethylene.

[0318] Aspect 54. A process for recycling plastic waste according to any one of Aspects 1-52, said process further comprising the following steps:

[0319] At least a portion of the ethylene effluent is provided as feed for a catalytic reaction with benzene to form recycled ethylbenzene.

[0320] Aspect 55. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0321] At least a portion of the ethylene effluent is provided as feed for a catalytic reaction to form a recycled n-α olefin.

[0322] Aspect 56. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0323] At least a portion of the ethylene effluent is fed as a feed to a polymerization reactor for a catalytic reaction with n-α-olefins to form a recycled ethylene-α-olefin copolymer.

[0324] Aspect 57. A process for recycling plastic waste according to any one of aspects 43-56, wherein the weight or fraction of the recycled products attributable to the pyrolysis gas or the plastic waste is determined by mass balance.

[0325] Aspect 58. A process for recycling plastic waste according to any one of aspects 43-57, said process further comprising the following steps:

[0326] According to the International Sustainability and Carbon Certification (ISCC) standard, any one or more of the circular products are certified based on the weight or fraction of the circular products attributable to the pyrolysis gas or the plastic waste, as determined by mass balance and free attribution methods.

[0327] Aspect 59. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0328] At least a portion of the propylene effluent is fed to one or more downstream processing units to provide a recycled product selected from: polypropylene homopolymer, polypropylene copolymer, acrylonitrile, propylene oxide, cumene, n-butyraldehyde, isobutyraldehyde, allyl chloride, acrylate, or isopropanol.

[0329] Aspect 60. The process for recycling plastic waste according to aspect 59, wherein:

[0330] The one or more downstream processing units provide recycled acrylonitrile, and

[0331] The recycled acrylonitrile is fed to one or more subsequent processing units to provide a recycled product selected from: polyacrylonitrile, modified polyacrylonitrile copolymer, acrylonitrile butadiene styrene (ABS), styrene-acrylonitrile resin (SAN), nitrile elastomer, acrylonitrile copolymer, hexamethylenediamine, nylon 6,6, acrylamide, polyacrylamide homopolymer, or polyacrylamide copolymer.

[0332] Aspect 61. The process for recycling plastic waste according to aspect 59, wherein:

[0333] The one or more downstream processing units provide cyclic propylene oxidation, and

[0334] The recycled propylene oxide is fed to one or more subsequent processing units to provide a recycled product selected from propylene glycol, polyester, poly(propylene glycol) homopolymer, poly(propylene glycol) copolymer, or polyurethane.

[0335] Aspect 62. The process for recycling plastic waste according to aspect 59, wherein:

[0336] The one or more downstream processing units provide recycled n-butyraldehyde, and

[0337] The recycled n-butyraldehyde is fed to one or more subsequent processing units to provide a recycled product selected from poly(vinyl butyral), n-butyric acid, n-butyric anhydride, or cellulose acetate butyrate.

[0338] Aspect 63. The process for recycling plastic waste according to aspect 59, wherein:

[0339] The one or more downstream processing units provide recycled isobutyraldehyde, and

[0340] The recycled isobutyraldehyde is fed to one or more subsequent processing units to provide a recycled product selected from neopentyl glycol, polyester, or polyurethane.

[0341] Aspect 64. The process for recycling plastic waste according to aspect 59, wherein:

[0342] The one or more downstream processing units provide recycled allyl chloride, and

[0343] The recycled allyl chloride is fed to one or more subsequent processing units to provide a recycled product selected from epichlorohydrin or epoxy resin.

[0344] Aspect 65. The process for recycling plastic waste according to aspect 59, wherein:

[0345] The one or more downstream processing units provide recycled acrylate, and

[0346] The recycled acrylate is fed to one or more subsequent processing units to provide a recycled product selected from acrylic homopolymers or copolymers.

[0347] Aspect 66. The process for recycling plastic waste according to aspect 59, wherein:

[0348] The one or more downstream processing units provide recycled isopropanol, and

[0349] The recycled isopropanol is fed to one or more subsequent processing units to provide a recycled product selected from the following: acetone, bisphenol A, epoxy resin, polycarbonate, polysulfone, methacrylic acid, poly(methyl methacrylate) homopolymer or poly(methyl methacrylate) copolymer.

[0350] Aspect 67. The process for recycling plastic waste according to any one of the preceding aspects, said process further comprising the following steps:

[0351] At least a portion of the propylene effluent is fed as feed to the polymerization reactor to form recycled polypropylene.

[0352] Aspect 68. A process for recycling plastic waste according to any one of aspects 59-67, wherein the weight or fraction of the recycled products attributable to the pyrolysis gas or the plastic waste is determined by mass balance.

[0353] Aspect 69. A process for recycling plastic waste according to any one of aspects 59-68, said process further comprising the following steps:

[0354] According to the International Sustainability and Carbon Certification (ISCC) standard, any one or more of the circular products are certified based on the weight or fraction of the circular products attributable to the pyrolysis gas or the plastic waste, as determined by mass balance and free attribution methods.

[0355] Aspect 70. A process for recycling plastic waste according to any one of the preceding aspects, wherein the separation step provides a recycled product further comprising butene and butane effluent, the process further comprising the following steps:

[0356] At least a portion of the butene and butane effluents is fed to one or more downstream processing units to provide a recycled product selected from: recycled butadiene, maleic anhydride, butene oxide, 1-butene, mixed butene, isobutene, or butane.

[0357] Aspect 71. The process for recycling plastic waste according to aspect 70, wherein:

[0358] The one or more downstream processing units provide recycled n-diene, and

[0359] The recycled butadiene is fed to one or more subsequent processing units to provide a recycled product selected from: recycled styrene, polybutadiene elastomers, polybutadiene resins, hexamethylenediamine, nylon, chloroprene, chloroprene rubber elastomers, 1,5-cyclooctadiene, ethylene-propylene terpolymer elastomers, 1,5,9-cyclododecanetriene, dodecanoic acid, nylon 6,12, quaana, lauryl lactam, nylon 12, OH-terminated polymers and copolymers, polyurethane elastomers, or 1,4-hexadiene.

[0360] Aspect 72. The process for recycling plastic waste according to aspect 70, wherein:

[0361] The one or more downstream processing units provide recycled maleic anhydride, and

[0362] The recycled maleic anhydride is fed to one or more subsequent processing units to provide a recycled product selected from recycled polyesters, alkyd resins, or styrene-maleic anhydride copolymers.

[0363] Aspect 73. The process for recycling plastic waste according to aspect 70, wherein:

[0364] The one or more downstream processing units provide recycled butene oxidation, and

[0365] The recycled butene oxide is fed to one or more subsequent processing units to provide a recycled product selected from recycled poly(butene oxide) or polyurethane.

[0366] Aspect 74. The process for recycling plastic waste according to aspect 70, wherein:

[0367] The one or more downstream processing units provide recycled 1-butene, mixed butene, and isobutene, and

[0368] The recycled 1-butene, mixed butene, and isobutene are fed into one or more subsequent processing units to provide a recycled product selected from recycled poly(1-butene), poly(butene), poly(isobutene), or butyl rubber.

[0369] Aspect 75. The process for recycling plastic waste according to aspect 70, wherein:

[0370] The one or more downstream processing units provide recycled butane, and

[0371] The recycled butane is fed to one or more subsequent processing units to provide a recycled product selected from recycled acetic acid.

[0372] Aspect 76. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit is operated under conditions selected to increase, optimize, or maximize the ratio of pyrolysis gas in the pyrolysis unit effluent to pyrolysis liquid in the pyrolysis unit effluent.

[0373] Aspect 77. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit is operated under conditions selected to increase, optimize, or maximize the ratio of the C2-C3 fraction of the pyrolysis gas to the C4-C5 fraction of the pyrolysis gas.

[0374] Aspect 78. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit is operated under conditions selected to increase, optimize, or maximize the proportion of ethylene in the pyrolysis gas.

[0375] Aspect 79. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas is selected to increase, optimize, or maximize the C5 and lighter (C6) content. ≤5 Hydrocarbons relative to C6 and any heavier (C6) hydrocarbons ≥6 The pyrolysis unit is operated under conditions of a certain proportion of hydrocarbons.

[0376] Aspect 80. A process for recycling plastic waste according to any one of the preceding aspects, wherein the plastic waste is processed in the pyrolysis unit at a temperature of about 450°C to about 800°C.

[0377] Aspect 81. A process for recycling plastic waste according to any one of the preceding aspects, wherein the plastic waste is processed in the pyrolysis unit at a temperature of about 600°C to about 800°C.

[0378] Aspect 82. A process for recycling plastic waste according to any one of the preceding aspects, wherein the plastic waste is processed under catalytic conditions in the presence of a catalyst in the pyrolysis unit.

[0379] Aspect 83. A process for recycling plastic waste according to any one of the preceding aspects, wherein the plastic waste is processed in the pyrolysis unit under catalytic conditions using a catalyst comprising alumina, aluminosilicate (e.g., zeolite or silica-alumina), silica-alumina-phosphate, transition metal oxide (e.g., titanium oxide, zirconium oxide, hafnium oxide or niobium oxide), polyoxometalates, heteropolyoxometalates, polystyrene sulfonate resin, sulfonated carbon, solid phosphoric acid or niobic acid.

[0380] Aspect 84. A process for recycling plastic waste according to any one of the preceding aspects, wherein the plastic waste is processed in the pyrolysis unit under non-catalytic conditions in the absence of a catalyst.

[0381] Aspect 85. The process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit operates continuously.

[0382] Aspect 86. The process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis unit operates intermittently.

[0383] Aspect 87. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas contains about 15% by weight to about 40% by weight of ethylene, or alternatively about 18% by weight to about 38% by weight of ethylene.

[0384] Aspect 88. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas comprises about 25% by weight to about 60% by weight of C2 hydrocarbons (ethane and ethylene), or alternatively about 30% by weight to about 55% by weight of C2 hydrocarbons.

[0385] Aspect 89. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas contains about 15% to about 35% propylene, or alternatively about 17% to about 32% propylene.

[0386] Aspect 90. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas comprises about 17% by weight to about 45% by weight of C3 hydrocarbons (propane and propylene), or alternatively about 20% by weight to about 42% by weight of C3 hydrocarbons.

[0387] Aspect 91. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas is purified before the separation unit containing the pyrolysis gas is fed into the separation unit.

[0388] Aspect 92. A process for recycling plastic waste according to any one of the preceding aspects, wherein the plastic waste includes polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyamide, polycarbonate, polyurethane, polyester, copolymers thereof, filled polymers thereof, complexes thereof, natural or synthetic rubber, tires, or any combination thereof.

[0389] Aspect 93. A process for recycling plastic waste according to any one of the preceding aspects, wherein the plastic waste comprises a chlorinated polymer, and at least a portion of the chlorinated polymer has been removed from the plastic waste prior to pyrolysis of the plastic waste in the pyrolysis unit.

[0390] Aspect 94. A process for recycling plastic waste according to any one of the preceding aspects, wherein the plastic waste comprises polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET), polyamide, polycarbonate, polyurethane, or polyester.

[0391] Aspect 95. The process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas or the pyrolysis oil contains non-hydrocarbon contaminants.

[0392] Aspect 96. A process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas or the pyrolysis oil contains non-hydrocarbon contaminants selected from inorganic acids, organic acids, binary compounds of Group 15 elements and hydrogen, binary compounds of Group 16 elements and hydrogen, organic compounds containing Group 15 elements, or organic compounds containing Group 16 elements.

[0393] Aspect 97. The process for recycling plastic waste according to any one of the preceding aspects, wherein the pyrolysis gas or the pyrolysis oil contains non-hydrocarbon contaminants selected from: HCl, HBr, phosphine, arsine, antimony, alcohols, organic acids, nitrogen oxides, chloroform, C1-C3 hydrocarbon chlorides or C1-C3 hydrocarbon fluorides.

[0394] Aspect 98. A process for recycling plastic waste according to any one of the preceding aspects, wherein (a) the pyrolysis gas is pretreated with a caustic alkali or an amine before being fed to the separation unit or (b) the pyrolysis gas is fed to the condensation unit.

[0395] Aspect 99. A process for recycling plastic waste according to any one of the preceding aspects, wherein (a) the pyrolysis gas is pretreated with a metal oxide catalyst bed before being fed to the separation unit or (b) the pyrolysis gas is fed to the condensation unit.

[0396] Aspect 100. The process for recycling plastic waste according to aspect 99, wherein the metal oxide catalyst bed is selected from zinc oxide, calcium oxide or iron oxide.

[0397] Aspect 101. A process for recycling plastic waste according to any one of the preceding aspects, wherein (a) the pyrolysis gas is pretreated with a molecular sieve or promoted or activated alumina before being fed to the separation unit or (b) the pyrolysis gas is fed to the condensation unit.

[0398] Aspect 102. The process for recycling plastic waste according to any one of the preceding aspects, the process further comprising the step of: feeding at least a portion of the ethylene effluent into a polymerization reactor to form recycled polyethylene,

[0399] The amount of recycled polyethylene produced is at least 10% higher than that produced in a corresponding process using only liquid pyrolysis effluent feedstock, as quantified by the percentage (%) of gas production from the pyrolysis unit per unit weight of plastic feed.

[0400] Aspect 103. The process for recycling plastic waste according to aspect 102, wherein the amount of recycled polyethylene produced is at least 15% higher than that produced in a corresponding process using only liquid pyrolysis effluent feedstock, as quantified by the percentage (%) of gas yield from the pyrolysis unit per unit weight of plastic feed.

[0401] Aspect 104. The process for recycling plastic waste according to aspect 103, wherein the amount of recycled polyethylene produced is about 10% to about 25% higher than that produced in a corresponding process using only liquid pyrolysis effluent feedstock, as quantified by the percentage (%) of gas yield from said pyrolysis unit per unit weight of plastic feedstock.

[0402] Aspect 105. A process for recycling plastic waste according to any one of Aspects 1-104, wherein the carbon footprint of any independently selected recycled product is reduced by about 15% to about 40% compared to the carbon footprint of the corresponding non-recycled product generated in the absence of the pyrolysis gas and the pyrolysis oil.

[0403] Aspect 106. A process for recycling plastic waste according to any one of Aspects 1-104, wherein the carbon footprint of any independently selected recycling product is reduced by about 20% to about 35% compared to the carbon footprint of the corresponding non-recycling product generated in the absence of the pyrolysis gas and the pyrolysis oil.

[0404] Aspect 107. A process for recycling plastic waste according to any one of Aspects 1-104, wherein the carbon footprint of any independently selected recycling product is reduced by about 25% to about 30% compared to the carbon footprint of the corresponding non-recycling product generated in the absence of the pyrolysis gas and the pyrolysis oil.

[0405] Aspect 108. A process for recycling plastic waste according to any one of Aspects 1-107, wherein the plastic waste is pyrolyzed in an amount of up to about 5% by weight of the original feedstock required to produce equal amounts of the ethylene effluent, the propylene effluent and the light (C2-C3) saturated hydrocarbon effluent.

[0406] Aspect 109. A process for recycling plastic waste according to any one of Aspects 1-107, wherein the plastic waste is pyrolyzed in an amount of about 1% to about 10% by weight of the original feedstock required to produce the same amount of the ethylene effluent, the propylene effluent and the light (C2-C3) saturated hydrocarbon effluent.

[0407] Aspect 110. A process for recycling plastic waste according to any one of Aspects 1-107, wherein the plastic waste is pyrolyzed in an amount sufficient to provide feed to the separation unit of up to about 5% by weight.

[0408] Aspect 111. A process for recycling plastic waste according to any one of Aspects 1-107, wherein the plastic waste is pyrolyzed in an amount sufficient to provide feed to the separation unit from about 1% to about 10% by weight.

[0409] Aspect 112. A process for recycling plastic waste, the process comprising:

[0410] (a) Pyrolyzing plastic waste in a pyrolysis unit to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil, and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 fractions having C2-C3 fractions and C4-C5 fractions, and lighter (C5 and C4-C5 fractions). C≤5 )hydrocarbon;

[0411] (b) A heavy hydrocarbon feed stream is fed into a fluidized catalytic cracking (FCC) reactor to produce an FCC effluent containing naphtha (C6-C4). 10 Hydrocarbons) and C5 and lighter (C ≤5 )hydrocarbon;

[0412] (c) Providing a fractionation unit feed to the fractionation unit, the fractionation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the FCC effluent; and

[0413] (d) Separating the feed from the fractionation unit to provide a recycled product, the recycled product comprising: C5 and lighter (C5) compounds. ≤5 The first fraction of hydrocarbons and the effluent containing heavy hydrocarbons (C 6+ The second fraction of hydrocarbon effluent.

[0414] Aspect 113. The process for recycling plastic waste according to aspect 112, wherein the pyrolysis gas is fed directly into the fractionation unit.

[0415] Aspect 114. The process for recycling plastic waste according to aspect 112, wherein the FCC effluent and the pyrolysis gas are combined to form the fractionation unit feed, and then the fractionation unit feed is fed into the fractionation unit.

[0416] Aspect 115. A process for recycling plastic waste according to any one of Aspects 112-114, wherein the heavy hydrocarbon feed stream is fed to a fluidized catalytic cracker (FCC) preprocessor to form a treated stream, and then the treated stream is fed to the FCC reactor.

[0417] Aspect 116. The process for recycling plastic waste according to aspect 115, wherein the treated stream has a lower sulfur content, a lower aromatic compound content, or both, compared to the sulfur content and / or aromatic compound content in the heavy hydrocarbon feed stream.

[0418] Aspect 117. A process for recycling plastic waste according to any one of Aspects 112-116, wherein the feed to the fractionation unit further comprises at least a portion of the pyrolysis oil.

[0419] Aspect 118. A process for recycling plastic waste according to any one of aspects 112-117, said process further comprising the following steps:

[0420] Make the heavy substance (C) 6+ At least a portion of the second fractionation effluent of the hydrocarbon is recycled to the fluidized catalytic cracker (FCC) reactor.

[0421] Aspect 119. A process for recycling plastic waste according to any one of Aspects 112-117, said process further comprising the following steps:

[0422] The substance containing heavy matter (C) 6+ At least a portion of the second fraction effluent from the hydrocarbon is fed into the reforming unit or Units, respectively, to provide respective reformate streams containing recycled aromatics or Product flow.

[0423] Aspect 120. The process for recycling plastic waste according to aspect 119, wherein:

[0424] The reforming product stream or the The product stream contains recycled benzene, and

[0425] The recycled benzene is fed to one or more subsequent processing units to provide a recycled product selected from ethylbenzene, benzenesulfonic acid, chlorobenzene, cumene, cyclohexane, nitrobenzene, or maleic anhydride.

[0426] Aspect 121. The process for recycling plastic waste according to aspect 119, wherein:

[0427] The reforming product stream or the The product stream contains recycled toluene, and

[0428] The recycled toluene is fed to one or more subsequent processing units to provide a recycled product selected from dinitrotoluene, toluene diisocyanate, or carbamate.

[0429] Aspect 122. The process for recycling plastic waste according to aspect 119, wherein:

[0430] The reforming product stream or the The product stream contains recycled o-xylene, and

[0431] The recycled o-xylene is fed to one or more subsequent processing units to provide a recycled product selected from phthalic anhydride, alkyd resin, polyester resin, polyester polyol, urethane, or polyurethane.

[0432] Aspect 123. The process for recycling plastic waste according to aspect 119, wherein:

[0433] The reforming product stream or the The product stream contains recycled m-xylene, and

[0434] The recycled m-xylene is fed to one or more subsequent processing units to provide a recycled product selected from isophthalic acid, polyester, alkyd resin, polyamide resin, diphenyl isophthalate, or polybenzimidazole.

[0435] Aspect 124. The process for recycling plastic waste according to aspect 119, wherein:

[0436] The reforming product stream or the The product stream contains recycled p-xylene, and

[0437] The recycled p-xylene is fed to one or more subsequent processing units to provide a recycled product selected from terephthalic acid, polyethylene terephthalate, or polybutylene terephthalate.

[0438] Aspect 125. A process for recycling plastic waste according to any one of aspects 119-124, wherein the reformed product stream or the The product stream further contains hydrogen and aliphatic hydrocarbons.

[0439] Aspect 126. A process for recycling plastic waste according to any one of aspects 119-125, wherein the reformed product stream or the The fraction of aromatic hydrocarbons in the product stream that belong to the plastic waste or pyrolysis gases.

[0440] Aspect 127. A process for recycling plastic waste according to any one of Aspects 119-126, wherein the fractions of benzene, toluene, o-xylene, m-xylene, p-xylene, or any recycling products attributable to the plastic waste or the pyrolysis gases generated in the one or more subsequent processing units are determined by mass balance.

[0441] Aspect 128. A process for recycling plastic waste according to any one of Aspects 119-127, said process further comprising the step of: certifying benzene, toluene, o-xylene, m-xylene, p-xylene or any recycled product attributable to said plastic waste or said pyrolysis gas as recycled, based on the weight or fraction of said recycled products attributable to said plastic waste as determined by mass balance and free attribution methods, according to the International Sustainable Development and Carbon Certification (ISCC) standard.

[0442] Aspect 129. A process for recycling plastic waste according to any one of Aspects 112-128, said process further comprising the step of: dissolving C5 and lighter (C5) plastic waste in a container. ≤5 At least a portion of the first fractionated effluent of the hydrocarbon is fed into a steam cracker to form a steam cracker product stream comprising ethylene and light (C2-C3) saturated hydrocarbons.

[0443] Aspect 130. The process for recycling plastic waste according to aspect 129, the process further comprising the following steps:

[0444] The product stream from the steam cracker is fed into the separation unit; and

[0445] The feed to the separation unit is separated to provide ethylene effluent, propylene effluent and light (C2-C3) saturated hydrocarbon effluent.

[0446] Aspect 131. The process for recycling plastic waste according to aspect 130, the process further comprising the following steps:

[0447] At least a portion of the ethylene effluent or the propylene effluent is fed into a polymerization reactor to form recycled polyethylene or recycled polypropylene.

[0448] Aspect 132. A process for recycling plastic waste according to any one of Aspects 130-131, wherein the fractions of ethylene, propylene, polyethylene, or polypropylene in the ethylene effluent attributable to the plastic waste or the pyrolysis gas are determined by mass balance.

[0449] Aspect 131. A process for recycling plastic waste according to any one of Aspects 130-132, said process further comprising the following steps:

[0450] At least a portion of the light (C2-C3) saturated hydrocarbon effluent is recycled back to the steam cracker.

Claims

1. A process for recycling plastic waste, the process comprising: (a) Pyrolyzing plastic waste in a pyrolysis unit under a first set of pyrolysis conditions to produce a pyrolysis unit effluent containing pyrolysis gas and pyrolysis oil in a known ratio and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas contains C5 and lighter hydrocarbons, including ethylene, propylene and butene, the ethylene, propylene and butene being referred to as EPB; (b) The pyrolysis gas is supplied to a condensation unit to form a first condenser effluent having a higher proportion of C4-C5 hydrocarbons than the pyrolysis gas and a second condenser effluent having a higher proportion of C2-C3 hydrocarbons than the pyrolysis gas; (c) Feeding the first feed stream and at least a portion of the pyrolysis oil into a steam cracker furnace to produce a steam cracker furnace effluent comprising ethylene, propylene and light C2-C3 saturated hydrocarbons; (d) Feeding the separation unit to the separation unit, the separation unit feed comprising at least a portion of the effluent from the second condenser and at least a portion of the effluent from the steam cracker furnace; (e) Separating the feed to the separation unit to provide a recycled product comprising ethylene effluent, propylene effluent, and light C2-C3 saturated hydrocarbon effluent; and (f) Recycle at least a portion of the light C2-C3 saturated hydrocarbon effluent to the steam cracker furnace.

2. The process for recycling plastic waste according to claim 1, the process further comprising feeding at least a portion of the effluent from the first condenser into the steam cracker furnace.

3. The process for recycling plastic waste according to claim 2, wherein the first condenser effluent and the first feed stream are combined before being fed to the steam cracker furnace.

4. The process for recycling plastic waste according to claim 1, 2, or 3, the process further comprising the following steps: (a') is a market price that is equivalent to the market price of the reference liquid product for the pyrolysis oil formed under the first set of pyrolysis conditions; (b') Determine the market price of the combination of EPB in the pyrolysis gases formed under the first set of pyrolysis conditions; and (c') (1) When the market price of the combined EPB is higher than the market price of the pyrolysis oil, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis gas to pyrolysis oil in the effluent of the pyrolysis unit; or (2) When the market price of the pyrolysis oil is higher than the market price of the combined EPB formed under the first set of conditions, a second set of pyrolysis conditions is applied to increase the proportion of pyrolysis oil to pyrolysis gas in the effluent of the pyrolysis unit.

5. The process for recycling plastic waste according to claim 4, wherein the pyrolysis oil comprises multiple fractions, and assigning a market price to the pyrolysis oil includes assigning a market price to each fraction of the pyrolysis oil equal to the market price of an equivalent reference liquid product for each fraction.

6. The process for recycling plastic waste according to claim 5, wherein the market price of the pyrolysis oil comprises a weighted average of the equivalent reference liquid product for each fraction.

7. The process for recycling plastic waste according to claim 5, wherein the fraction of the pyrolysis oil comprises any combination of fractions selected from diesel, gasoline, naphtha, kerosene, gas oil, and wax.

8. The process for recycling plastic waste according to claim 4, wherein the reference liquid product comprises gasoline, diesel, or a blend of gasoline and diesel.

9. The process for recycling plastic waste according to claim 4, wherein the reference liquid product comprises a blend of gasoline and diesel having 95% to 5% gasoline and 5% to 95% diesel.

10. The process for recycling plastic waste according to claim 1, wherein a portion of the pyrolysis oil is recycled as a feedstock or co-feedstock to a refining unit or to a crude oil refining unit to produce recycled naphtha or recycled natural gas liquid.

11. The process for recycling plastic waste according to claim 1, wherein the pyrolysis unit is co-located with the steam cracker furnace.

12. The process for recycling plastic waste according to claim 1, wherein the first feed stream leading to the steam cracker furnace comprises liquefied petroleum gas, liquid natural gas, light C2-C5 hydrocarbons, or naphtha C6-C5 hydrocarbons. 10 .

13. The process for recycling plastic waste according to claim 1, the process further comprising the following steps: At least a portion of the ethylene effluent is fed to one or more downstream processing units to provide a recycled product selected from: α-olefins, ethylene homopolymers, ethylene-α-olefin copolymers, ethylene-ionomer copolymers, chlorosulfonated polyethylene, vinyl chloride, ethylene oxide, ethylbenzene, acetaldehyde, vinyl acetate, or polyvinyl acetate.

14. The process for recycling plastic waste according to claim 13, wherein the recycled product is selected from C4-C. 30+ n-α-olefins or Ethylene - C4-C 30 +α-olefin copolymer.

15. The process for recycling plastic waste according to claim 13, wherein the recycling product is an ethylene-propylene copolymer.

16. The process for recycling plastic waste according to claim 13, wherein: The one or more downstream processing units provide a recycled α-olefin selected from the following: 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene; and The recycled α-olefin is fed to one or more subsequent processing units to provide a recycled product selected from poly-α-olefin or ethylene-α-olefin copolymers.

17. The process for recycling plastic waste according to claim 1, the process further comprising the following steps: At least a portion of the ethylene effluent is provided as feed for a catalytic reaction to form recycled polyethylene, recycled ethylbenzene, recycled n-alpha olefin, or recycled ethylene-alpha olefin copolymer.

18. The process for recycling plastic waste according to claim 1, the process further comprising the following steps: At least a portion of the propylene effluent is fed to one or more downstream processing units to provide a recycled product selected from: polypropylene homopolymer, polypropylene copolymer, acrylonitrile, propylene oxide, cumene, n-butyraldehyde, isobutyraldehyde, allyl chloride, acrylate, or isopropanol.

19. The process for recycling plastic waste according to claim 1, wherein the separation step provides a recycled product further comprising butene and butane effluent, the process further comprising the following steps: At least a portion of the butene and butane effluents is fed to one or more downstream processing units to provide a recycled product selected from: recycled butadiene, maleic anhydride, butene oxide, 1-butene, mixed butene, isobutene, or butane.

20. The process for recycling plastic waste according to claim 1, wherein the pyrolysis unit is operated under conditions selected to increase the ratio of pyrolysis gas in the pyrolysis unit effluent to pyrolysis liquid in the pyrolysis unit effluent.

21. The process for recycling plastic waste according to claim 1, wherein the plastic waste is processed in the pyrolysis unit at a temperature of 450°C to 800°C.

22. The process for recycling plastic waste according to claim 1, wherein the plastic waste is processed in the pyrolysis unit under catalytic conditions in the presence of a catalyst, said catalyst comprising alumina, aluminosilicate, silica-alumina-phosphate, transition metal oxide, polyoxometalate, heteropolyoxometalate, polystyrene sulfonate resin, sulfonated carbon, solid phosphoric acid, or niobic acid.

23. The process for recycling plastic waste according to claim 22, wherein the aluminosilicate is selected from zeolite or silica-alumina.

24. The process for recycling plastic waste according to claim 22, wherein the transition metal oxide is selected from titanium oxide, zirconium oxide, hafnium oxide, or niobium oxide.

25. The process for recycling plastic waste according to claim 1, wherein the plastic waste includes polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyamide, polycarbonate, polyurethane, polyester, copolymers thereof, filled polymers thereof, complexes thereof, natural or synthetic rubber, tires, or any combination thereof.

26. The process for recycling plastic waste according to claim 1, the process further comprising the following steps: At least a portion of the ethylene effluent is fed into a polymerization reactor to form recycled polyethylene. The amount of recycled polyethylene produced is at least 10% higher than that produced in a corresponding process using only liquid pyrolysis effluent feedstock, quantified as a percentage of gas production per unit weight of plastic feed through the pyrolysis unit.

27. The process for recycling plastic waste according to claim 1, wherein the weight or fraction of the recycled products attributable to the pyrolysis gas or the plastic waste is determined by mass balance.

28. The process for recycling plastic waste according to claim 1, the process further comprising the following steps: According to international sustainability and carbon certification standards, any one or more of the recycled products from the separation unit are certified as recycled products based on the weight or fraction of the recycled products attributable to the pyrolysis gas or the plastic waste, as determined by mass balance and free attribution methods.

29. A process for recycling plastic waste, the process comprising: (a) Pyrolyzing plastic waste in a pyrolysis unit to produce a pyrolysis unit effluent comprising pyrolysis gas and pyrolysis oil, and separating the pyrolysis gas from the pyrolysis oil, wherein the pyrolysis gas comprises C5 having C2-C3 fractions and C4-C5 fractions, and lighter C... ≤5 hydrocarbon; (b) A heavy hydrocarbon feed stream is fed into a fluidized catalytic cracker (FCC) reactor to produce an FCC effluent containing naphtha C6-C. 10 Hydrocarbons and C5 and lighter C ≤5 hydrocarbon; (c) Providing a fractionation unit feed to the fractionation unit, the fractionation unit feed comprising at least a portion of the pyrolysis gas and at least a portion of the FCC effluent; and (d) Separate the feed from the fractionation unit to provide a recycled product comprising: C5 and lighter C ≤5 The first fraction of hydrocarbons and the effluent containing heavy C 6+ The second fractionated effluent of hydrocarbons; (e) The pyrolysis gas is supplied to the condensation unit to form a first condenser effluent having a higher proportion of C4-C5 hydrocarbons than the pyrolysis gas and a second condenser effluent having a higher proportion of C2-C3 hydrocarbons than the pyrolysis gas. (f) The C5 and lighter C ≤5 At least a portion of the first fraction of the hydrocarbon effluent and at least a portion of the pyrolysis oil are fed into a steam cracker to form a steam cracker product stream comprising ethylene and light C2-C3 saturated hydrocarbons. (g) The product stream from the steam cracker and at least a portion of the effluent from the second condenser are fed into the separation unit; (h) Separating the feed to the separation unit to provide ethylene effluent, propylene effluent, and light C2-C3 saturated hydrocarbon effluent; and (i) Recycle at least a portion of the light C2-C3 saturated hydrocarbon effluent to the steam cracker.

30. The process for recycling plastic waste according to claim 29, wherein the feed to the fractionation unit further comprises at least a portion of the pyrolysis oil.

31. The process for recycling plastic waste according to claim 29, the process further comprising the following steps: Make the heavy C 6+ At least a portion of the second fractionated effluent of the hydrocarbon is recycled to the fluidized catalytic cracker (FCC) reactor.

32. The process for recycling plastic waste according to claim 29, the process further comprising the following steps: The substance containing heavy C 6+ At least a portion of the second fractionation effluent of the hydrocarbon is fed into a reforming unit or an AROMAX® unit to provide a reforming product stream or an AROMAX® product stream, respectively, containing recycled aromatic hydrocarbons.

33. The process for recycling plastic waste according to claim 32, wherein: The reforming product stream or the AROMAX® product stream includes recycled products selected from benzene, toluene, o-xylene, m-xylene, or p-xylene; and At least one recycled product is fed to one or more subsequent processing units to provide subsequent recycled products, said subsequent recycled products being selected from ethylbenzene, benzenesulfonic acid, chlorobenzene, cumene, cyclohexane, nitrobenzene, maleic anhydride, dinitrotoluene, toluene diisocyanate, urethane, phthalic anhydride, alkyd resin, polyester resin, polyester polyol, urethane, polyurethane, isophthalic acid, polyamide resin, diphenyl isophthalate, polybenzimidazole, terephthalic acid, polyethylene terephthalate, or polybutylene terephthalate.

34. The process for recycling plastic waste according to claim 29, the process further comprising the following steps: At least a portion of the ethylene effluent or the propylene effluent is fed into a polymerization reactor to form recycled polyethylene or recycled polypropylene.

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