Pyrolysis process and system for recovering waste

Abstract

A pyrolysis process and system is provided that utilizes hydrogen or steam to enhance pyrolysis oil produced from recycled plastic waste. More specifically, the disclosed pyrolysis processes and systems may be configured to co-feed hydrogen or steam and various types of waste plastics, including post-consumer and post-industrial waste, into a pyrolysis unit to produce a desired pyrolysis oil.

Description

[0001] This application is a divisional application of a patent application for an invention named "Pyrolysis Method and System for Recycling Waste", with a priority date of October 31, 2019, a filing date of October 29, 2020, and an application number of 202080075830.4. Background Art

[0002] Waste materials, especially non - biodegradable waste materials, have a negative impact on the environment when disposed of in landfills after a single use. Therefore, from an environmental perspective, it is desirable to recycle as much waste as possible. However, from an economic perspective, recycling waste materials can be challenging.

[0003] While some waste materials are relatively easy and inexpensive to recycle, other waste materials require extensive and costly treatment for reuse. In addition, different types of waste materials typically require different types of recycling processes. In many cases, it is necessary to perform expensive physical sorting of the waste materials into relatively pure, single - component waste volumes.

[0004] To maximize recycling efficiency, it is desirable for large - scale production facilities to be able to process feedstocks with recycled components derived from various waste materials. Commercial facilities involved in the production of non - biodegradable products can greatly benefit from using feedstocks with recycled components, since the positive environmental impact of using recycled - component feedstocks can offset the negative environmental impact of producing non - biodegradable products.

[0005] In addition, pyrolysis oils produced by conventional pyrolysis methods typically contain large amounts of aromatic hydrocarbons and impurities such as oxygenates. Therefore, due to the presence of aromatic hydrocarbon components, such pyrolysis oils may not be easily further processed in downstream crackers and / or may require additional, expensive downstream treatment to remove impurities, which may result in unwanted by - products during downstream processing of the pyrolysis oils.

[0006] We have found that co - feeding hydrogen or steam - containing gas with recycled waste feedstock to a pyrolysis unit can inhibit the production of carbon monoxide and carbon dioxide in the resulting pyrolysis oil by forming water and allow for effective removal of oxygenates. In addition, we have found that adding hydrogen or steam - containing gas to the pyrolysis unit can hydrogenate olefins to alkanes, which inhibits the formation of aromatic hydrocarbons in the resulting pyrolysis oil. Additionally, we have found that adding steam to the pyrolysis reactor can promote the water - gas shift reaction, resulting in in - situ hydrogen generation. Therefore, introducing steam - containing gas into the pyrolysis reactor can provide a cheaper source of hydrogen in the pyrolysis reaction. Consequently, these pyrolysis oils are generally more fluid and exhibit superior heat transfer characteristics. Summary of the Invention

[0007] In certain embodiments, the present invention relates to the large-scale production of one or more materials having recycled components. The recycled components of the product can be derived from recycled waste and / or from recycled pyrolysis oil (r-pyrolysis oil) produced via pyrolysis of recycled waste. In certain embodiments, the pyrolysis unit that produces r-pyrolysis oil can be co-located with the production facility. In other embodiments, the r-pyrolysis oil can be derived from a remote pyrolysis unit and transported to the production facility.

[0008] In certain embodiments, the present invention relates to a method for preparing pyrolysis oil. Generally, the method includes: (a) introducing a pyrolysis feed and a reducing gas stream into a pyrolysis unit, wherein the pyrolysis feed includes at least one recycled waste; and (b) pyrolyzing at least a portion of the pyrolysis feed to form a pyrolysis effluent comprising pyrolysis oil. The resulting pyrolysis oil: (i) comprises less than 15 wt% aromatic hydrocarbon components; (ii) comprises at least 25 wt% alkane components; and (iii) exhibits a density of less than 0.9 g / cm 3 at 15 °C.

[0009] In certain embodiments, the present invention relates to a method for preparing pyrolysis oil. Generally, the method includes: (a) introducing a pyrolysis feed and a reducing gas stream into a pyrolysis unit, wherein the pyrolysis feed includes at least one recycled waste; and (b) pyrolyzing at least a portion of the pyrolysis feed in the absence of a catalyst to form a pyrolysis effluent comprising pyrolysis oil. The resulting pyrolysis oil: (i) comprises less than 15 wt% aromatic hydrocarbon components; (ii) comprises at least 25 wt% alkane components; and (iii) exhibits a density of less than 0.9 g / cm 3 at 15 °C.

[0010] Another method includes: (a) introducing a pyrolysis feed and a steam-containing stream into a pyrolysis unit, wherein the pyrolysis feed includes at least one recycled waste; and (b) pyrolyzing at least a portion of the pyrolysis feed to form a pyrolysis effluent comprising pyrolysis oil. The resulting pyrolysis oil: (i) comprises less than 15 wt% aromatic hydrocarbon components; (ii) comprises at least 25 wt% alkane components; and (iii) exhibits a density of less than 0.9 g / cm 3 at 15 °C. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 is a diagram of a process for preparing one or more recycled component compositions into an r-composition using a recycled component pyrolysis oil composition (r-pyrolysis oil).

[0012] Figure 2 is a diagram of an exemplary pyrolysis system for at least partially converting one or more recycled wastes, particularly recycled plastic wastes, into various useful r-products.

[0013] Figure 3 is a schematic diagram of the pyrolysis treatment for producing olefin-containing products.

[0014] Figure 4 is a flowchart showing the steps related to the cracking furnace and separation zone of a system for producing an r-composition obtained from cracked r-pyrolysis oil and non-recycled cracker feedstock.

[0015] Figure 5 is a schematic diagram of a cracking furnace suitable for receiving r-pyrolysis oil.

[0016] Figure 6 shows a furnace coil configuration with multiple tubes.

[0017] Figure 7 shows various feed locations where r-pyrolysis oil enters the cracking furnace.

[0018] Figure 8 shows a cracking furnace with a vapor-liquid separator.

[0019] Figure 9 is a block diagram showing the treatment of the recovered component furnace effluent.

[0020] Figure 10 shows a fractionation scheme for the separation section that separates and isolates the main r-composition, including a demethanizer, a deethanizer, a debutanizer, and a fractionation tower, and the main r-composition includes r-propylene, r-ethylene, r-butene, etc.

[0021] Figure 11 shows a laboratory-scale cracking unit design.

[0022] Figure 12 illustrates the design features of a plant-based experimental feeding of r-pyrolysis oil to a gas-feed cracking furnace.

[0023] Figure 13 is a boiling point curve graph of r-pyrolysis oil obtained by gas chromatography analysis, with 74.86% C8+, 28.17% C15+, 5.91% aromatics, 59.72% paraffins, and 13.73% unidentified components.

[0024] Figure 14 is a boiling point curve graph of r-pyrolysis oil obtained by gas chromatography analysis.

[0025] Figure 15 is a boiling point curve graph of r-pyrolysis oil obtained by gas chromatography analysis.

[0026] Figure 16 is a boiling point curve graph of r-pyrolysis oil distilled in the laboratory and obtained by chromatographic analysis.

[0027] Figure 17 Boiling point curve of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350 °C, 50% boils between 95 °C and 200 °C, and at least 10% boils at 60 °C.

[0028] Figure 18 Boiling point curve of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 150 °C, 50% boils between 80 °C and 145 °C, and at least 10% boils at 60 °C.

[0029] Figure 19 Boiling point curve of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350 °C, at least 10% boils at 150 °C, and 50% boils between 220 °C and 280 °C.

[0030] Figure 20 Boiling point curve of r-pyrolysis oil distilled in the laboratory with 90% boiling point between 250 - 300 °C.

[0031] Figure 21 Boiling point curve of r-pyrolysis oil distilled in the laboratory with 50% boiling point between 60 - 80 °C.

[0032] Figure 22 Boiling point curve of r-pyrolysis oil distilled in the laboratory with an aromatic hydrocarbon content of 34.7%.

[0033] Figure 23 Boiling point curve of r-pyrolysis oil used in the factory trial experiment.

[0034] Figure 24 Graph of the carbon distribution of the pyrolysis oil used in the factory experiment.

[0035] Figure 25 Graph of the carbon distribution of the cumulative weight percentage of the pyrolysis oil used in the factory experiment. Detailed implementation mode

[0036] The terms "containing" and "including" are synonymous with "comprising". When indicating a numerical series, it should be understood that each number is modified to be the same as the first or last number in the numerical series or sentence. For example, each number is, as the case may be, "at least" or "up to" or "not exceeding"; and each number is in an "or" relationship. For example, "at least 10, 20, 30, 40, 50, 75 wt. %..." means the same as "at least 10 wt. %, or at least 20 wt. %, or at least 30 wt. %, or at least 40 wt. %, or at least 50 wt. %, or at least 75 wt. %"; and "not exceeding 90 wt. %, 85, 70, 60..." means the same as "not exceeding 90 wt. %, or not exceeding 85 wt. %, or not exceeding 70 wt. %...."; and "at least 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by weight..." means the same as "at least 1 wt. %, or at least 2 wt. %, or at least 3 wt. %..."; and "at least 5, 10, 15, 20 and / or not exceeding 99, 95, 90 weight percentages" means the same as "at least 5 wt. %, or at least 10 wt. %, or at least 15 wt. %, or at least 20 wt. %, and / or not exceeding 99 wt. %, or not exceeding 95 wt. %, or not exceeding 90 weight percentages..."; or "at least 500, 600, 750 °C..." means the same as "at least 500 °C, or at least 600 °C, or at least 750 °C...".

[0037] Unless otherwise specified, all concentrations or amounts are by weight. "Olefin-containing effluent" is the furnace effluent obtained by cracking a cracker feed containing r-pyrolysis oil. "Non-recovered-olefin-containing effluent" is the furnace effluent obtained by cracking a cracker feed without r-pyrolysis oil. The hydrocarbon mass flow rates, MF1 and MF2, are in units of thousands of pounds per hour (klb / hr), unless otherwise specified as molar flow rates.

[0038] As used herein, "containing" and "including" are open-ended and synonymous with "comprising".

[0039] The term "recovered component" is used as a noun herein to mean i) a physical component (e.g., a compound, molecule or atom) at least a part of which is directly or indirectly derived from recovered waste, or ii) an adjective used to modify a particular composition (e.g., a compound, polymer, feedstock, product or stream) at least a part of which is directly or indirectly derived from recovered waste.

[0040] As used herein, "reclaimed component composition", "reclaimed composition", and "r-composition" refer to a composition having reclaimed components.

[0041] The term "pyrolysis reclaimed component" is used herein as a noun and (i) refers to a physical component (e.g., a compound, molecule, or atom) that is at least partially directly or indirectly derived from the pyrolysis of reclaimed waste, or (ii) as an adjective modifying a particular composition (e.g., a feedstock, product, or stream) that is at least partially directly or indirectly derived from the pyrolysis of reclaimed waste. For example, a pyrolysis reclaimed component can be directly or indirectly derived from pyrolysis reclaimed oil, pyrolysis reclaimed gas, or the cracking of pyrolysis reclaimed oil, e.g., via a thermal steam cracker or a fluid catalytic cracker.

[0042] As used herein, "pyrolysis reclaimed component composition", "pyrolysis reclaimed composition", and "pr-composition" refer to a composition (e.g., a compound, polymer, feedstock, product, or stream) having pyrolysis reclaimed components. A pr-composition is a subset of an r-composition, wherein at least a portion of the reclaimed components of the r-composition are directly or indirectly derived from the pyrolysis of reclaimed waste.

[0043] As used herein, a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "directly derived" or "derived directly" from reclaimed waste has at least one physical component traceable to the reclaimed waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from reclaimed waste has a reclaimed component quota associated therewith and may or may not contain a physical component traceable to the reclaimed waste.

[0044] As used herein, a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "directly derived" or "derived directly" from the pyrolysis of reclaimed waste has at least one physical component traceable to the pyrolysis of the reclaimed waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from the pyrolysis of reclaimed waste has a reclaimed component quota associated therewith and may or may not contain a physical component traceable to the pyrolysis of the reclaimed waste.

[0045] As used herein, "pyrolysis oil" or "pyoil" refers to a composition of matter that is liquid when measured at 25°C and 1 atm and at least a portion of which is obtained by pyrolysis.

[0046] As used herein, "recovered component pyrolysis oil", "recovered pyrolysis oil", "pyrolysis recovered component pyrolysis oil", and "r-pyrolysis oil" refer to pyrolysis oil at least a portion of which is obtained by pyrolysis and which has recovered components.

[0047] As used herein, "pyrolysis gas" and "pyrolysis gas" refer to a composition of matter that is gaseous when measured at 25°C and 1 atm and at least a portion of which is obtained by pyrolysis.

[0048] As used herein, "recovered component pyrolysis gas", "recovered pyrolysis gas", "pyrolysis component pyrolysis gas", and "r-pyrolysis gas" refer to pyrolysis gas at least a portion of which is obtained by pyrolysis and which has recovered components.

[0049] As used herein, "Et" is an ethylene component (e.g., feedstock, product, or stream), and "Pr" is a propylene component (e.g., feedstock, product, or stream).

[0050] As used herein, "recovered component ethylene", "r-ethylene", and "r-Et" refer to Et having recovered components; "recovered component propylene", "r-propylene", and "r-Pr" refer to Pr having recovered components.

[0051] As used herein, "pyrolysis recovered component ethylene" and "pr-Et" refer to r-Et having pyrolysis recovered components; "pyrolysis recovered component propylene" and "pr-Pr" refer to r-Pr having pyrolysis recovered components.

[0052] As used herein, "EO" is an ethylene oxide composition (e.g., feedstock, product, or stream).

[0053] As used herein, "recovered component ethylene oxide" and "r-EO" refer to EO having recovered components.

[0054] As used herein, "pyrolysis component ethylene oxide" and "pr-EO" refer to r-EO having pyrolysis recovered components.

[0055] As used throughout, a general description of a compound, composition, or stream does not require the presence of the substance, but also does not exclude and may include the substance. For example, "EO" or "any EO" can include ethylene oxide prepared by any method, and may or may not contain recycled components, and may be prepared from virgin feedstock or recycled feedstock, and may or may not contain r-EO or pr-EO. Similarly, r-EO may or may not include pr-EO, although mention of r-EO does require it to have recycled components. In another example, "Et" or "any Et" can include ethylene prepared by any method, and may or may not have recycled components, and may or may not include r-Et or pr-Et. Similarly, r-Et may or may not include pr-Et, although mention of r-Et does require it to have recycled components.

[0056] "Pyrolysis recycled component" is a specific subset / type (species) of "recycled component" (genus). Whenever "recycled component" and "r-" are used herein, such use shall be interpreted as expressly disclosing "pyrolysis recycled component" and "pr-" and providing claim support therefor, even if not expressly stated as such. For example, whenever the term "recycled component ethylene oxide" or "r-EO" is used herein, it shall be interpreted as also expressly disclosing "pyrolysis recycled component ethylene oxide" and "pr-EO" and providing claim support therefor.

[0057] As used throughout, whenever cracking of r-pyrolysis oil is mentioned, such cracking can be carried out in a liquid feed furnace or a gas feed furnace or in any cracking process by a pyrolyzer or a thermal steam cracker. In one embodiment or in combination with any mentioned embodiment, the cracking is not catalytic or is carried out in the absence of an added catalyst, or is not a fluid catalytic cracking process.

[0058] As used throughout, whenever pyrolysis of recycled waste or r-pyrolysis oil is mentioned, all embodiments also include the option of (i) cracking the effluent of the pyrolysis recycled waste or the r-pyrolysis oil and / or (ii) cracking the effluent or the r-pyrolysis oil as feed to the tubes of a gas feed furnace or a gas furnace / cracker.

[0059] As used throughout, "entity family" means at least one individual or entity that directly or indirectly controls another person or entity, is controlled by another person or entity, or is under common control with another person or entity, where control means ownership of at least 50% of the voting shares, or shared management, common use of facilities, equipment, and employees, or family interests. As used throughout, mention of a person or entity provides claim support for any person or entity in the entity family and includes such any person or entity.

[0060] In one embodiment or in combination with any other recited embodiment, the reference to r-Et also includes pr-Et, or pr-Et directly or indirectly obtained from the cracking of r-pyrolysis oil or from r-pyrolysis gas; and r-EO also includes pr-EO, or pr-EO directly or indirectly obtained from the cracking of r-pyrolysis oil or from r-pyrolysis gas.

[0061] In one embodiment or in combination with any recited embodiment, a method for preparing an r-EO composition by reacting Et with oxygen is provided. Et can be r-Et or pr-Et or dr-Et. In one embodiment, the method for preparing r-EO begins with feeding r-Et into a reactor for preparing EO.

[0062] Figure 1 FIG. is a schematic illustration of an embodiment of a process for producing one or more recycle component compositions (such as ethylene, propylene, butadiene, hydrogen, and / or pyrolysis gasoline) (r-compositions) using a recycle component pyrolysis oil composition (r-pyrolysis oil) or in combination with any embodiment recited herein.

[0063] As Figure 1 shown, the recycle waste can be subjected to pyrolysis in a pyrolysis unit 10 to produce a pyrolysis product / effluent comprising a recycle component pyrolysis oil composition (r-pyrolysis oil). The r-pyrolysis oil can be fed together with a non-recycle cracker feed (such as propane, ethane, and / or natural gasoline) into a cracker 20. A recycle component cracker effluent (r-cracker effluent) can be produced from the cracker and then separated in a separation train 30. In one embodiment, or in combination with any embodiment recited herein, the r-compositions can be separated and recovered from the r-cracker effluent. The r-propylene stream can mainly contain propylene, and the r-ethylene stream can mainly contain ethylene.

[0064] As used herein, a furnace includes a convection zone and a radiation zone. The convection zone includes tubes and / or coils inside a convection box, and the tubes and / or coils can also extend outside the convection box downstream of a coil inlet at an inlet of the convection box. For example, as Figure 5 shown, the convection zone 310 includes coils and pipes inside a convection box 312, and can optionally extend outside the convection box 312 and return inside the convection box 312 or be interconnected therewith by pipes 314. The radiation zone 320 includes radiation coils / tubes 324 and burners 326. The convection zone 310 and the radiation zone 320 can be contained in a single integral box or in separate discrete boxes. The convection box 312 does not have to be a separate discrete box. As Figure 5 shown, the convection box 312 is integrated with a combustion chamber 322.

[0065] Unless otherwise specified, all component amounts provided herein (e.g., for feeds, raw materials, streams, compositions, and products) are expressed on a dry basis.

[0066] As used herein, "r-pyoil" or "r-pyrolysis oil" are used interchangeably and refer to a material composition that is liquid when measured at 25 °C and 1 atmosphere of pressure, and at least a portion of which is obtained from pyrolysis and has a recycled component. In one embodiment or in combination with any recited embodiment, at least a portion of the composition is obtained from the pyrolysis of recycled waste (e.g., waste plastic or waste stream).

[0067] In one embodiment or in combination with any recited embodiment, "r-ethylene" can be a composition comprising: (a) ethylene obtained by cracking a cracker feed containing r-pyoil, or (b) ethylene having a recycled component value attributable to at least a portion of the ethylene; and "r-propylene" can be a composition comprising (a) propylene obtained by cracking a cracker feed containing r-pyoil, or (b) propylene having a recycled component value attributable to at least a portion of the propylene.

[0068] A reference to an "r-ethylene molecule" refers to an ethylene molecule that is directly or indirectly derived from recycled waste and a reference to a "pr-ethylene molecule" refers to an ethylene molecule that is directly or indirectly derived from an r-pyoil effluent (r-pyoil or r-pyrolysis gas).

[0069] As used herein, the term "major" means greater than 50 weight percent, unless expressed as a mole percent, in which case it means greater than 50 mol%. For example, a stream, composition, feed, or product that is predominantly propane is a stream, composition, feed, or product that contains greater than 50 weight percent propane, or if expressed as mol%, is a product that contains greater than 50 mol% propane.

[0070] As used herein, "site" means the largest continuous geographic boundary owned by an ethylene oxide manufacturer, or by a person or entity within its family of entities, or a combination of persons or entities, where the geographic boundary contains one or more manufacturing facilities, at least one of which is an ethylene oxide manufacturing facility.

[0071] As used herein, the term "major" means greater than 50 weight percent, unless expressed as a mole percent, in which case it means greater than 50 mol%. For example, a stream, composition, feed, or product that is predominantly propane is a stream, composition, feed, or product that contains greater than 50 weight percent propane, or if expressed as mol%, is a product that contains greater than 50 mol% propane.

[0072] As used herein, a composition "directly derived" from cracked pyrolysis oil has at least one physical component traceable to an r-composition, at least a portion of which is obtained by cracking r-pyrolysis oil or obtained together with cracked r-pyrolysis oil, while a composition "indirectly derived from" cracked r-pyrolysis oil has an associated recycled component quota and may or may not contain a physical component traceable to an r-composition, at least a portion of which is obtained by cracking r-pyrolysis oil or obtained together with cracked r-pyrolysis oil.

[0073] As used herein, "recycled component value" and "r-value" refer to a unit of measure representative of the amount of material sourced from recycled waste. The r-value can be sourced from any type of recycled waste processed in any type of process.

[0074] As used herein, the terms "pyrolysis recycled component value" and "pr-value" refer to a unit of measure representative of the amount of material sourced from the pyrolysis of recycled waste. The pr-value is a specific subset / type of r-value associated with the pyrolysis of recycled waste. Thus, the term r-value encompasses but does not require a pr-value.

[0075] A specific recycled component value (r-value or pr-value) can be by mass or percentage or any other unit of measure and can be determined according to a standard system for tracing, allocating, and / or inventorying recycled components in various compositions. The recycled component value can be deducted from the recycled component inventory and applied to a product or composition to attribute recycled components to the product or composition. Unless otherwise stated, the recycled component value is not necessarily sourced from the manufacture or cracking of r-pyrolysis oil. In one embodiment or in combination with any recited embodiment, at least a portion of the r-pyrolysis oil from which a quota is obtained is also cracked in a cracking furnace as described in one or more embodiments throughout this document.

[0076] In one embodiment or in combination with any recited embodiment, at least a portion of the recycled component quota or recycled component value deposited into the recycled component inventory is obtained from r-pyrolysis oil. Desirably, at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or up to 100% of the following is obtained from r-pyrolysis oil: (a) the quota, or (b) deposited into the recycled component inventory, or (c) the recycled component value in the recycled component inventory, or (d) the recycled component value applied to a composition to produce a recycled component product, intermediate, or article (recycled PIA).

[0077] Recycled PIA is a product, intermediate, or article that can include a compound or a composition containing a compound or polymer, and / or an article having an associated recycled component value. The PIA does not have an associated recycled component value. PIA includes but is not limited to ethylene oxide or alkylene glycols (e.g., ethylene glycol).

[0078] As used herein, "recycled content quota" or "quota" means a recycled content value that is: (a) transferred from a starting composition (e.g., a compound, polymer, feedstock, product, or stream) to a receiving composition (the composition receiving the quota, e.g., a compound, polymer, feedstock, product, or stream), where at least a portion of the starting composition is obtained from recycled waste or has a recycled content value at least partially derived from recycled waste, optionally from r-pyrolysis oil, and the receiving composition may or may not have physical components traceable to a composition at least partially obtained from recycled waste; or (b) deposited by a starting composition (e.g., a compound, polymer, feedstock, product, or stream) into a recycling inventory, where at least a portion of the original composition is obtained from or has a recycled content value or pr value at least partially derived from recycled waste.

[0079] As used herein, "pyrolysis recycled content quota" and "pyrolysis quota" or "pr-quota" means a recycled content value that is: (a) transferred from a starting composition (e.g., a compound, polymer, feedstock, product, or stream) to a receiving composition (e.g., a compound, polymer, feedstock, product, or stream), where at least a portion of the starting composition is obtained from the pyrolysis of recycled waste or has a recycled content value at least partially derived from the pyrolysis of recycled waste, and the receiving composition may or may not have physical components traceable to a composition at least partially obtained from the pyrolysis of recycled waste; or (b) deposited by a starting composition (e.g., a compound, polymer, feedstock, product, or stream) into a recycling inventory, where at least a portion of the original composition is obtained from or has a recycled content value at least partially derived from the pyrolysis of recycled waste.

[0080] The pyrolysis recycled content quota is a specific type of recycled content quota related to the pyrolysis of recycled waste. Thus, the term recycled content quota includes the pyrolysis recycled content quota.

[0081] In one embodiment or in combination with any of the embodiments mentioned, the thermal pyrolysis recycle composition quota or pyrolysis quota may have a recycle composition value that is: (a) transferred from a starting composition (e.g., a compound, polymer, feedstock, product, or stream) to a receiving composition (e.g., a compound, polymer, feedstock, product, or stream or PIA), where at least a portion of the starting composition is obtained from the cracking of r-pyrolysis oil (e.g., liquid or gas thermal steam cracking), or transferred from a recycle waste used to prepare the r-pyrolysis oil for cracking, or transferred from or to be cracked r-pyrolysis oil, or it has a recycle composition value with at least a portion derived from the cracking of r-pyrolysis oil (e.g., liquid or gas thermal steam cracking), and the receiving composition may or may not have physical components of a composition traceable to at least a portion of it being obtained from the cracking of r-pyrolysis oil; or (b) deposited into a recycle inventory and obtained from a composition (e.g., a compound, polymer, feedstock, product, or stream), where the composition has a recycle composition value with at least a portion obtained from or having at least a portion derived from the cracking of r-pyrolysis oil (e.g., liquid or gas thermal steam cracking) (regardless of whether the r-pyrolysis oil is cracked when the quota is deposited into the recycle composition inventory, provided that the r-pyrolysis oil from which the quota is withdrawn is ultimately cracked).

[0082] The quota may be an allotment or a credit.

[0083] The recycle composition quota may include a recycle composition allotment or a recycle composition credit obtained by transfer or use of raw materials. In one embodiment or in combination with any of the embodiments mentioned, the composition receiving the recycle composition quota may be a non-recycle composition, thereby converting the non-recycle composition into an r-composition.

[0084] As used herein, "non-recycle" refers to a composition (e.g., a compound, polymer, feedstock, product, or stream) that is not directly or indirectly derived from recycle waste.

[0085] As used herein, in the context of the feed to a cracker or furnace, "non-recycle feed" refers to a feed that is not obtained from a recycle waste stream. Once the non-recycle feed obtains a recycle composition quota (e.g., through a recycle composition credit or recycle composition allotment), the non-recycle feed becomes a recycle composition feed, composition, or recycle PIA.

[0086] As used herein, the term "reclaimed component allocation" refers to a type of reclaimed component quota where an entity or individual supplying a composition sells or transfers the composition to a receiving individual or entity, and the individual or entity preparing the composition has a quota, at least a portion of which can be associated with the composition sold or transferred by the supplying individual or entity to the receiving individual or entity. The supplying entity or individual can be controlled by the same entity or individual or various affiliates controlled by an entity family, or they can be from different entity families. In one embodiment or in combination with any of the embodiments mentioned, the reclaimed component allocation travels with the composition and downstream derivatives of the composition. In one embodiment or in combination with any of the embodiments mentioned, the allocation can be deposited into a reclaimed component inventory, withdrawn from the reclaimed component inventory as an allocation, and applied to a composition to produce an r-composition or recycled PIA.

[0087] As used herein, "reclaimed component credit" and "credit" refer to a reclaimed component quota where the quota is not limited to being associated with a composition made from cracked r-pyrolysis oil or its downstream derivatives, but has flexibility obtained from r-pyrolysis oil and (i) is applied to a composition or PIA made by a process other than a cracking feedstock in a furnace, or (ii) is applied to downstream derivatives of a composition through one or more intermediate feedstocks, where the compositions are made by a process other than a cracking feedstock in a furnace, or (iii) can be sold or transferred to an individual or entity other than the quota owner, or (iv) can be sold or transferred by an individual other than the composition supplier transferring to the receiving entity or individual. For example, when a quota is obtained from r-pyrolysis oil and the quota owner applies the quota to a BTX composition or its fraction, the quota can be a credit, where the BTX composition or its fraction is made by the owner or within its entity family, obtained through the refining and fractionation of petroleum rather than from a cracker effluent product; or if the quota owner sells the quota to a third party to allow the third party to resell the product or apply the credit to one or more compositions of the third party, it can be a credit.

[0088] The credit can be available for sale, transfer, or use, or be sold, transferred, or used, or: (a) the composition is not sold, or (b) the composition is sold or transferred, but the quota is not associated with the sale or transfer of the composition, or (c) is deposited into a reclaimed inventory or withdrawn from a reclaimed component inventory, where the reclaimed inventory does not trace the molecules of the reclaimed component feedstock to the molecules of the resulting composition made with the reclaimed component feedstock, or the reclaimed inventory has such a tracing ability but does not trace the specific quota applied to the composition.

[0089] In one embodiment or in combination with any of the embodiments mentioned, quotas may be deposited into a recycled component inventory, and credits or allocations may be withdrawn from the inventory and applied to a composition. This would be the case where quotas are generated by pyrolysis of recycled waste, or by cracking of r-pyrolysis oil or r-pyrolysis oil, or by any other method of preparing a first composition from recycled waste, and the allocation associated with the first component is deposited into the recycled component inventory, and the recycled component value is deducted from the recycled component inventory and applied to a second composition that is not a derivative of the first composition or is not actually prepared from the first composition as a raw material. In one embodiment or in combination with any of the embodiments mentioned, the recycled component allocation travels with the combination and the downstream derivatives of the combination. In one embodiment or in combination with any of the embodiments mentioned, an allocation may be deposited into the recycled component inventory and withdrawn from the recycled component inventory as an allocation and applied to a composition to produce an r-composition or recycled PIA.

[0090] In one embodiment or in combination with any of the embodiments mentioned, the composition receiving the quota is used as a raw material to prepare downstream derivatives of the composition, and such a composition is the product of a cracker feedstock cracked in a cracker furnace. In one embodiment or in combination with any of the embodiments mentioned, a process is provided, wherein: (a) r-pyrolysis oil is obtained, (b) a recycled component value (or quota) is obtained from the r-pyrolysis oil and (i) deposited into the recycled component inventory, the quota (or credit) is withdrawn from the recycled component inventory and applied to any composition to obtain an r-composition, or (ii) directly applied to any composition without depositing into the recycled component inventory to obtain an r-composition; and (c) optionally, at least a portion of the r-pyrolysis oil is cracked in a cracking furnace according to any of the designs or processes described herein; and (d) optionally, at least a portion of the composition in step b is derived from a cracker feedstock in a cracker furnace, optionally, the composition has been obtained by any of the feedstocks including r-pyrolysis oil and the methods described herein.

[0091] Steps (b) and (c) do not have to occur simultaneously. In one embodiment or in combination with any of the embodiments mentioned, they occur within one year of each other, or within six (6) months of each other, or within three (3) months of each other, or within one (1) month of each other, or within two (2) weeks of each other, or within one (1) week of each other, or within three (3) days of each other. The process allows for the passage of time between the time a entity or individual receives r-pyrolysis oil and generates a quota (which may occur upon receipt or possession of r-pyrolysis oil or deposit into the inventory) and the actual processing of the r-pyrolysis oil in a cracking furnace.

[0092] As used herein, "recycle content inventory" and "inventory" mean a group or collection of quotas (allocations or credits) from which the deposits and deductions of quotas under any unit can be traced. The inventory can be in any form (electronic or paper), use any one or more software programs, or use various modules or applications that together trace deposits and deductions as a whole. Desirably, the total amount of recycle content taken out (or applied to a composition) does not exceed the recycle content quota in the recycle content inventory or the total amount deposited (from any source, not only from the cracking of r-pyrolysis oil). However, if a deficit in the recycle content value is achieved, the recycle content inventory is rebalanced to achieve a zero or positive available recycle content value. The timing of rebalancing can be determined and managed according to the rules of a particular certification system adopted by the olefin-containing effluent manufacturer or a member of its entity family, or alternatively, it is rebalanced within one (1) year, or six (6) months, or three (3) months, or one (1) month of achieving the deficit. The timing of depositing quotas into the recycle content inventory, applying quotas (or credits) to a composition to prepare an r-composition, and cracking r-pyrolysis oil need not be simultaneous or in any particular order. In one embodiment or in combination with any of the embodiments mentioned, the step of cracking a particular volume of r-pyrolysis oil occurs after the recycle content value or quota from that volume of r-pyrolysis oil is deposited into the recycle content inventory. Additionally, the quota or recycle content value taken out from the recycle content inventory need not be traceable to r-pyrolysis oil or cracked r-pyrolysis oil, but can be obtained from any waste recycle stream and any method of processing the recycled waste stream. Desirably, at least a portion of the recycle content value in the recycle content inventory is obtained from r-pyrolysis oil, optionally, at least a portion of the r-pyrolysis oil is processed in one or more cracking processes as described herein, optionally within one year of each other, and optionally, at least a portion of the volume of r-pyrolysis oil (from which the recycle content value is deposited into the recycle content inventory) is also processed through any one or more of the cracking processes described herein.

[0093] Determining whether an r-composition is directly or indirectly derived from cracked r-pyrolysis oil is not based on the presence of intermediate steps or entities in the supply chain, but rather on whether at least a portion of the r-composition fed to the reactor used to prepare the final product (such as EO or AD) is traceable to an r-composition prepared from recycled waste.

[0094] Determining whether a pr composition is directly or indirectly derived from the pyrolysis of recycled waste (e.g., derived from the cracking of r-pyrolysis oil or derived from r-pyrolysis gas) is not based on the presence of intermediate steps or entities in the supply chain, but rather on whether at least a portion of the pr composition fed into the reactor used to prepare the final product (e.g., EO) can be traced back to a pr composition prepared by the pyrolysis of recycled waste.

[0095] As described above, if at least a portion of the atoms or molecules in the reactant feedstock used to prepare the product can be optionally traced via one or more intermediate steps or entities to at least a portion of the r-composition that constitutes the r-composition produced by the cracking of recycled waste or r-pyrolysis oil fed into the cracking furnace or as the effluent from the cracking furnace, then the final product is considered to be directly derived from the cracked r-pyrolysis oil or recycled waste.

[0096] The r-composition as an effluent can be in the form of a crude product, which requires refining to separate the specific r-composition. After refining and / or purifying and compressing to produce the specific r-composition of the desired grade, the r-composition manufacturer can typically sell such r-composition to an intermediate entity, which then sells the r-composition or one or more of its derivatives to another intermediate entity used to prepare intermediate products, or directly to the product manufacturer. Any number of intermediates and intermediate derivatives can be prepared before the final product is prepared.

[0097] The actual volume of the r-composition, whether condensed as a liquid, supercritical, or stored as a gas, can remain in the equipment where it is prepared, or it can be transported to a different location, or held in an off-site storage facility before being used by an intermediate or product manufacturer. For tracking purposes, once the r-composition prepared from recycled waste (e.g., by cracking r-pyrolysis oil or from r-pyrolysis gas) is mixed with another volume of composition (e.g., r-ethylene mixed with non-recycled ethylene) in, for example, a storage tank, salt dome, or cavern, then at that point the entire tank, dome, or cavern becomes the r-composition source, and for tracking purposes, withdrawals from such storage facilities are taken from the r-composition source until after feeding of the r-composition into the tank has stopped and the entire volume or inventory of the storage facility is turned over or withdrawn and / or replaced with non-recycled composition. Similarly, this also applies to any downstream storage facilities for storing derivatives of the r-composition, such as r-Et and pr-Et compositions.

[0098] An r-composition is considered to be indirectly derived from recycled waste or the pyrolysis of recycled waste or the cracking of r-pyrolysis oil if the r-composition is associated with a recycled content quota and may or may not contain physical components of the r-composition that are traceable to recycled waste or the pyrolysis of recycled waste or the cracking of r-pyrolysis oil. For example, (i) a product manufacturer may operate within a legal framework, or an association framework, or an industry-recognized framework to require recycled content, for example, through a system of credits transferred to the product manufacturer, regardless of where or from whom the r-composition, or its derivatives, or the reactant feedstock for the manufactured product is purchased or acquired, or (ii) a supplier of an r-composition or its derivatives ("supplier") operates within a quota framework that allows the recycled content value or pr value to be associated with or applied to a portion or all of the compounds within an olefin-containing effluent or its derivatives to prepare the r-composition, and transfers the recycled content value or quota to the manufacturer of the product or any intermediary that obtains a supply of the r-composition from the supplier. In such a system, it is not necessary to trace the source of the olefin volume used to manufacture the r-composition from recycled waste / pyrolyzed recycled waste, but rather any ethylene composition prepared by any method may be used and have a recycled content quota associated with such ethylene composition, or r-EO or r-AD manufacturers do not need to separately trace the source of the r-Et or r-EO feedstock of the composition obtained by cracking r-pyrolysis oil or pyrolyzed recycled waste, but rather any ethylene or ethylene oxide obtained from any source may be used as a feedstock to separately prepare EO or AD and have a recycled content quota associated with such EO or AD to prepare r-EO or r-AD.

[0099] Examples of how a recycle component is obtained in an Et composition for preparing ethylene oxide include: (i) A cracker facility where an r-olefin (e.g., r-ethylene) prepared in the facility, by cracking r-pyrolysis oil or obtained from r-pyrolysis gas, can be in continuous or intermittent fluid communication, and via intermediate facilities directly or indirectly, with an olefin-derived petrochemical (e.g., EO or AD) forming facility (which can be a storage container to the olefin-derived petrochemical facility or directly to an olefin-derived petrochemical forming reactor) through interconnected pipes, optionally through one or more storage containers and valves or interlocks, and the r-olefin (e.g., r-ethylene) feedstock through the interconnected pipes: (a) is withdrawn from the cracker facility when or after the r-olefin (e.g., r-ethylene) is prepared and during the time the r-olefin (e.g., r-ethylene) is piped to the olefin-derived (e.g., EO or AD) petrochemical forming facility; or (b) is withdrawn at any time from one or more storage tanks, provided that at least one storage tank is fed with r-olefin (e.g., r-ethylene), as long as the entire volume of one or more storage tanks is replaced with a feed free of r-olefin (e.g., r-ethylene); or (ii) Propylene containing or having been fed with r-olefin (e.g., r-ethylene) is transported from a storage container, dome, or facility, or in an isotainer, by truck or rail or ship or a device other than a pipe, until the entire volume of the container, dome, or facility has been replaced with an olefin (e.g., ethylene) feedstock free of r-olefin (e.g., r-ethylene); or (iii) A petrochemical manufacturer of an olefin-derived (e.g., EO or AD) product certifies, represents, or advertises to its consumers or the public that its olefin-derived petrochemical product contains a recycle component or is obtained from feedstock obtained from a recycle component, where such recycle component is claimed to be wholly or partly based on obtaining an r-olefin (e.g., ethylene feedstock associated with a quota of ethylene made from cracking r-pyrolysis oil or obtained from r-pyrolysis gas) or (iv) A petrochemical manufacturer of an olefin-derived (e.g., EO or AD) product has obtained: (a) the amount of olefin (such as ethylene or propylene) made from r-pyrolysis oil as certified, represented, or advertised; or (b) a credit or allocation of an olefin supply has been transferred to the petrochemical manufacturer of an olefin-derived (e.g., EO or AD) product to meet the certification requirements or make its representation or advertisement; or (c) the olefin has a related recycle component value, where the recycle component value is obtained from r-pyrolysis oil or cracked r-pyrolysis oil or an olefin through one or more intermediate independent entities, the olefin being obtained from cracked r-pyrolysis oil or from r-pyrolysis gas.

[0100] As described above, the recycle component can be a pyrolysis recycle component directly or indirectly derived from recycled waste (e.g., from cracking r-pyrolysis oil or from r-pyrolysis gas).

[0101] In one embodiment or in combination with any of the embodiments mentioned, various methods are provided for allocating recycle components among various olefin-containing effluent volumes or their compounds made by any one entity or combination of entities in an olefin-containing effluent entity family. For example, the cracker owner or operator of the olefin-containing effluent, or any one of its entity family, or the site, may:

[0102] (a) Employ a symmetric distribution of recycle component values among at least two compounds within the olefin-containing effluent or among the PIAs, based on the same fractional percentage of recycle components in one or more feeds or based on the quota amount received. For example, if 5 wt% of the total cracker feed added to the furnace is r-pyrolysis oil, one or more compounds in the olefin-containing effluent may contain 5 wt% recycle component value, or one or more compounds may contain 5 wt% recycle component value minus any yield losses, or one or more PIAs may contain 5% recycle component value. In this case, the amount of recycle components in the compound is proportional to all other products receiving the recycle component value; or

[0103] (b) Employ an asymmetric distribution of recycle component values among the compounds in the olefin-containing effluent or among its PIAs. In this case, the recycle component value associated with a compound or PIA may exceed the recycle component value associated with other compounds or PIAs. For example, one volume or batch of the olefin-containing effluent may receive a greater amount of recycle component value than other batches or volumes of the olefin-containing effluent, or one or a combination of compounds in the olefin-containing effluent, to receive a disproportionately higher amount of recycle component value relative to other compounds in the olefin-containing effluent or other PIAs, some of which may receive no recycle component value. One volume of the olefin-containing effluent or PIA may contain 20 mass% recycle components, and another volume or PIA may contain 0% recycle components, even if the two volumes may be identical in composition and produced continuously, provided that the recycle component value withdrawn from the recycle component inventory and applied to the olefin-containing effluent does not exceed the recycle component value deposited into the recycle component inventory, or if there is a shortfall, the overdraft is rebalanced to zero or to a positive credit available state as described above, or if there is no recycle component inventory, provided that the total amount of recycle component value associated with any one or more compounds in the olefin-containing effluent does not exceed the quota obtained from r-pyrolysis oil or exceeds the quota, then rebalance. In the asymmetric distribution of recycle components, the manufacturer can adapt the recycle components to the volume of the olefin-containing effluent or to the compounds of interest in the olefin-containing effluent or PIA, which are sold according to customer needs, thereby providing flexibility among customers, some of whom may require more recycle components than other customers in the r-compounds or recycled PIAs.

[0104] In one embodiment or in combination with any embodiment mentioned herein, the symmetrical and asymmetrical distributions of the recycled components can be proportional on a site-wide basis or on a multi-site basis. In one embodiment or in combination with any of the embodiments mentioned, the recycled components obtained from r-pyrolysis oil can be within a Site, and the recycled component values from the r-pyrolysis oil can be applied to one or more olefin-containing effluent volumes or to one or more compounds in the olefin-containing effluent volume or to one or more PIAs prepared from the compounds in the olefin-containing effluent at the same site. The recycled component values can be applied symmetrically or asymmetrically to one or more different olefin-containing effluent volumes or to one or more compounds within the olefin-containing effluent or to the PIAs prepared at the site.

[0105] In one embodiment or in combination with any of the embodiments mentioned, the recycled component input or generation (recycled component feedstock or quota) can be to or at a first site, and the recycled component values from the said input are transferred to a second site and applied to one or more compositions prepared at the second site. The recycled component values can be applied symmetrically or asymmetrically to the compositions at the second site. The recycled component values "derived directly or indirectly from cracked r-pyrolysis oil" or "obtained from cracked r-pyrolysis oil" or recycled component values originating from cracked r-pyrolysis oil do not imply the time when the recycled component values or quotas are taken, captured, deposited into the recycled component inventory or transferred. The timing of depositing the quota or recycled component values into the recycled component inventory or realizing, identifying, capturing or transferring it is flexible and can be as early as when the r-pyrolysis oil is received at a site within the entity family that owns it or when the entity or individual that owns or operates the cracking facility brings the r-pyrolysis oil into the inventory or within the entity family. Thus, the quota or recycled component values of the volume of r-pyrolysis oil that can be obtained, captured, deposited into the recycled component inventory or transferred to the product can be obtained without having fed that volume into the cracking furnace and cracked. The quota can also be obtained during the feeding of the r-pyrolysis oil to the cracker, during cracking or when preparing the r-composition. The quota taken when the r-pyrolysis oil is owned, received and deposited into the recycled component inventory is a quota associated with, obtained from or originating from cracked r-pyrolysis oil, even if the r-pyrolysis oil has not been cracked at the time the quota is taken or deposited, provided that the r-pyrolysis oil is cracked at some point in the future.

[0106] In one embodiment, the r-composition, or its downstream reaction product, or the recycled PIA has an amount of recycled component associated with it, or containing, or labeled, advertised or certified as containing, of at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, or at least 0.5 wt.%, or at least 0.75 wt.%, or at least 1 wt.%, or at least 1.25 wt.%, or at least 1.5 wt.%, or at least 1.75 wt.%, or at least 2 wt.%, or at least 2.25 wt.%, or at least 2.5 wt.%, or at least 2.75 wt.%, or at least 3 wt.%, or at least 3.5 wt.%, or at least 4 wt.%, or at least 4.5 wt.%, or at least 5 wt.%, or at least 6 wt.%, or at least 7 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%, or at least 45 wt.%, or at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.%, or at least 65 wt.%; and / or the amount can be at most 100 wt.%, or at most 95 wt.%, or at most 90 wt.%, or at most 80 wt.%, or at most 70 wt.%, or at most 60 wt.%, or at most 50 wt.%, or at most 40 wt.%, or at most 30 wt.%, or at most 25 wt.%, or at most 22 wt.%, or at most 20 wt.%, or at most 18 wt.%, or at most 16 wt.%, or at most 15 wt.%, or at most 14 wt.%, or at most 13 wt.%, or at most 11 wt.%, or at most 10 wt.%, or at most 8 wt.%, or at most 6 wt.%, or at most 5 wt.%, or at most 4 wt.%, or at most 3 wt.%, or at most 2 wt.%, or at most 1 wt.%, or at most 0.9 wt.%, or at most 0.8 wt.%, or at most 0.7 wt.%. The recycled component value associated with the r-composition, r-compound or its downstream reaction product can be associated by applying a quota (credit or allocation) to any manufactured or sold composition, compound, or PIA. The quota can be included in a quota inventory created, maintained or operated by or for the manufacturer of the recycled PIA or r-composition. The quota can be obtained from any source along any manufacturing chain of the product, provided it is derived from the cracking of a feedstock containing r-pyrolysis oil.

[0107] In one embodiment or in combination with any of the embodiments mentioned, a recycled PIA manufacturer can manufacture recycled PIA or process reactants (e.g., any compound of an olefin-containing cracker effluent) obtained from a supplier (e.g., a cracker manufacturer or one of its entity families) from any source to manufacture recycled PIA, regardless of whether such reactants have any recycled components, and: (i) obtain from the same reactant supplier a recycled component quota applied to the reactants, or (ii) obtain a recycled component quota from any individual or entity without the reactants being provided by the individual or entity transferring the recycled component quota.

[0108] The quota in (i) is obtained from the reactant supplier, who also supplies the reactants to the recycled PIA manufacturer or within its entity family. The situation described in (i) allows the recycled PIA manufacturer to obtain the supply of non-recycled component reactants and also obtain a recycled component quota from the supplier. In one embodiment or in combination with any of the embodiments mentioned, a reactant supplier (e.g., of propylene, ethylene, butene, etc.) transfers a recycled component quota to the recycled PIA manufacturer and transfers the supply of reactants to the recycled PIA manufacturer, where the recycled component quota is not associated with the supplied reactants or even with any reactants prepared by the reactant supplier. The recycled component quota does not have to be associated with the amount of recycled components in the supplied reactants or the reactants used to prepare recycled PIA, or with the olefin-containing effluent. This allows for flexibility between the reactant supplier and the recycled PIA manufacturer in allocating recycled components among the various products they each prepare. However, in each of these cases, the recycled component quota is associated with the cracked r-pyrolysis oil.

[0109] In one embodiment or in combination with any of the embodiments mentioned, a reactant supplier transfers a recycled component quota to the recycled PIA manufacturer and transfers the supply of reactants to the recycled PIA manufacturer, where the recycled component quota is associated with the reactants. The transfer of the quota can be carried out simply by supplying reactants with an associated recycled component. Optionally, the supplied reactants are r-compounds separated from an olefin-containing effluent obtained by cracking r-pyrolysis oil, and at least a portion of the recycled component quota is associated with the r-compounds (or r-reactants). The recycled component quota transferred to the recycled PIA manufacturer can be provided in advance with the reactants, optionally in batches, or with each batch of reactants, or allocated between the parties as needed.

[0110] (ii) The quota in (ii) is obtained by the recycled PIA manufacturer (or its entity family) from any individual or entity without obtaining the supply of reactants from that individual or entity. The individual or entity may be a reactant manufacturer that does not supply reactants to the recycled PIA manufacturer or its entity family, or the individual or entity may be a manufacturer that does not manufacture reactants. In either case, the situation in (ii) allows the recycled PIA manufacturer to obtain a recycled component quota without having to purchase any reactants from the entity or individual supplying the recycled component quota. For example, an individual or entity may transfer the recycled component quota to the recycled PIA manufacturer or its entity family through a buy / sell mode or contract without the need to purchase or sell the quota (e.g., as an exchange of products that are not reactants), or the individual or entity may directly sell the quota to one of the recycled PIA manufacturer or its entity family. Alternatively, an individual or entity may transfer a product other than reactants together with its associated recycled component quota to the recycled PIA manufacturer. This is attractive for recycled PIA manufacturers with a diverse business of preparing various PIAs rather than those required to be manufactured from the supplied reactants.

[0111] The quota may be deposited into a recycled component inventory (e.g., a quota inventory). In one embodiment or in combination with any of the embodiments mentioned, the quota is generated by a manufacturer of an olefin-containing effluent. The manufacturer may also manufacture PIA, whether or not the recycled component is applied to the PIA, and whether or not the recycled component (if applied to the PIA) is taken from the recycled component inventory. For example, an olefin-containing effluent manufacturer of an olefin-containing effluent may: (a) deposit the quota into the inventory and only store it; or (b) deposit the quota of the olefin-containing effluent into the inventory and apply the quota from the inventory to one or more compounds within the olefin-containing effluent or to any PIA manufactured by the manufacturer, or (c) sell or transfer the quota from the recycled component inventory to a third party, where at least one quota obtained as described above is deposited into the recycled component inventory.

[0112] If desired, any amount of any recycled component quota can be deducted and applied to the PIA to produce recycled PIA, or applied to the non-recycled olefin-containing effluent to produce an olefin-containing effluent. For example, quotas can be generated with various sources for creating the quota. Some recycled component quotas (credits) can be derived from the methanolysis of recycled waste, or from the gasification of other types of recycled waste, or from the mechanical recycling of waste plastics or metals, or from any other chemical or mechanical recycling technology. The recycled component inventory may or may not track the source or basis for obtaining the recycled component value, or the inventory may not permit the association of the source or basis of the quota with the quota applied to the r-composition. It is sufficient that the quota is deducted from the recycled component inventory and applied to the PIA or the non-recycled olefin-containing effluent, regardless of the source of the quota, so long as the recycled component quota obtained from the r-pyrolysis oil exists in the recycled component inventory at the time of withdrawal, or the recycled component quota is obtained as specified by the recycled PIA manufacturer in step (i) or step (ii), regardless of whether the recycled component quota is actually deposited into the recycled component inventory.

[0113] In one embodiment or in combination with any of the embodiments mentioned, the recycled component quota obtained in step (i) or (ii) is deposited into a quota inventory. In one embodiment or in combination with any of the embodiments mentioned, the recycled component quota deducted from the recycled component inventory and applied to the PIA or the non-recycled olefin-containing effluent (or any compound therein) is derived from the r-pyrolysis oil.

[0114] As used throughout, the recycled component inventory can be owned by the owner of the cracker that processes the r-pyrolysis oil or one of its entity families, the olefin-containing effluent owner or the recycled PIA manufacturer, or operated by any of them, or owned or operated by any of them but at least partially benefited by any of them, or licensed by any of them or licensed to any of them. Similarly, the cracker olefin-containing effluent manufacturer or the recycled PIA manufacturer can also include any of their entity families. For example, while any of them may not own or operate the inventory, one of their entity families can own such a platform, or license it from an independent supplier, or operate it for any of them. Alternatively, an independent entity can own and / or operate the inventory and operate and / or manage at least a portion of the inventory for a service fee for any of them.

[0115] In one embodiment or in combination with any of the embodiments mentioned, the recycled PIA manufacturer obtains a supply of reactants from a supplier and also obtains a quota from the supplier, where such quota is derived from r-pyrolysis oil and optionally the quota is associated with the reactants supplied by the supplier. In one embodiment or in combination with any of the embodiments mentioned, at least a portion of the quota obtained by the recycled PIA manufacturer is: (a) applied to the PIA prepared by supplying the reactants; (b) applied to the PIA made from the same type of reactants but not made from the volume of the supplied reactants, such as the PIA made from the same type of reactants that has been made and stored in inventory or the PIA to be manufactured in the future; or (c) deposited into inventory, and the quota applied to the PIA is deducted from the inventory, where the PIA is made from a different type of reactants than the supplied reactants, or (d) deposited into inventory and stored.

[0116] It is not necessary to use r-reactants to prepare recycled PIA in all embodiments, or to obtain recycled PIA from the recycled component quota associated with the reactants. Additionally, it is not necessary to apply the quota to the feedstock to prepare the recycled PIA to which the recycled component is applied. Instead, as described above, the quota can be deposited into an electronic inventory even when associated with the reactants at the time of obtaining the reactants. However, in one embodiment or in combination with any of the embodiments mentioned, the reactants associated with the quota are used to prepare recycled PIA. In one embodiment or in combination with any of the embodiments mentioned, the recycled PIA is obtained from a recycled component quota associated with r-reactants or r-pyrolysis oil or cracked r-pyrolysis oil.

[0117] In one embodiment or in combination with any of the embodiments mentioned, the olefin-containing effluent manufacturer generates a quota from r-pyrolysis oil and: (a) applies the quota to any PIA directly or indirectly (e.g., through a reaction scheme of several intermediates) made from the cracked r-pyrolysis oil olefin-containing effluent; or (b) applies the quota to any PIA not directly or indirectly prepared from the cracked r-pyrolysis oil olefin-containing effluent, such as in the case of PIA that has been prepared and stored in inventory or PIA to be prepared in the future; or (c) deposits it into inventory, and any quota applied to the PIA is deducted from the inventory; and the deposited quota is associated or not associated with the specific quota applied to the PIA; or (d) is deposited into inventory and stored for future use.

[0118] Also provided are packages or combinations that recycle PIA and recycling component identifiers associated with the recycled PIA, where the identifier is or includes an indication that the recycled PIA contains or is derived from or associated with recycled components. The package can be any suitable package for containing polymers and / or articles, such as plastic or metal drums, railroad cars, isotainers, totes, polytotes, bales, IBC totes, bottles, compressed bales, oil drums, plastic bags, spools, rovings, wraps, or cardboard packages. The identifier can be a certificate document, a product specification stating recycled components, a label, a logo or certification mark from a certifying agency, which indicates that the article or package contains content or the recycled PIA contains content, or is made from a source or associated with recycled components, or it can be an electronic statement accompanied by the recycled PIA manufacturer with a purchase order or product, or posted as a statement, display on a website, or a logo indicating that the recycled PIA contains or is made from a source associated with or containing recycled components, or it can be an electronically transmitted advertisement associated with the recycled PIA in each case by a website or in a website, by email, or by television or through a trade show. The identifier does not need to state or indicate that the recycled components are derived from r-pyrolysis oil. Instead, the identifier can merely convey or communicate that the recycled PIA has or is derived from recycled components, regardless of the source. However, the recycled PIA has a recycled component quota that is at least partially associated with r-pyrolysis oil.

[0119] In one embodiment or in combination with any of the embodiments mentioned, information about the recycled components of the recycled PIA can be communicated to a third party, where such recycled component information is based on or derived from at least a portion of an allotment or credit. The third party can be an olefin-containing effluent manufacturer or a customer of the recycled PIA manufacturer, or it can be any other individual or entity or government organization other than the entity that owns any of them. The transmission can be electronic, through a document, through an advertisement, or any other means of communication.

[0120] In one embodiment or in combination with any of the embodiments mentioned, a system or package is provided that includes: (a) recycled PIA, and (b) an identifier, such as a credit, label, or certificate associated with the PIA, where the identifier is an indication that the PIA has or is derived from recycled components (which do not have to identify the source of the recycled components or the quota), provided that the recycled PIA prepared therefrom has a quota, or is prepared from reactants that are at least partially associated with r-pyrolysis oil.

[0121] The system can be a physical combination, such as a package having at least some recycled PIA as its contents, and the package has a label, such as an identification, that identifies an ingredient having or derived from recycled ingredients. Alternatively, whenever it transfers or sells recycled PIA having or derived from recycled ingredients, a label or certificate can be issued to a third party or customer as part of the entity's standard operating procedure. The identifier does not have to be physically on the recycled PIA or the package, and does not have to be on any physical document accompanying the recycled PIA or associated with the recycled PIA or the package. For example, the identifier can be an electronic document, certificate, or authentication mark associated with selling recycled PIA to a customer. The identifier itself only needs to convey or communicate that the recycled PIA has or is derived from recycled ingredients, regardless of the source. In one embodiment or in combination with any of the embodiments mentioned, an article made from recycled PIA can have an identifier, such as a stamp or mark embedded or adhered to the article or the package. In one embodiment or in combination with any of the embodiments mentioned, the identifier is an electronic recycled ingredient credit from any source. In one embodiment or in combination with any of the embodiments mentioned, the identifier is an electronic recycled ingredient credit sourced in r-pyrolysis oil.

[0122] Recycled PIA can be made from reactants, whether or not the reactants are recycled ingredient reactants. Once the PIA is prepared, it can be designated as having recycled ingredients based on and derived from at least a portion of a quota. The quota can be taken or deducted from a recycled ingredient inventory. The amount deducted and / or applied to the PIA can correspond to any method, such as a mass balance method.

[0123] In one embodiment, recycled PIA can be prepared by having a recycled ingredient inventory, reacting reactants in a synthesis process to prepare PIA, extracting a quota from the recycled ingredient inventory having a recycled ingredient value, and applying the recycled ingredient value to the PIA, thereby obtaining recycled PIA. The amount of the quota deducted from the inventory is flexible and will depend on the amount of recycled ingredients applied to the PIA. If not a full amount, it is sufficient to correspond to at least a portion of the recycled ingredients applied to the PIA. The recycled ingredient quota applied to the PIA does not have to be sourced from r-pyrolysis oil, but can be sourced from any other method of generating a quota from recycled waste, such as methanol alcoholysis or gasification of recycled waste, as long as the recycled ingredient inventory also contains a quota or has a quota deposited therein that is sourced from r-pyrolysis oil. However, in one embodiment or in combination with any of the embodiments mentioned, the recycled ingredient quota applied to the PIA is a quota obtained from r-pyrolysis oil.

[0124] Examples of applying recycled components to PIA or non-recycled olefin effluents or compounds therein are as follows: (1) A PIA manufacturer applies at least a portion of a quota to PIA to obtain recycled PIA, where the quota is associated with r-pyrolysis oil and the reactants used to prepare PIA do not contain any recycled components; or (2) A PIA manufacturer applies at least a portion of a quota to PIA to obtain recycled PIA, where the quota is obtained from recycled component reactants, regardless of whether the volume of the reactants is used to prepare recycled PIA; or (3) A PIA manufacturer applies at least a portion of a quota to PIA to prepare recycled PIA, where the quota is obtained from r-pyrolysis oil, and: (a) all recycled components in the r-pyrolysis oil are applied to determine the amount of recycled components in the recycled PIA, or (b) only a portion of the recycled components in the r-pyrolysis oil feedstock are applied to determine the amount of recycled components in the recycled PIA, and the remaining portion is stored in the recycled component inventory for future use or for application to other PIA, or for increasing the recycled components on existing recycled PIA, or a combination thereof, or (c) the recycled components in the r-pyrolysis oil feedstock are not applied to PIA but are stored in the inventory, and the recycled components from any source are deducted from the inventory and applied to PIA to prepare recycled PIA; or (4) A recycled PIA manufacturer applies at least a portion of a quota to the reactants used to manufacture recycled PIA, thereby obtaining PIA, where the quota is obtained by transferring or purchasing the same reactants used to manufacture PIA, and the quota is associated with the recycled components in the reactants; or (5) A recycled PIA manufacturer applies at least a portion of a quota to the reactants used to manufacture recycled PIA, thereby obtaining PIA, where the quota is obtained by transferring or purchasing the same reactants used to manufacture PIA, and the quota is not associated with the recycled components in the reactants but is associated with the recycled components of the monomers used to prepare the reactants; or (6) A recycled PIA manufacturer applies at least a portion of a quota to the reactants used to manufacture recycled PIA, thereby obtaining PIA, where the quota is not obtained by transferring or purchasing the reactants, and the quota is associated with the recycled components in the reactants; or (7) A recycled PIA manufacturer applies at least a portion of a quota to the reactants used to manufacture PIA, thereby obtaining recycled PIA, where the allocation is not obtained by transferring or purchasing the reactants, and the quota is not associated with the recycled components in the reactants but is associated with the recycled components of any monomers used to manufacture the reactants; or (8) A recycled PIA manufacturer obtains a quota derived from r-pyrolysis oil, and: (a) does not apply a portion of the quota to the reactants to prepare PIA, but applies at least a portion of the quota to PIA to prepare recycled PIA;Or (b) less than the entire portion is applied to the reactants for preparing recycled PIA, and the remaining portion is stored in inventory or applied to PIA to be prepared in the future or to existing recycled PIA in inventory to increase its recycled content value.;

[0125] In one embodiment or in combination with any of the embodiments mentioned, recycled PIA or articles made therefrom may be offered for sale or sold as recycled PIA containing recycled content or obtained with recycled content. The offer to sell or sell may be accompanied by certification or indication of a recycled content claim associated with the recycled PIA.

[0126] Designating at least a portion of the recycled PIA or olefin-containing effluent as corresponding to at least a portion of a quota (e.g., an allotment or credit) can be done in various ways and according to the system employed by the recycled PIA manufacturer or olefin-containing effluent manufacturer, which may vary by manufacturer. For example, the designation may occur only internally, by an entry in the books or files of the manufacturer or other inventory software program, or by a specification, packaging, advertisement, or statement on the product, by a logo associated with the product, by a certification declaration associated with the product being sold, or by a formula that calculates the amount deducted from inventory relative to the amount of recycled content applied to the product.

[0127] Optionally, recycled PIA may be sold. In one embodiment or in combination with any of the embodiments mentioned, a method of offering for sale or selling a polymer and / or an article is provided, by: (a) obtaining or generating a recycled content quota by any one of a recycled PIA manufacturer, an olefin-containing effluent manufacturer, or a member of their entity family (collectively referred to as the manufacturer), and the quota may be obtained by any method described herein and deposited into a recycled content inventory, the source of the recycled content quota being r-pyrolysis oil, (b) converting reactants in a synthesis process to prepare PIA, and the reactants may be any reactants or r-reactants, (c) designating (e.g., assigning or associating) the recycled content to at least a portion of the PIA from the recycled content inventory to prepare recycled PIA, wherein the inventory contains at least one entry as a quota associated with r-pyrolysis oil. The designation may be the amount of the quota deducted from the inventory, or the amount of the recycled content declared or determined by the recycled PIA manufacturer in its account. Thus, the amount of the recycled content does not necessarily have to be physically applied to the recycled PIA product. The designation may be an internal designation to or made by: the manufacturer, or a service provider having a contractual relationship with the manufacturer, and (d) offering for sale or selling the recycled PIA containing or obtained with the following recycled content, the recycled content at least partially corresponding to the designation. The amount of the recycled content represented as being included in the recycled PIA offered for sale or sold is related or associated with the designation. The amount of the recycled content may be a 1:1 relationship between the amount of the recycled content declared on the recycled PIA offered for sale or sold and the amount of the recycled content allocated or designated by the recycled PIA manufacturer to the recycled PIA.

[0128] The steps need not be sequential and may be independent of each other. For example, step a) of obtaining the quota and the step of preparing the recycled PIA may be carried out simultaneously.

[0129] As used throughout, the step of deducting a quota from the recycled content inventory need not be applied to recycled PIA products. The deduction also does not mean that the quantity disappears or is removed from the inventory log. The deduction can be an adjustment entry, a withdrawal, an entry added as a debit, or any other algorithm that adjusts inputs and outputs based on the amount of recycled content associated with the product and one or the cumulative deposited quota amounts in the inventory. For example, the deduction can be a simple step of deducting / debiting entries from one column and adding / crediting to another column within the same program or book, or an algorithm for automated deduction and entry / addition and / or application or assignment to a product information board. The step of applying a quota to PIA, where such quota is deducted from the inventory, also need not physically apply the quota to the recycled PIA product or to any document issued in connection with the recycled PIA product sold. For example, a recycled PIA manufacturer can ship the recycled PIA product to a customer and satisfy the “application” of the quota for the recycled PIA product by electronically transmitting the recycled content credit to the customer.

[0130] The use of r - pyrolysis oil is also provided, which includes converting r - pyrolysis oil in a gas cracking furnace to prepare an olefin - containing effluent. The use of r - pyrolysis oil is also provided, which includes converting reactants in a synthesis process to prepare PIA and applying at least a portion of a quota to the PIA, where the quota is associated with the r - pyrolysis oil or its source is a quota inventory, and where at least one deposit into the inventory is associated with the r - pyrolysis oil.

[0131] In one embodiment or in combination with any of the embodiments mentioned, recycled PIA obtained by any of the above methods is provided.

[0132] Reactants can be stored in storage containers and transported to a recycled PIA manufacturing facility by truck, pipeline, or ship, or as further described below, an olefin - containing effluent manufacturing facility can be integrated with the PIA facility. Reactants can be transported or transferred to an operator or facility for preparing polymers and / or articles.

[0133] In one embodiment, the method of preparing recycled PIA can be an integrated method. One such example is a method of preparing recycled PIA by the steps of: (a) cracking r - pyrolysis oil to prepare an olefin - containing effluent; and (b) separating compounds in the olefin - containing effluent to obtain separated compounds; and (c) reacting any reactants in a synthesis process to prepare PIA; (d) depositing a quota into a quota inventory, the quota being derived from the r - pyrolysis oil; and (e) applying any quota from the inventory to the PIA, thereby obtaining recycled PIA.

[0134] In one embodiment or in combination with any of the embodiments mentioned, two or more facilities can be integrated and recycled PIA can be prepared. The facilities for preparing recycled PIA or olefin-containing effluent can be independent facilities or facilities integrated with each other. For example, a system for producing and consuming reactants can be established as follows: (a) providing an olefin-containing effluent manufacturing facility configured to produce reactants; (b) providing a PIA manufacturing facility having a reactor configured to receive the reactants from the olefin-containing effluent manufacturing facility; and (c) providing a supply system between the two facilities that is in fluid communication and capable of supplying the reactants from the olefin-containing effluent manufacturing facility to the PIA manufacturing facility, where the olefin-containing effluent manufacturing facility generates or participates in generating a quota and cracking r-pyrolysis oil, and: (i) applying the quota to the reactants or to the PIA, or (ii) depositing the quota into a quota stock, and optionally withdrawing shares from the stock and applying them to the reactants or to the PIA.

[0135] The recycled PIA manufacturing facility can prepare recycled PIA by applying recycled components to the recycled PIA made from the reactants by receiving any reactants from the olefin-containing effluent manufacturing facility and deducting the quota from its stock and applying them to the PIA.

[0136] In one embodiment or in combination with any of the embodiments mentioned, a system for producing recycled PIA is also provided as follows: (a) providing an olefin-containing effluent manufacturing facility configured to produce an output composition containing an olefin-containing effluent; (b) providing a reactant manufacturing facility configured to receive the compounds separated from the olefin-containing effluent and prepare one or more downstream products of the compounds through a reaction scheme to prepare an output composition containing reactants; (c) providing a PIA manufacturing facility having a reactor configured to receive the reactants and prepare an output composition containing PIA; (d) a supply system that provides fluid communication between at least two of these facilities and is capable of supplying the output composition of one manufacturing facility to another or more of the manufacturing facilities.

[0137] The PIA manufacturing facility can prepare recycled PIA. In this system, the olefin-containing effluent manufacturing facility can put its output in fluid communication with the reactant composition manufacturing facility, and in turn, the reactant compound or composition manufacturing facility can put its output in fluid communication with the PIA manufacturing facility. Alternatively, the manufacturing facilities of a) and b) can be in fluid communication separately, or only b) and c) in fluid communication. In the latter case, the PIA manufacturing facility can prepare recycled PIA by deducting the quota from the recycled component stock and applying them to the PIA. The quota obtained and stored in the stock can be obtained by any of the methods mentioned above.

[0138] Fluid communication can be gaseous, liquid, or both. The fluid communication does not need to be continuous and can be interrupted by storage tanks, valves, or other purification or treatment facilities, as long as the fluid can be transported from the manufacturing facility to subsequent facilities through an interconnected pipeline network without using trucks, trains, ships, or airplanes. Additionally, the facilities can share the same site, or in other words, one site can contain two or more facilities. Further, the facilities can also share a storage tank site or storage tanks for auxiliary chemicals, or can also share utilities, steam, or other heat sources, etc., but are still considered separate facilities because their unit operations are separate. Facilities are typically defined by a unit boundary line.

[0139] In one embodiment or in combination with any of the embodiments mentioned, an integrated process includes at least two facilities that are co-located within 5 miles, or 3 miles, or 2 miles, or 1 mile (as a straight-line measurement) of each other. In one embodiment or in combination with any of the embodiments mentioned, at least two facilities are owned by the same entity family.

[0140] In one embodiment, an integrated recycle PIA production and consumption system is also provided. The system includes: (a) a manufacturing facility for olefin-containing effluent configured to produce an output composition containing olefin-containing effluent; (b) a reactant manufacturing facility configured to receive a compound separated from the olefin-containing effluent and prepare one or more downstream products of the compound through a reaction scheme to prepare an output composition containing reactants; (c) a PIA manufacturing facility having a reactor configured to receive the reactants and prepare an output composition containing PIA; (d) a pipeline system that interconnects at least two of the facilities, optionally interconnected with intermediate processing equipment or storage facilities, the pipeline system being capable of withdrawing an output composition from one facility and receiving the output at any one or more of the other facilities.

[0141] The system does not necessarily require fluid communication between two facilities, although fluid communication is desirable. For example, a compound separated from the olefin-containing effluent can be transported to the reactant facility through an interconnected pipeline network, which can be interrupted by other processing equipment, such as equipment for treatment, purification, pumping, compression, or equipment suitable for combining streams or storage facilities, all of which include optional metering, valves, or interlock devices. The equipment can be fixed to the ground or fixed to a structure fixed to the ground. The interconnected pipelines do not need to be connected to the reactant reactor or cracker, but are connected to the transfer and receiving points at their respective facilities. The interconnected pipeline system does not need to connect all three facilities to each other, but the interconnected pipeline system can be between facilities a)-b), or b)-c), or between a)-b)-c).

[0142] There is also provided a cyclic manufacturing method, which includes: (1) providing r-pyrolysis oil, and (2) cracking the r-pyrolysis oil to produce an olefin-containing effluent, and (i) reacting the compounds separated from the olefin-containing effluent to prepare recycled PIA, or (ii) combining the recycled quota obtained from the r-pyrolysis oil with the PIA prepared from the compounds separated from the non-recycled olefin-containing effluent to produce recycled PIA; and (3) taking out at least a part of any of the recycled PIA or any other articles, compounds or polymers prepared from the recycled PIA as a raw material to prepare the r-pyrolysis oil.

[0143] In the above process, a full cycle or closed-loop process is provided, in which the recycled PIA can be recycled multiple times.

[0144] Examples of articles included in PIA are fibers, yarns, tows, continuous filaments, staple fibers, rovings, fabrics, textiles, sheets, films (such as polyolefin films), sheets, composite sheets, plastic containers and consumer products.

[0145] In one embodiment or in combination with any of the embodiments mentioned, the recycled PIA is a polymer or article of the same family or class as the polymer or article used to prepare the r-pyrolysis oil.

[0146] In one embodiment or in combination with any of the embodiments mentioned, the composition, polymer or article made of or made with the recycled PIA received back belongs to the same family or class as the composition, polymer or article used to manufacture the r-pyrolysis oil.

[0147] The terms "recycled waste", "waste stream" and "recycled waste stream" are used interchangeably and refer to any type of waste or waste-containing stream that is reused in a production process rather than permanently disposed of (e.g., in a landfill or incinerator). The recycled waste stream is the flow or accumulation of recycled waste from industrial and consumer sources, at least part of which is recycled.

[0148] The recycled waste stream includes materials, products and articles (collectively referred to as "materials" when used alone). Recycled waste can be solid or liquid. Examples of solid recycled waste streams include plastics, rubber (including tires), textiles, wood, biological waste, modified cellulose, wet laid products and any other materials capable of pyrolysis. Examples of liquid waste streams include industrial sludge, oils (including those derived from plants and petroleum), recycled lubricating oils, or vegetable or animal oils, and any other chemical streams from industrial plants.

[0149] In one embodiment or in combination with any of the embodiments mentioned, the recycled waste stream to be pyrolyzed includes at least in part a stream containing post-industrial materials, or post-consumer materials, or both post-industrial and post-consumer materials. In one embodiment or in combination with any of the embodiments mentioned, post-consumer materials are materials that have been used at least once for their intended application for any duration regardless of wear, or have been sold to an end-use consumer, or have been discarded into a recycling bin by any individual or entity other than a manufacturer or business engaged in the manufacture or sale of the materials.

[0150] In one embodiment or in combination with any of the embodiments mentioned, post-industrial materials are materials that have been manufactured and not used for their intended application, or not sold to an end-use customer, or discarded by a manufacturer or any other entity involved in the sale of the materials. Examples of post-industrial materials include reprocessed, reground, scrap, trim, out-of-specification materials, and finished materials transferred from a manufacturer to any downstream customer (e.g., manufacturer to wholesaler to distributor) but not yet used or sold to an end-use customer.

[0151] The form of the recycled waste stream that can be fed into the pyrolysis unit is not limited and can include any form of article, product, material, or part thereof. A part of an article can take the form of a sheet, extruded profile, molded article, film, laminate, foam sheet, fragment, flake, granule, fiber, agglomerate, briquette, powder, debris, strip, or a sheet of any shape with various shapes, or any other form other than the original form of the article and is suitable for feeding into the pyrolysis unit.

[0152] In one embodiment or in combination with any of the embodiments mentioned, the recycled waste is reduced in size. The reduction in size can be carried out in any way, including shredding, tearing, harrowing, confrication, pulverizing, cutting the raw material, molding, compressing, or dissolving in a solvent.

[0153] The recycled waste plastics can be separated as a type of polymer stream, or can be a stream of mixed recycled waste plastics. The plastics can be any organic synthetic polymer that is solid at 25°C and 1 atm. The plastics can be thermosetting, thermoplastic or elastomeric plastics. Examples of plastics include high density polyethylene and its copolymers, low density polyethylene and its copolymers, polypropylene and its copolymers, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyesters (including polyethylene terephthalate), copolyesters and terephthalate copolyesters (e.g., containing residues of TMCD, CHDM, propylene glycol or NPG monomers), polyethylene terephthalate, polyamides, poly(methyl methacrylate), polytetrafluoroethylene, acrylonitrile-butadiene-styrene (ABS), polyurethanes, cellulose and its derivatives, such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate; regenerated cellulose products such as viscose and rayon, epoxy resins, polyamides, phenolic resins, polyacetals, polycarbonates, polyphenyl alloys, polypropylene and its copolymers, polystyrene, styrene compounds, vinyl compounds, styrene-acrylonitrile, thermoplastic elastomers, and urea-based polymers and polymers containing melamine.

[0154] Suitable recycled waste plastics also include any of those having resin ID codes 1 - 7 within the chasing arrow triangle established by SPI. In one embodiment or in combination with any of the embodiments mentioned, the r-pyrolysis oil is made from a recycled waste stream, at least a portion of which contains plastics that are not normally recycled. These include plastics having the numbers 3 (polyvinyl chloride), 5 (polypropylene), 6 (polystyrene) and 7 (others). In one embodiment or in combination with any of the embodiments mentioned, the recycled waste stream to be pyrolyzed contains less than 10 weight percent, or no more than 5 weight percent, or no more than 3 weight percent, or no more than 2 weight percent, or no more than 1 weight percent, or no more than 0.5 weight percent, or no more than 0.2 weight percent, or no more than 0.1 weight percent, or no more than 0.05 weight percent of plastic number 3 (polyvinyl chloride), or optionally plastic numbers 3 and 6, or optionally plastic numbers 3, 6 and 7.

[0155] Examples of recycled rubbers include natural and synthetic rubbers. The form of the rubber is not limited and includes tires.

[0156] Examples of recycled waste wood include softwood and hardwood, wood chips, pulp or finished products. Sources of large amounts of recycled waste wood are industry, construction or demolition.

[0157] Examples of recycled biological waste include domestic biological waste (e.g., food), green or garden biological waste, and biological waste from the industrial food processing industry.

[0158] Examples of recycled textiles include natural and / or synthetic fibers, rovings, yarns, nonwoven fiber webs, cloth, fabric, and products made of or containing any of the foregoing items. Textiles can be woven, knitted, knotted, stitched, tufted, pressed together of fibers, such as in a felting operation, embroidered, laced, crocheted, woven, or nonwoven fiber webs and materials. Textiles include fabric and fibers, waste, or off-specification fibers or yarns or textiles separated from textiles or other products containing fibers, or any other source of loose fibers and yarns. Textiles also include staple fibers, continuous fibers, threads, tow bands, twisted and / or staple yarns, greige goods made of yarn, finished textiles made by wet processing of greige goods, and garments made of finished textiles or any other textiles. Textiles include apparel, furnishings, and industrial-type textiles.

[0159] Examples of recycled textiles in the apparel category (things worn by humans or made for the body) include sport coats, suits, pants and casual or work pants, shirts, socks, sportswear, dresses, intimate apparel, outerwear such as raincoats, low-temperature jackets and coats, sweaters, protective clothing, uniforms, and accessories such as scarves, hats, and gloves. Examples of textiles in the furnishings category include furniture upholstery and covers, rugs and mats, curtains, bedding such as sheets, pillowcases, duvets, quilts, mattress covers; linens, tablecloths, towels, and blankets. Examples of industrial textiles include transportation (automobile, aircraft, train, bus) seats, floor mats, luggage liners, and headliners; outdoor furniture and mats, tents, backpacks, luggage, ropes, conveyor belts, calender roll felts, polishing cloths, rags, soil erosion textiles and geotextiles, agricultural mats and screens, personal protective equipment, bulletproof vests, medical bandages, sutures, tapes, etc.

[0160] The recycled nonwoven web can also be a dry-laid nonwoven web. Examples of suitable articles that can be formed from a dry-laid nonwoven web as described herein can include those for personal, consumer, industrial, food service, medical, and other types of end uses. Specific examples can include, but are not limited to, baby wipes, flushable wipes, disposable diapers, training pants, feminine hygiene products such as sanitary napkins and tampons, adult incontinence pads, underwear or panties, and pet training pads. Other examples include a variety of different dry or wet wipes, including those for consumer (such as personal care or household) and industrial (such as food service, healthcare, or professional) use. The nonwoven web can also be used as pillows, mattress pads, and furniture upholstery, batting for quilts and duvet covers. In the medical and industrial fields, the nonwoven web of the present invention can be used for medical and industrial face masks, protective clothing, caps and shoe covers, disposable sheets, surgical gowns, drapes, bandages, and medical dressings. Additionally, the nonwoven web can be used for environmental textiles, such as geotextiles and tarpaulins, oil pads, and chemical absorbent pads, and building materials, such as sound insulation or heat insulation, tents, wood and soil covers, and sheets. The nonwoven web can also be used for other consumer end uses, such as carpet backing, packaging of consumer, industrial, and agricultural products, heat insulation or sound insulation, and various types of clothing. The dry-laid nonwoven web can also be used for a variety of filtration applications, including transportation (e.g., automotive or aviation), commercial, residential, industrial, or other professional applications. Examples can include filter elements for consumer or industrial air or liquid filters (e.g., gasoline, oil, water), including nanofiber webs for microfiltration and end uses such as tea bags, coffee filters, and dryer sheets. In addition, the nonwoven web can be used to form a variety of components for automobiles, including but not limited to brake pads, trunk liners, carpet tufting, and bottom fillers.

[0161] The recycled textiles can include a single type or multiple types of natural fibers and / or a single type or multiple types of synthetic fibers. Examples of textile fiber combinations include all-natural, all-synthetic, two or more types of natural fibers, two or more types of synthetic fibers, one type of natural fiber and one type of synthetic fiber, one type of natural fiber and two or more types of synthetic fibers, two or more types of natural fibers and one type of synthetic fiber, and two or more types of natural fibers and two or more types of synthetic fibers.

[0162] Examples of recycled wet-laid products include cardboard, office paper, newsprint and magazines, printing and writing paper, toilet paper, tissue / towel paper, packaging / container board, specialty paper, clothing, bleached board, corrugating medium, wet-laid molded products, unbleached kraft paper, decorative laminates, security paper and currency, extra-large format graphics, specialty products, and food and beverage products.

[0163] Examples of modified cellulose include cellulose acetate, diacetate cellulose, triacetate cellulose, regenerated cellulose such as viscose, rayon, and Lyocel TM The product is in any form, such as a tow band, staple fiber, continuous fiber, film, sheet, molded or stamped product, and is included in or on any article such as a cigarette filter rod, ophthalmic product, screwdriver handle, optical film, and coating.

[0164] Examples of recycled vegetable or animal oils include oils recovered from animal processing facilities and recycled waste from restaurants.

[0165] The sources for obtaining recycled post-consumer or post-industrial recycled waste are not limited and can include recycled waste present in and / or separated from the municipal solid waste recycle stream ("MSW"). For example, the MSW stream can be processed and sorted into several discrete components, including textiles, fibers, paper, wood, glass, metal, etc. Other textile sources include those obtained by collection agencies, or those obtained by textile brand owners or alliances or organizations or on behalf of or for the above organizations, or those obtained by brokers, or those obtained from post-industrial sources such as waste from mills or commercial production facilities, unsold textiles from wholesalers or distributors, from mechanical and / or chemical sorting or separation facilities, from landfills, or stranded on docks or ships.

[0166] In one embodiment or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit can contain in each case at least one, or at least two, or at least three, or at least four, or at least five, or at least six different types of recycled waste in a weight percentage of at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99. The reference to "type" is determined by resin ID codes 1-7. In one embodiment or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit contains polyvinyl chloride and / or polyethylene terephthalate in a weight percentage of less than 25, or not exceeding 20, or not exceeding 15, or not exceeding 10, or not exceeding 5, or not exceeding 1 in each case. In one embodiment or in combination with any of the embodiments mentioned, the recycled waste stream contains at least one, two, or three plasticized plastics.

[0167] Figure 2 An exemplary pyrolysis system 110 is described, which can be used to at least partially convert one or more recycled wastes, particularly recycled plastic wastes, into various useful pyrolysis-derived products. It should be understood that Figure 2The pyrolysis system shown is merely an example of a system in which the present disclosure may be implemented. The present invention may be applied to a variety of other systems in which it is desired to effectively and efficiently pyrolyze recycled waste, particularly recycled plastic waste, into various desired end products. This will now be described in more detail Figure 2 The exemplary pyrolysis system shown.

[0168] As Figure 2 shown, the pyrolysis system 110 may include a waste plastic source 112 for supplying one or more waste plastics to the system 110. The plastic feedstock 112 may be, for example, a hopper, a storage bin, a railcar, a long-haul trailer, or any other device that can hold or store waste plastics. In one embodiment or in combination with any of the embodiments mentioned herein, the waste plastics supplied by the plastic source 112 may be in the form of solid particles, such as fragments, flakes, or powders. Although not described in Figure 2 this document, the pyrolysis system 110 may also include additional sources of other types of recycled waste that can be used to provide other feed types to the system 110.

[0169] In one embodiment or in combination with any of the embodiments mentioned herein, the waste plastics may include one or more post-consumer waste plastics, such as high-density polyethylene, low-density polyethylene, polypropylene, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyethylene terephthalate, polyamides, poly(methyl methacrylate), polytetrafluoroethylene, or combinations thereof. In one embodiment or in combination with any of the embodiments mentioned herein, the waste plastics may include high-density polyethylene, low-density polyethylene, polypropylene, or combinations thereof. As used herein, "post-consumer" refers to non-virgin plastics that have previously been introduced into the consumer market.

[0170] As used herein, "post-consumer waste plastics" refers to waste plastics introduced and derived from the consumer market. As used herein, "post-industrial waste plastics" refers to waste plastics that are not post-consumer waste plastics.

[0171] In one embodiment or in combination with any embodiment mentioned herein, a feedstock containing waste plastics can be supplied from a plastics source 112. In one embodiment or in combination with any embodiment mentioned herein, the feedstock containing waste plastics can include high density polyethylene, low density polyethylene, polypropylene, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyethylene terephthalate, polyamides, poly(methyl methacrylate), polytetrafluoroethylene, modified celluloses (such as cellulose acetate, diacetate cellulose, triacetate cellulose, cellulose acetate butyrate, cellulose acetate propionate, regenerated cellulose such as viscose or rayon), copolyesters (such as ethylene glycol modified polyethylene terephthalate, TMCD modified polyester, CHDM modified polyester, or TMCD modified CHDM and terephthalate copolyesters), ABS, or combinations thereof.

[0172] In one embodiment or in combination with any embodiment mentioned herein, the feedstock containing waste plastics can include at least one, two, three, or four different types of waste plastics, each in a weight percentage of at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99.

[0173] In one embodiment or in combination with any embodiment mentioned herein, the plastic waste can include polyvinyl chloride and / or polyethylene terephthalate, each in a weight percentage of no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 1. In one embodiment or in combination with any embodiment mentioned herein, the feedstock containing waste plastics can include at least one, two, or three plasticizers. The reference to "type" is determined by resin ID codes 1-7.

[0174] As Figure 2 shown, the solid waste plastic feedstock from the plastics source 112 can be supplied to a feedstock pretreatment unit 114. In the feedstock pretreatment unit 114, the introduced waste plastics can undergo a number of pretreatments to facilitate subsequent pyrolysis reactions. Such pretreatments can include, for example, washing, mechanical agitation, flotation, size reduction, or any combination thereof. In one embodiment or in combination with any embodiment mentioned herein, the introduced plastic waste can be subjected to mechanical agitation or size reduction operations to reduce the particle size of the plastic waste. Such mechanical agitation can be provided by any mixing, shearing, or grinding device known in the art, which can reduce the average particle size of the introduced plastics by at least 10%, or at least 25%, or at least 50%, or at least 75%.

[0175] Next, the pre-treated plastic feedstock can be introduced into the plastic feed system 116. The plastic feed system 116 can be configured to introduce the plastic feed into the pyrolysis reactor 118. The plastic feed system 116 can include any system known in the art capable of feeding solid plastic into the pyrolysis reactor 118. In one embodiment or in combination with any embodiment mentioned herein, the plastic feed system 116 can include a screw feeder, a hopper, a pneumatic conveying system, mechanical metal bars or chains, or a combination thereof.

[0176] When in the pyrolysis reactor 118, at least a portion of the plastic feed can be subjected to a pyrolysis reaction, which produces a pyrolysis effluent comprising pyrolysis oil (e.g., r-pyrolysis oil) and pyrolysis gas (e.g., r-pyrolysis gas). The pyrolysis reactor 118 can be, for example, an extruder, a tubular reactor, a tank, a stirred tank reactor, a riser reactor, a fixed bed reactor, a fluidized bed reactor, a rotary kiln, a vacuum reactor, a microwave reactor, an ultrasonic or supersonic reactor, or an autoclave, a membrane reactor, or a combination of these reactors.

[0177] Generally, pyrolysis is a process involving the chemical and thermal decomposition of the introduced feed. Although all pyrolysis processes can generally be characterized by a reaction environment substantially free of oxygen, the pyrolysis process can be further defined by, for example, the pyrolysis reaction temperature in the reactor, the residence time in the pyrolysis reactor, the reactor type, the pressure in the pyrolysis reactor, and the presence or absence of a pyrolysis catalyst.

[0178] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis reaction can include heating and converting the plastic feedstock in an atmosphere substantially free of oxygen or in an atmosphere containing less oxygen relative to ambient air. In one embodiment or in combination with any embodiment mentioned herein, the atmosphere within the pyrolysis reactor 118 can contain oxygen in a total percentage not exceeding 5, or not exceeding 4, or not exceeding 3, or not exceeding 2, or not exceeding 1, or not exceeding 0.5 in each case.

[0179] In one embodiment or in combination with any embodiment mentioned herein, lift gas and / or feed gas can be used to introduce the plastic feedstock into the pyrolysis reactor 118 and / or to facilitate the various reactions within the pyrolysis reactor 118.

[0180] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process can be carried out in the presence of lift gas and / or feed gas, the lift gas and / or feed gas comprising an inert gas such as nitrogen, carbon dioxide, and / or steam, consisting essentially of an inert gas, or consisting of an inert gas. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process can be carried out in the presence of a reducing gas such as hydrogen and / or carbon monoxide.

[0181] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process can be carried out in the presence of a lift gas and / or a feed gas, wherein the lift gas and / or the feed gas contains steam, consists essentially of steam, or consists of steam. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process is carried out in the presence of a feed gas and / or a lift gas containing at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95 or at least 99 wt% of steam. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process is carried out in the presence of a feed gas and / or a lift gas containing no more than 99, no more than 90, no more than 80, no more than 70, no more than 60, no more than 50, no more than 40, no more than 30, no more than 20 or no more than 10 wt% of steam.

[0182] In one embodiment or in combination with any embodiment mentioned herein, steam can be present in an amount sufficient to remove at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 99% of the nitrogen and / or chlorine initially present in the pyrolysis feedstock.

[0183] Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process can be carried out in the presence of a lift gas and / or a feed gas, wherein the lift gas and / or the feed gas contains a reducing gas, such as hydrogen, carbon monoxide or a combination thereof, consists essentially of a reducing gas, or consists of a reducing gas. The reducing gas can serve as the feed gas and / or the lift gas and can facilitate the introduction of the plastic feed into the pyrolysis reactor 118. The reducing gas can be added together with the plastic waste before being introduced into the pyrolysis reactor 118 and / or can be directly added to the pyrolysis reactor.

[0184] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process is carried out in the presence of a feed gas and / or lift gas comprising at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95 or at least 99 wt% of at least one reducing gas. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process is carried out in the presence of a feed gas and / or lift gas comprising no more than 99, no more than 90, no more than 80, no more than 70, no more than 60, no more than 50, no more than 40, no more than 30, no more than 20 or no more than 10 wt% of at least one reducing gas.

[0185] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process is carried out in the presence of a reducing gas comprising at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95 or at least 99 wt% of hydrogen. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process is carried out in the presence of a reducing gas comprising no more than 99, no more than 90, no more than 80, no more than 70, no more than 60, no more than 50, no more than 40, no more than 30, no more than 20 or no more than 10 wt% of hydrogen.

[0186] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process is carried out in the presence of a reducing gas comprising at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95 or at least 99 wt% of carbon monoxide. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process is carried out in the presence of a reducing gas comprising no more than 99, no more than 90, no more than 80, no more than 70, no more than 60, no more than 50, no more than 40, no more than 30, no more than 20 or no more than 10 wt% of carbon monoxide.

[0187] In one embodiment or in combination with any embodiment mentioned herein, a reducing gas may be present in an amount sufficient to remove at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% of the nitrogen and / or chlorine initially present in the pyrolysis feedstock.

[0188] In one embodiment or in combination with any embodiment mentioned herein, the temperature in the pyrolysis reactor 118 may be adjusted to facilitate the production of certain end products. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 may be at least 325 °C, or at least 350 °C, or at least 375 °C, or at least 400 °C, or at least 425 °C, or at least 450 °C, or at least 475 °C, or at least 500 °C, or at least 525 °C, or at least 550 °C, or at least 575 °C, or at least 600 °C, or at least 625 °C, or at least 650 °C, or at least 675 °C, or at least 700 °C, or at least 725 °C, or at least 750 °C, or at least 775 °C, or at least 800 °C Additionally, or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 may be no more than 1,100 °C, or no more than 1,050 °C, or no more than 1,000 °C, or no more than 950 °C, or no more than 900 °C, or no more than 850 °C, or no more than 800 °C, or no more than 750 °C, or no more than 700 °C, or no more than 650 °C, or no more than 600 °C, or no more than 550 °C, or no more than 525 °C, or no more than 500 °C, or no more than 475 °C, or no more than 450 °C, or no more than 425 °C, or no more than 400 °C. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 may be in the range of 325 to 1,100 °C, 350 to 900 °C, 350 to 700 °C, 350 to 550 °C, 350 to 475 °C, 500 to 1,100 °C, 600 to 1,100 °C, or 650 to 1,000 °C.

[0189] In one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be at least 1 second, or at least 2 seconds, or at least 3 seconds, or at least 4 seconds, or at least 10 seconds, or at least 20 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes, or at least 75 minutes, or at least 90 minutes. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be no more than 6 hours, or no more than 5 hours, or no more than 4 hours, or no more than 3 hours, or no more than 2 hours, or no more than 1 hour, or no more than 0.5 hours. In one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be in the range of 30 minutes to 4 hours, or 30 minutes to 3 hours, or 1 hour to 3 hours, or 1 hour to 2 hours.

[0190] In one embodiment or in combination with any embodiment mentioned herein, the pressure within the pyrolysis reactor 118 can be maintained at a pressure of at least 0.1 bar, or at least 0.2 bar, or at least 0.3 bar, and / or no more than 60 bar, or no more than 50 bar, or no more than 40 bar, or no more than 30 bar, or no more than 20 bar, or no more than 10 bar, or no more than 8 bar, or no more than 5 bar, or no more than 2 bar, or no more than 1.5 bar, or no more than 1.1 bar. In one embodiment or in combination with any embodiment mentioned herein, the pressure within the pyrolysis reactor 118 can be maintained at approximately atmospheric pressure or in the range of 0.1 to 100 bar, or 0.1 to 60 bar, or 0.1 to 30 bar, or 0.1 to 10 bar, or 1.5 bar, 0.2 to 1.5 bar, or 0.3 to 1.1 bar.

[0191] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis catalyst may be introduced into the plastic feed and / or directly into the pyrolysis reactor 118 before introduction into the pyrolysis reactor 118 to produce r-catalytic pyrolysis oil or r-pyrolysis oil prepared by a catalytic pyrolysis process. In one embodiment or in combination with any embodiment mentioned herein, the catalyst may comprise: (i) solid acids such as zeolites (e.g., ZSM-5, mordenite, β, ferrierite, and / or zeolite-Y); (ii) superacids such as sulfonated, phosphorylated, or fluorinated forms of zirconia, titania, alumina, silica-alumina, and / or clays; (iii) solid bases such as metal oxides, mixed metal oxides, metal hydroxides, and / or metal carbonates, particularly those of alkali metals, alkaline earth metals, transition metals, and / or rare earth metals; (iv) hydrotalcites and other clays; (v) metal hydrides, particularly those of alkali metals, alkaline earth metals, transition metals, and / or rare earth metals; (vi) alumina and / or silica-alumina; (vii) homogeneous catalysts such as Lewis acids, metal tetrachloroaluminates, or organic ionic liquids; (viii) activated carbon; or (ix) combinations thereof. The catalyst may include platinum, nickel, palladium, ruthenium, rhodium, nickel, mordenite, or combinations thereof.

[0192] In one embodiment or in combination with any embodiment mentioned herein, the catalyst may include a homogeneous catalyst or a heterogeneous catalyst.

[0193] In one embodiment or in combination with any embodiment mentioned herein, the catalyst may include a catalyst having a mesoporous structure, such as MCM-41, FSM-16, Al-SBA-15, or combinations thereof.

[0194] In one embodiment or in combination with any embodiment mentioned herein, the catalyst may include silica-aluminum, alumina, mordenite, zeolite, microporous catalyst, macroporous catalyst, or combinations thereof.

[0195] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 occurs substantially in the absence of a catalyst, particularly the above-mentioned catalysts. In such an embodiment, a non-catalytic, heat-retaining inert additive, such as sand, may still be introduced into the pyrolysis reactor 118 to facilitate heat transfer within the reactor 118. Such a catalyst-free pyrolysis process may be referred to as "thermal pyrolysis".

[0196] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 can occur in the substantially absence of a pyrolysis catalyst, at a temperature in the range of 350 to 550 °C, at a pressure in the range of 0.1 to 60 bar, and with a residence time of 0.2 seconds to 4 hours or 0.5 hours to 3 hours.

[0197] Referring again to Figure 2 , the pyrolysis effluent 120 leaving the pyrolysis reactor 118 generally includes pyrolysis gas, pyrolysis vapor, and residual solids. As used herein, the vapor produced during the pyrolysis reaction may be interchangeably referred to as "pyrolysis oil", which refers to the vapor when condensed into its liquid state. In one embodiment or in combination with any of the embodiments mentioned herein, the solids in the pyrolysis effluent 20 may include carbon, ash, unreacted plastic solids, other unreacted solids from the feedstock, and / or particles of spent catalyst (if a catalyst is used).

[0198] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis effluent 120 may contain pyrolysis vapor in each case in a weight percentage of at least 20, or at least 25, or at least 30, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, which can then be condensed to the resulting pyrolysis oil (e.g., r-pyrolysis oil). Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis effluent 120 may contain pyrolysis vapor in each case in a weight percentage of not more than 99, or not more than 95, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis effluent 120 may contain 20 to 99 weight percent, 40 to 90 weight percent, or 55 to 90 weight percent of pyrolysis vapor.

[0199] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain, in each case, at least 1, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75 weight percent of pyrolysis gas (e.g., r-pyrolysis gas). As used herein, "pyrolysis gas" refers to a composition produced by pyrolysis and is a gas at standard temperature and pressure (STP). Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 20 may contain, in each case, no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15 weight percent of pyrolysis vapor. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain from 1 to 90 weight percent, or from 5 to 60 weight percent, or from 10 to 60 weight percent, or from 10 to 30 weight percent, or from 5 to 30 weight percent of pyrolysis gas.

[0200] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain, in each case, no more than 15, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6, or no more than 5, or no more than 4 or no more than 3 weight percent of residual solids.

[0201] In one embodiment or in any combination of the embodiments mentioned, there is provided a cracker feedstock composition comprising pyrolysis oil (r-pyrolysis oil), and the r-pyrolysis oil composition comprises recycled component catalytic pyrolysis oil (r-catalytic pyrolysis oil) and recycled component pyrolysis oil (r-pyrolysis oil). R-pyrolysis oil is pyrolysis oil prepared without the addition of a pyrolysis catalyst. The cracker feedstock may include at least 5, 10, 15 or 20 weight percent of r-catalytic pyrolysis oil, which may optionally have been hydrotreated. The r-pyrolysis oil and r-catalytic pyrolysis oil containing r-pyrolysis oil may be cracked according to any of the processes described herein to provide an olefin-containing effluent stream. The r-catalytic pyrolysis oil may be blended with r-pyrolysis oil to form a blend stream that is cracked in a cracker unit. Optionally, the blend stream may contain no more than 10, 5, 3, 2, 1 weight percent of unhydrotreated r-catalytic pyrolysis oil.

[0202] In one embodiment or in combination with any of the embodiments mentioned, the r-pyrolysis oil is free of r-catalytic pyrolysis oil.

[0203] As Figure 2 shown, the converted effluent 120 from the pyrolysis reactor 118 can be introduced into the solid separator 122. The solid separator 122 can be any conventional device capable of separating solids from gases and vapors, such as a cyclone separator or a gas filter or a combination thereof. In one embodiment or in combination with any embodiment mentioned herein, the solid separator 122 removes most of the solids from the converted effluent 120. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the solid particles 124 recovered in the solid separator 122 can be introduced into an optional regenerator 126 for regeneration, typically by combustion. After regeneration, at least a portion of the hot regenerated solids 128 can be introduced directly into the pyrolysis reactor 118. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the solid particles 124 recovered in the solid separator 122 can be introduced directly back into the pyrolysis reactor 118, particularly if the solid particles 124 contain a significant amount of unconverted plastic waste. Solids can be removed from the regenerator 126 via line 145 and discharged from the system.

[0204] Returning Figure 2 , the remaining gas and vapor conversion products 130 from the solid separator 122 can be introduced into the fractionation tower 132. In the fractionation tower 132, at least a portion of the pyrolysis oil vapor can be separated from the cracked gas, thereby forming a cracked gas product stream 134 and a pyrolysis oil vapor stream 136. Suitable systems for use as the fractionation tower 132 can include, for example, distillation towers, membrane separation units, quench towers, condensers, or any other known separation units known in the art. In one embodiment or in combination with any embodiment mentioned herein, any residual solids 146 accumulated in the fractionation tower 132 can be introduced into the optional regenerator 126 for additional processing.

[0205] In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the pyrolysis oil vapor stream 136 can be introduced into a quench unit 138 to at least partially quench the pyrolysis vapors into their liquid form (i.e., pyrolysis oil). The quench unit 138 can include any suitable quench system known in the art, such as a quench tower. The resulting liquid pyrolysis oil stream 140 can be removed from the system 110 and used in other downstream applications described herein. In one embodiment or in combination with any embodiment mentioned herein, the liquid pyrolysis oil stream 140 may not be subjected to any additional processing, such as hydrotreating and / or hydrogenation, before being used in any of the downstream applications described herein.

[0206] In one embodiment or in combination with any of the embodiments described herein, at least a portion of the pyrolysis oil vapor stream 136 can be introduced into a hydrotreating unit 142 for further refining. The hydrotreating unit 142 can include a hydrocracker, a catalytic cracker operating with a hydrogen feed stream, a hydrotreating unit, and / or a hydrogenation unit. In the hydrotreating unit 142, the pyrolysis oil vapor stream 136 can be treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil and remove undesirable by-products from the pyrolysis oil. The resulting hydrotreated pyrolysis oil vapor stream 144 can be removed and introduced into a quench unit 138. Alternatively, the pyrolysis oil vapor can be cooled, liquefied, and then treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil. In this case, hydrogenation or hydrotreating is carried out in the liquid-phase pyrolysis oil. In this embodiment, post-hydrogenation or post-hydrotreating does not require a quench step.

[0207] The pyrolysis system 110 described herein can produce pyrolysis oil (e.g., r-pyrolysis oil) and pyrolysis gas (e.g., r-pyrolysis gas), which can be directly used in various downstream applications based on their desired formulations. Various characteristics and properties of the pyrolysis oil and pyrolysis gas are described below. It should be noted that while all of the following characteristics and properties can be listed separately, it is contemplated that each of the following characteristics and / or properties of the pyrolysis oil or pyrolysis gas is not mutually exclusive and can exist in any combination.

[0208] The pyrolysis oil can mainly contain hydrocarbons having 4 to 30 carbon atoms per molecule (e.g., C4 to C 30 hydrocarbons). As used herein, the term "Cx" or "Cx hydrocarbon" refers to a hydrocarbon compound that includes a total of x carbons per molecule and includes all olefins, paraffins, aromatic hydrocarbons, and isomers having that number of carbon atoms. For example, each of n-, iso-, and tert-butane and butene and butadiene molecules will fall within the general description "C4".

[0209] In one embodiment or in combination with any of the embodiments described herein, the pyrolysis oil fed to the cracking furnace can have a C4-C content of at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent in each case, based on the weight of the pyrolysis oil. 30 hydrocarbon content, based on the weight of the pyrolysis oil.

[0210] In one embodiment or in combination with any of the embodiments described herein, the pyrolysis oil fed to the furnace can mainly contain C5-C 25 、C5-C 22 or C5-C 20Hydrocarbons, or may contain in each case a weight percentage of at least about 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 of C5-C 25 、C5-C 22 or C5-C 20 hydrocarbons, based on the weight of the pyrolysis oil.

[0211] The gas furnace can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock, thus eliminating the need to subject the pyrolysis oil feedstock to separation techniques to deliver the smaller or lighter hydrocarbon fractions to the cracking furnace. In one embodiment or in any of the embodiments mentioned, after being transported from the pyrolysis manufacturer and before feeding the pyrolysis oil into the cracking furnace, the pyrolysis oil does not undergo a separation process for separating the heavy hydrocarbon fraction from the lighter hydrocarbon fraction relative to each other. Feeding the pyrolysis oil into the gas furnace allows the use of pyrolysis oil containing a heavy tail or a higher carbon number equal to or higher than 12. In one embodiment or in any of the embodiments mentioned, the pyrolysis oil fed to the cracking furnace is a C5-C 25 hydrocarbon stream that contains at least 1 wt.%, or at least 3 wt.%, or at least 5 wt.%, or at least 8 wt.%, or at least 10 wt.%, or at least 12 wt.%, or at least 15 wt.%, or at least 18 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%, or at least 45 wt.%, or at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.% of hydrocarbons in the range of C 12 to C 25 (including the end values), or in the range of C 14 to C 25 (including the end values), or in the range of C 16 to C 25 (including the end values).

[0212] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a C6-C content of at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55 in each case by weight percentage, based on the weight of the pyrolysis oil. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a C6-C content of no more than 98.5, or no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60 in each case by weight percentage. 12 hydrocarbon content, based on the weight of the pyrolysis oil. 12Hydrocarbon content. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a C6-C content of 10 to 95 weight percent, 20 to 80 weight percent, or 35 to 80 weight percent 12 Hydrocarbon content.

[0213] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a C content of at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30 weight percent in each case 13 -C 23 Hydrocarbon content. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a C content of not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40 weight percent in each case 13 to C 23 Hydrocarbon content. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a C content of 1 to 80 weight percent, 5 to 65 weight percent, or 10 to 60 weight percent 13 to C 23 Hydrocarbon content.

[0214] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil or r-pyrolysis oil fed to the cracking furnace, or the r-pyrolysis oil that receives a feed mainly of C2-C4 raw materials before the feed pyrolysis oil and fed to the cracking furnace (and the mention of r-pyrolysis oil or pyrolysis oil throughout the text includes any one of these embodiments) may have a C content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5 weight percent in each case 24+ Hydrocarbon content. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a C content of not more than 15, or not more than 10, or not more than 9, or not more than 8, or not more than 7, or not more than 6 24+ Hydrocarbon content, in each case by weight percent. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a C content of 1 to 15 weight percent, 3 to 15 weight percent, 2 to 5 weight percent, or 5 to 10 weight percent 24+ Hydrocarbon content.

[0215] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have the following ratio of C6-C12 hydrocarbon content to C13-C23 hydrocarbon content: at least 1:1, at least 1.5:1, at least 2:1, at least 2.5:1, at least 3:1, at least 4:1, or at least 5:1 and / or not more than 20:1, not more than 15:1, or not more than 10:1.

[0216] The pyrolysis oil may also include various amounts of olefins, aromatic hydrocarbons, and other compounds. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil contains olefins and / or aromatic hydrocarbons in a weight percentage of at least 1, or at least 2, or at least 5, or at least 10, or at least 15, or at least 20 in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may contain olefins and / or aromatic hydrocarbons in a weight percentage of not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 15, or not more than 10, or not more than 5, or not more than 2, or not more than 1 in each case.

[0217] In one embodiment or in combination with any embodiment mentioned herein, the aromatic hydrocarbon content of the pyrolysis oil may be not more than 25, or not more than 20, or not more than 15, or not more than 14, or not more than 13, or not more than 12, or not more than 11, or not more than 10, or not more than 9, or not more than 8, or not more than 7, or not more than 6, or not more than 5, or not more than 4, or not more than 3, or not more than 2, or not more than 1, in each case as a weight percentage. In one embodiment or in combination with any mentioned embodiment, the aromatic hydrocarbon content of the pyrolysis oil is not higher than 15, or not higher than 10, or not higher than 8, or not higher than 6, in each case as a weight percentage.

[0218] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a naphthene content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15 in each case as a weight percentage. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a naphthene content of not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 10, or not more than 5, or not more than 2, or not more than 1, or not more than 0.5, or an undetectable amount in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a naphthene content of not more than 5, or not more than 2, or not more than 1 wt.%, or an undetectable amount. Alternatively, the pyrolysis oil may contain 1 to 50 weight percent, 5 to 50 weight percent, or 10 to 45 weight percent of naphthenes, especially if the r-pyrolysis oil is subjected to a hydrotreating process.

[0219] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane content of at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane content of not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55 weight percent in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane content of 25 to 90 weight percent, 35 to 90 weight percent, or 40 to 80 weight percent, or 40 to 70 weight percent, or 40 to 65 weight percent.

[0220] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a normal alkane content of at least 5, or at least 10, or at least 15, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a normal alkane content of not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55 weight percent in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a normal alkane content of 25 to 90 weight percent, 35 to 90 weight percent, or 40 to 70 weight percent, or 40 to 65 weight percent, or 50 to 80 weight percent.

[0221] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane to olefin weight ratio of at least 0.2:1, or at least 0.3:1, or at least 0.4:1, or at least 0.5:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1:1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane to olefin weight ratio of not more than 3:1, or not more than 2.5:1, or not more than 2:1, or not more than 1.5:1, or not more than 1.4:1, or not more than 1.3:1. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane to olefin weight ratio of 0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1:4.5:1, or 0.2:1 to 4:1, or 0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

[0222] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a weight ratio of n-alkanes to isoalkanes of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a weight ratio of n-alkanes to isoalkanes of not more than 100:1, or not more than 7, or not more than 5:1, or not more than 50:1, or not more than 40:1, or not more than 30:1. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a weight ratio of n-alkanes to isoalkanes in the range of 1:1 to 100:1, 4:1 to 100:1 or 15:1 to 100:1.

[0223] It should be noted that all of the above hydrocarbon weight percentages can be determined using gas chromatography - mass spectrometry (GC - MS).

[0224] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may exhibit a density of at least 0.6 g / cm 3 3, or at least 0.65 g / cm 3 3, or at least 0.7 g / cm 3 3 at 15 °C. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may exhibit a density of not more than 1 g / cm 3 3, or not more than 0.95 g / cm 3 3, or not more than 0.9 g / cm 3 3, or not more than 0.85 g / cm 3 3 at 15 °C. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil shows a density of 0.6 to 1 g / cm 3 3, 0.65 to 0.95 g / cm 3 3 or 0.7 to 0.9 g / cm 3 3 at 15 °C.

[0225] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may exhibit an API gravity of at least 28, or at least 29, or at least 30, or at least 31, or at least 32, or at least 33 at 15°C. Additionally, or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may exhibit an API gravity of no more than 50, or no more than 49, or no more than 48, or no more than 47, or no more than 46, or no more than 45, or no more than 44 at 15°C. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil exhibits an API gravity at 15°C in the range of 28 to 50, 29 to 58, or 30 to 44.

[0226] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a mid-boiling point of at least 75°C, or at least 80°C, or at least 85°C, or at least 90°C, or at least 95°C, or at least 100°C, or at least 105°C, or at least 110°C, or at least 115°C. The value may be measured according to ASTM D-2887 or the procedure described in the working examples. If the value is obtained by either method, then the mid-boiling point with the said value is satisfied. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a mid-boiling point of no more than 250°C, or no more than 245°C, or no more than 240°C, or no more than 235°C, or no more than 230°C, or no more than 225°C, or no more than 220°C, or no more than 215°C, or no more than 210°C, or no more than 205°C, or no more than 200°C, or no more than 195°C, or no more than 190°C, or no more than 185°C, or no more than 180°C, or no more than 175°C, or no more than 170°C, or no more than 165°C, or no more than 160°C, or no more than 155°C, or no more than 150°C, or no more than 145°C, or no more than 140°C, or no more than 135°C, or no more than 130°C, or no more than 125°C, or no more than 120°C. The value may be measured according to ASTM D-2887 or the procedure described in the working examples. If the value is obtained by either method, then the mid-boiling point with the said value is satisfied. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a mid-boiling point in the range of 75 to 250°C, 90 to 225°C, or 115 to 190°C. As used herein, "mid-boiling point" means the median boiling point temperature of the pyrolysis oil when 50 weight percent of the pyrolysis oil boils above the mid-boiling point and 50 weight percent of the pyrolysis oil boils below the mid-boiling point.

[0227] In one embodiment or in combination with any embodiment mentioned herein, the boiling point range of the pyrolysis oil can be such that no more than 10% of the pyrolysis oil has an end boiling point (FBP) of 250 °C, 280 °C, 290 °C, 300 °C or 310 °C. To determine the FBP, the procedure according to ASTM D-2887 or as described in the working examples can be used, and if the value is obtained under either method, the FBP with the said value is satisfied.

[0228] Turning to the pyrolysis gas, the pyrolysis gas can have a methane content of at least 1, or at least 2, or at least 5, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20 weight percent. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas can have a methane content of not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25 weight percent in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas can have a methane content of 1 to 50 weight percent, 5 to 50 weight percent or 15 to 45 weight percent.

[0229] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas can have a C3 hydrocarbon content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 15, or at least 20, or at least 25 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas can have a C3 hydrocarbon content of not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30 weight percent in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas can have a C3 hydrocarbon content of 1 to 50 weight percent, 5 to 50 weight percent or 20 to 50 weight percent.

[0230] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25 weight percent in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of 1 to 50 weight percent, 5 to 50 weight percent or 20 to 50 weight percent.

[0231] In one embodiment or in combination with any embodiment mentioned herein, the combined C3 and C4 hydrocarbon content of the pyrolysis gas (including all hydrocarbons having a carbon chain length of C3 or C4) may be at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75 weight percent in each case. Additionally, or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a combined C3 / C4 hydrocarbon content of not more than 99, or not more than 90, or not more than 80, or not more than 70, or not more than 60, or not more than 50 weight percent in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a combined C3 / C4 hydrocarbon content of 10 to 90 weight percent, 25 to 90 weight percent or 25 to 80 weight percent.

[0232] Without wishing to be bound by theory, it is believed that higher pyrolysis temperatures (e.g., temperatures above 550 °C), the choice of a particular catalyst type or the absence of a particular catalyst (e.g., ZSM-5) can promote the production of C3 and C4 hydrocarbons.

[0233] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil of the present invention may be a recycled component pyrolysis oil composition (r-pyrolysis oil).

[0234] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can contain at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent of C4-C30 hydrocarbons in each case, and as used herein, hydrocarbons include aliphatic, alicyclic, aromatic, and heterocyclic compounds. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can mainly contain C5-C25, C5-C22, or C5-C20 hydrocarbons, or can contain at least 55, 60, 65, 70, 75, 80, 85, 90, or 95 weight percent of C5-C25, C5-C22, or C5-C20 hydrocarbons.

[0235] Various downstream applications that can utilize the pyrolysis oil and / or pyrolysis gas disclosed above are described in more detail below. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can undergo one or more treatment steps before being introduced into a downstream unit such as a cracking furnace. Examples of suitable treatment steps can include, but are not limited to, separating less desirable components (e.g., nitrogen-containing compounds, oxygen-containing compounds, and / or olefins and aromatic hydrocarbons), distillation to provide a specific pyrolysis oil composition, and preheating.

[0236] Now turning to Figure 3 , a schematic diagram of a pyrolysis oil treatment area in one embodiment or in combination with any embodiment mentioned herein is shown.

[0237] As Figure 3 shown in the treatment zone 220 shown, at least a portion of the r-pyrolysis oil 252 made from the recycle waste stream 250 in the cracking system 210 can pass through the treatment zone 220, e.g., a separator, which separates the r-pyrolysis oil into a light pyrolysis oil fraction 254 and a heavy pyrolysis oil fraction 256. The separator 220 used for such separation can be any suitable type, including a single-stage vapor-liquid separator or a "flash" column, or a multi-stage distillation column. The vessel can include or not include internals, and reflux and / or boil-up can or cannot be used.

[0238] In one embodiment or in combination with any embodiment mentioned herein, the C4-C7 content or the C8+ content of the heavy fraction can be at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 weight percent. The light fraction can include at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% of C3 and lighter (C 3- ) or C7 and lighter (C 7-) Content. In some embodiments, the separator can concentrate the desired components into the heavy fraction such that the heavy fraction can have a C4-C7 content or a C 8+ content that is at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 7, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150% greater than the C4-C7 content or the C 8+ content of the pyrolysis oil withdrawn from the pyrolysis zone. As Figure 3 shown, at least a portion of the heavy fraction can be sent to the cracking furnace 230 to be cracked as an r-pyrolysis oil composition or as part of a pyrolysis oil composition to form an olefin-containing effluent 258, as discussed in further detail below.

[0239] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil is hydrotreated in the treatment zone, while in other embodiments, the pyrolysis oil is not hydrotreated before entering a downstream unit such as a cracking furnace. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil is not pretreated at all before any downstream application and can be sent directly from the pyrolysis oil source. The temperature of the pyrolysis oil leaving the pretreatment zone can be in the range of 15 to 55 °C, 30 to 55 °C, 49 to 40 °C, 15 to 50 °C, 20 to 45 °C or 25 to 40 °C.

[0240] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can be combined with a non-recycled cracker stream to minimize the amount of less desirable compounds present in the combined cracker feed. For example, when the r-pyrolysis oil has a certain concentration of less desirable compounds (such as impurities like oxygenates, aromatic hydrocarbons or other compounds described herein), the r-pyrolysis oil can be combined with the cracker feedstock in an amount such that the total concentration of the less desirable compounds in the combined stream is at least 40, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95% less than the original content of the compounds in the r-pyrolysis oil stream (calculated as the difference between the r-pyrolysis oil and the combined stream divided by the r-pyrolysis oil content, expressed as a percentage). In some cases, the amount of non-recycled cracker feed to be combined with the r-pyrolysis oil stream can be determined by comparing the measured amount of one or more less desirable compounds present in the r-pyrolysis oil with the target value of these compounds to determine the difference, and then based on this difference, determining the amount of non-recycled hydrocarbons to be added to the r-pyrolysis oil stream. The amounts of r-pyrolysis oil and non-recycled hydrocarbons can be within one or more of the ranges described herein.

[0241] At least a portion of the r- and the cracking that can be directly or indirectly derived from the r-pyrolysis oil. The process for obtaining r-olefins from cracking (r-pyrolysis oil) can be as follows and as Figure 4as described in

[0242] Turning Figure 4 , which is a flowchart of the steps associated with the cracking furnace 20 and the separation zone 30 of a system for producing an r-composition obtained from cracked r-pyrolysis oil. As Figure 4 shown, a feed stream containing r-pyrolysis oil (r-pyrolysis oil-containing feed stream) can be introduced into the cracking furnace 20 alone or in combination with a non-recycled cracker feed stream. The pyrolysis unit that produces r-pyrolysis oil can be co-located with the production facility. In other embodiments, the r-pyrolysis oil can be sourced from a remote pyrolysis unit and transported to the production facility.

[0243] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil-containing feed stream can contain r-pyrolysis oil in an amount that is in each case at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 98, or at least 99, or at least or 100 weight percent and / or not more than 95, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, based on the total weight of the r-pyrolysis oil-containing feed stream.

[0244] In one embodiment or in combination with any embodiment mentioned herein, at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 97, or at least 98, or at least 99, or 100 weight percent and / or not more than 95, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 15, or not more than 10 weight percent of r-pyrolysis oil is obtained by pyrolysis of the waste stream. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock containing plastic waste. Desirably, in each case, at least 90, or at least 95, or at least 97, or at least 98, or at least 99, or at least or 100 wt.% of the r-pyrolysis oil is obtained by pyrolysis of a feedstock containing plastic waste, or a feedstock containing at least 50 wt.% plastic waste, or a feedstock containing at least 80 wt.% plastic waste, or a feedstock containing at least 90 wt.% plastic waste, or a feedstock containing at least 95 wt.% plastic waste.

[0245] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have any one or combination of the compositional features described above for pyrolysis oil.

[0246] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can contain at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent of C4-C 30 hydrocarbons, and as used herein, hydrocarbons include aliphatic, cycloaliphatic, aromatic, and heterocyclic compounds. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can mainly contain C5-C 25 、C5-C 22 or C5-C 20 hydrocarbons, or can contain at least 55, 60, 65, 70, 75, 80, 85, 90 or 95 weight percent of C5-C 25 、C5-C 22 or C5-C 20 hydrocarbons.

[0247] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the r-pyrolysis oil composition can contain C4-C12 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and cycloaliphatic hydrocarbons) and C 13 -C 22 Aliphatic compounds, in a weight ratio greater than 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on the weight of the r-pyrolysis oil.

[0248] In one embodiment or in combination with any of the embodiments mentioned herein or in conjunction with any of the embodiments mentioned, the r-pyrolysis oil composition may comprise C 13 -C 22 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and cycloaliphatic hydrocarbons) and C4-C 12 Aliphatic compounds, in a weight ratio greater than 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on the weight of the r-pyrolysis oil.

[0249] In one embodiment, the two aliphatic hydrocarbons (branched or unbranched alkanes and alkenes, and cycloaliphatic compounds) having the highest concentration in the r-pyrolysis oil are in the range of C5-C 18 , or C5-C 16 , or C5-C 14 , or C5-C 10 , or C5-C8 (including the end values).

[0250] The r-pyrolysis oil may include one or more of alkanes, naphthenes or cyclic aliphatic hydrocarbons, aromatic hydrocarbons, aromatic-containing hydrocarbons, alkenes, oxygenates and polymers, heteroatom compounds or polymers, and other compounds or polymers.

[0251] For example, in one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may contain alkanes (or straight-chain or branched-chain alkanes) in an amount of at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, and / or not more than 99, or not more than 97, or not more than 95, or not more than 93, or not more than 90, or not more than 87, or not more than 85, or not more than 83, or not more than 80, or not more than 78, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, not more than 25, not more than 30, or not more than 20, or not more than 15, in weight percentage in each case, based on the total weight of the r-pyrolysis oil. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an alkane content of 25 to 90, 35 to 90, or 40 to 80, or 40 to 70, or 40 to 65 weight percentage, or 5 to 50, or 5 to 40, or 5 to 35, or 10 to 35, or 10 to 30, or 5 to 25, or 5 to 20, in wt.% in each case based on the weight of the r-pyrolysis oil composition.

[0252] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may include cycloalkanes or cyclic aliphatic hydrocarbons in an amount of zero, or at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20, in weight percentage in each case, and / or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 15, or not more than 10, or not more than 5, or not more than 2, or not more than 1, or not more than 0.5, or an undetectable amount, in weight percentage in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have a cycloalkane content of not more than 5, or not more than 2, or not more than 1 wt.%, or an undetectable amount. Examples of the range of the amount of cycloalkanes (or cyclic aliphatic hydrocarbons) contained in the r-pyrolysis oil are 0-35, or 0-30, or 0-25, or 2-20, or 2-15, or 2-10, or 1-10, in wt.% in each case based on the weight of the r-pyrolysis oil composition.

[0253] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have an alkane to alkene weight ratio of at least 0.2:1, or at least 0.3:1, or at least 0.4:1, or at least 0.5:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1:1. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have an alkane to alkene weight ratio of no more than 3:1, or no more than 2.5:1, or no more than 2:1, or no more than 1.5:1, or no more than 1.4:1, or no more than 1.3:1. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have an alkane to alkene weight ratio in the range of 0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1 to 4.5:1, or 0.2:1 to 4:1, or 0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

[0254] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have a n-alkane to iso-alkane weight ratio of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have a n-alkane to iso-alkane weight ratio of no more than 100:1, or no more than 50:1, or no more than 40:1, or no more than 30:1. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have a n-alkane to iso-alkane weight ratio in the range of 1:1 to 100:1, 4:1 to 100:1 or 15:1 to 100:1.

[0255] In one embodiment, the r-pyrolysis oil contains aromatic hydrocarbons in each case by weight not exceeding 30, or not exceeding 25, or not exceeding 20, or not exceeding 15, or not exceeding 10, or not exceeding 8, or not exceeding 5, or not exceeding 2, or not exceeding 1, based on the total weight of the r-pyrolysis oil. As used herein, the term "aromatic hydrocarbons" refers to the total amount (by weight) of benzene, toluene, xylene and styrene. The r-pyrolysis oil may include at least 1, or at least 2, or at least 5, or at least 8, or at least 10 weight percent of aromatic hydrocarbons, in each case based on the total weight of the r-pyrolysis oil.

[0256] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include aromatic hydrocarbons in an amount of not more than 30, or not more than 25, or not more than 20, or not more than 15, or not more than 10, or not more than 8, or not more than 5, or not more than 2, or not more than 1, or undetectable, in each case by weight, based on the total weight of the r-pyrolysis oil. Aromatic-containing compounds include the above-mentioned aromatic hydrocarbons and any compounds containing an aromatic moiety, such as terephthalate residues and polycyclic aromatic hydrocarbons, such as naphthalene and tetrahydronaphthalene.

[0257] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include olefins in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20, or at least 30, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, in each case by weight percentage of olefins, and / or in an amount of not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 15, or not more than 10, in each case by weight, based on the weight of the r-pyrolysis oil. Olefins include monoolefins and diolefins. Examples of suitable ranges include, in each case, a wt.% ratio of the amount of olefins present of 5 to 45, or 10 to 35, or 15 to 30, or 40 to 85, or 45 to 85, or 50 to 85, or 55 to 85, or 60 to 85, or 65 to 85, or 40 to 80, or 45 to 80, or 50 to 80, or 55 to 80, or 60 to 80, or 65 to 80, 45 to 80, or 50 to 80, or 55 to 80, or 60 to 80, or 65 to 80, or 40 to 75, or 45 to 75, or 50 to 75, or 55 to 75, or 60 to 75, or 65 to 75, or 40 to 70, or 45 to 70, or 50 to 70, or 55 to 70, or 60 to 70, or 65 to 70, or 40 to 65, or 45 to 65, or 50 to 65, or 55 to 65, based on the weight of the r-pyrolysis oil.

[0258] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include oxygenates or polymers in an amount of zero or, in each case, at least 0.01 wt.%, or at least 0.1 wt.%, or at least 1 wt.%, or at least 2 wt.%, or at least 5 wt.%, and / or, in each case, not more than 20 wt.%, or not more than 15 wt.%, or not more than 10 wt.%, or not more than 8 wt.%, or not more than 6 wt.%, or not more than 5 wt.%, or not more than 3 wt.%, or not more than 2 wt.%, based on the weight of the r-pyrolysis oil. Oxygenates and polymers are those that contain oxygen atoms. Examples of suitable ranges include oxygenates present in an amount in the range of 0 - 20 wt.%, or 0 - 15 wt.%, or 0 - 10 wt.%, or 0.01 - 10 wt.%, or 1 - 10 wt.%, or 2 - 10 wt.%, or 0.01 - 8 wt.%, or 0.1 - 6 wt.%, or 1 - 6 wt.%, or 0.01 - 5 wt.%, based on the weight of the r-pyrolysis oil.

[0259] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the amount of oxygen atoms in the r-pyrolysis oil may be not more than 10 wt.%, or not more than 8 wt.%, or not more than 5 wt.%, or not more than 4 wt.%, or not more than 3 wt.%, or not more than 2.75 wt.%, or not more than 2.5 wt.%, or not more than 2.25 wt.%, or not more than 2 wt.%, or not more than 1.75 wt.%, or not more than 1.5 wt.%, or not more than 1.25 wt.%, or not more than 1 wt.%, or not more than 0.75 wt.%, or not more than 0.5 wt.%, or not more than 0.25 wt.%, or not more than 0.1 wt.%, or not more than 0.05 wt.%, in each case based on the weight of the r-pyrolysis oil. Examples of the amount of oxygen in the r-pyrolysis oil may be 0 - 8 wt.%, or 0 - 5 wt.%, or 0 - 3 wt.%, or 0 - 2.5 wt. or 0 - 2 wt.%, or 0.001 - 5 wt.%, or 0.001 - 4 wt.%, or 0.001 - 3 wt.%, or 0.001 - 2.75 wt.%, or 0.001 - 2.5 wt.%, or 0.001 - 2 wt.%, or 0.001 - 1.5 wt.%, or 0.001 - 1 wt.%, or 0.001 - 0.5 wt.%, or 0.001 - 1 wt.%, in each case based on the weight of the r-pyrolysis oil.

[0260] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may include heteroatom compounds or polymers in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20 weight percent, and / or not more than 25, or not more than 20, or not more than 15, or not more than 10, or not more than 8, or not more than 6, or not more than 5, or not more than 3, or not more than 2 weight percent, based on the weight of the r-pyrolysis oil. The heteroatom compounds or polymers are defined in this paragraph as any compounds or polymers containing nitrogen, sulfur or phosphorus. Any other atoms are not considered heteroatoms for determining the amount of heteroatoms, hetero-compounds or hetero-polymers present in the r-pyrolysis oil. The r-pyrolysis oil may contain heteroatoms in an amount not exceeding 5, or not exceeding 4, or not exceeding 3, or not exceeding 2.75, or not exceeding 2.5, or not exceeding 2.25, or not exceeding 2, or not exceeding 1.75, or not exceeding 1.5, or not exceeding 1.25, or not exceeding 1, or not exceeding 0.75, or not exceeding 0.5, or not exceeding 0.25, or not exceeding 0.1, or not exceeding 0.075, or not exceeding 0.05, or not exceeding 0.03, or not exceeding 0.02, or not exceeding 0.01, or not exceeding 0.008, or not exceeding 0.006, or not exceeding 0.005, or not exceeding 0.003, or not exceeding 0.002, in each case as wt.% based on the weight of the r-pyrolysis oil.

[0261] In one embodiment or in combination with any of the embodiments mentioned herein, the solubility of water in the r-pyrolysis oil at 1 atm and 25 °C is less than 2 wt.%, water, or not more than 1.5, or not more than 1, or not more than 0.5, or not more than 0.1, or not more than 0.075, or not more than 0.05, or not more than 0.025, or not more than 0.01, or not more than 0.005, in each case as wt.% water based on the weight of the r-pyrolysis oil. Desirably, the solubility of water in the r-pyrolysis oil is not more than 0.1 wt.%, based on the weight of the r-pyrolysis oil. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil contains not more than 2 wt.% of water, or not more than 1.5, or not more than 1, or not more than 0.5, desirably or not more than 0.1, or not more than 0.075, or not more than 0.05, or not more than 0.025, or not more than 0.01, or not more than 0.005, in each case as wt.% water based on the weight of the r-pyrolysis oil.

[0262] In one embodiment or in combination with any embodiment mentioned herein, the solids content in the r-pyrolysis oil is not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.2, or not more than 0.15, or not more than 0.1, or not more than 0.05, or not more than 0.025, or not more than 0.01, or not more than 0.005, or not more than 0.001, in each case wt.% solids based on the weight of the r-pyrolysis oil.

[0263] In one embodiment or in combination with any embodiment mentioned herein, the sulfur content of the r-pyrolysis oil is not more than 2.5 wt.%, or not more than 2, or not more than 1.75, or not more than 1.5, or not more than 1.25, or not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.1, or not more than 0.05, desirably or not more than 0.03, or not more than 0.02, or not more than 0.01, or not more than 0.008, or not more than 0.006, or not more than 0.004, or not more than 0.002, or not more than 0.001, in each case wt.% based on the weight of the r-pyrolysis oil.

[0264] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have the following component contents:

[0265] The carbon atom content is at least 75 wt.%, or at least 77, or at least 80, or at least 82, or at least 85, in each case wt.%, and / or at most 90, or at most 88, or at most 86, or at most 85, or at most 83, or at most 82, or at most 80, or at most 77, or at most 75, or at most 73, or at most 70, or at most 68, or at most 65, or at most 63, or at most 60, in each case wt.%, desirably at least 82% and at most 93%, and / or

[0266] The hydrogen atom content is at least 10 wt.%, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or not more than 19, or not more than 18, or not more than 17, or not more than 16, or not more than 15, or not more than 14, or not more than 13, or at most 11, in each case wt.%.

[0267] The oxygen atom content is not more than 10, or not more than 8, or not more than 5, or not more than 4, or not more than 3, or not more than 2.75, or not more than 2.5, or not more than 2.25, or not more than 2, or not more than 1.75, or not more than 1.5, or not more than 1.25, or not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.1, or not more than 0.05, in each case in wt.%,

[0268] in each case based on the weight of the r-pyrolysis oil.

[0269] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the amount of hydrogen atoms in the r-pyrolysis oil can be in the range of 10 - 20, or 10 - 18, or 11 - 17, or 12 - 16, or 13 - 16, or 13 - 15, or 12 - 15, in each case in wt.% based on the weight of the r-pyrolysis oil.

[0270] In one embodiment or in combination with any embodiment mentioned herein, the metal content of the r-pyrolysis oil is desirably low, such as not more than 2 wt.%, or not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.2, or not more than 0.15, or not more than 0.1, or not more than 0.05, in each case in wt.% based on the weight of the r-pyrolysis oil.

[0271] In one embodiment or in combination with any embodiment mentioned herein, the alkali metal, alkaline earth metal or mineral content of the r-pyrolysis oil is desirably low, such as not more than 2 wt.%, or not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.2, or not more than 0.15, or not more than 0.1, or not more than 0.05, in each case in wt.% based on the weight of the r-pyrolysis oil.

[0272] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of paraffins to naphthenes in the r-pyrolysis oil can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.25:1, or at least 4.5:1, or at least 4.75:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 13:1, or at least 15:1, or at least 17:1, based on the weight of the r-pyrolysis oil.

[0273] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of the combination of paraffins and naphthenes to aromatics can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.5:1, or at least 5:1, or at least 7:1, or at least 10:1, or at least 15:1, or at least 20:1, or at least 25:1, or at least 30:1, or at least 35:1, or at least 40:1, based on the weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, in the r-pyrolysis oil, the ratio of the combination of paraffins and naphthenes to aromatics can be in the range of 50:1 - 1:1, or 40:1 - 1:1, or 30:1 - 1:1, or 20:1 - 1:1, or 30:1 - 3:1, or 20:1 - 1:1, or 20:1 - 5:1, or 50:1 - 5:1, or 30:1 - 5:1, or 1:1 - 7:1, or 1:1 - 5:1, 1:1 - 4:1, or 1:1 - 3:1.

[0274] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a boiling point curve defined by one or more of its 10%, 50%, and 90% boiling points, as defined below. As used herein, "boiling point" refers to the boiling point of the composition determined by ASTM D2887 or according to the procedure described in the working examples. If the value is obtained by either method, the boiling point having the said value is satisfied. Additionally, as used herein, "x% boiling point" means that x weight percent of the composition boils at that boiling point according to any of these methods.

[0275] As used throughout, x% boiling at the temperature means that at least x% of the composition boils at the temperature. In one embodiment or in combination with any of the embodiments described herein, the 90% boiling point of the cracker feed stream or composition can be no more than 350, or no more than 325, or no more than 300, or no more than 295, or no more than 290, or no more than 285, or no more than 280, or no more than 275, or no more than 270, or no more than 265, or no more than 260, or no more than 255, or no more than 250, or no more than 245, or no more than 240, or no more than 235, or no more than 230, or no more than 225, or no more than 220, or no more than 215, no more than 200, no more than 190, no more than 180, no more than 170, no more than 160, no more than 150 or no more than 140, in each case in °C, and / or at least 200, or at least 205, or at least 210, or at least 215, or at least 220, or at least 225, or at least 230, in each case in °C, and / or no more than 25, 20, 15, 10, 5, or 2 weight percent of the r-pyrolysis oil can have a boiling point of 300 °C or higher.

[0276] Refer again to Figure 3, the r-pyrolysis oil can be introduced into the cracking furnace or coil or tube alone (e.g., in an amount of at least 85, or at least 90, or at least 95, or at least 99, or 100 wt.% pyrolysis oil, in each case based on the weight of the cracker feed stream) or in combination with one or more non-recycled cracker feed streams. When introduced into the cracker furnace, coil or tube together with the non-recycled cracker feed stream, the amount of r-pyrolysis oil present can be at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 12, or at least 15, or at least 20, or at least 25, or at least 30 wt.%, in each case, and / or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 15, or not more than 10, or not more than 8, or not more than 5, or not more than 2 wt.%, in each case based on the total weight of the combined stream. Thus, the non-recycled cracker feed stream or composition can be present in the combined stream in an amount of at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90 wt.%, in each case, and / or not more than 99, or not more than 95, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40 wt.%, in each case based on the total weight of the combined stream. Unless otherwise specified herein, the properties of the cracker feed stream as described below apply to the non-recycled cracker feed stream before (or in the absence of) combination with the stream containing r-pyrolysis oil, and to the combined cracker stream comprising both the non-recycled cracker feed and the r-pyrolysis oil feed.

[0277] In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed stream can comprise a composition mainly containing C2-C4 hydrocarbons, or mainly containing C5-C 22Hydrocarbon compositions. As used herein, the term "predominantly C2-C4 hydrocarbons" refers to a stream or composition containing at least 50 weight percent of a C2-C4 hydrocarbon component. Examples of specific types of C2-C4 hydrocarbon streams or compositions include propane, ethane, butane, and LPG. In one embodiment or in combination with any of the embodiments described herein, the cracker feed may contain at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.% based on the total weight of the feed, and / or not more than 100, or not more than 99, or not more than 95, or not more than 92, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, in each case the weight percentage of C2-C4 hydrocarbons or linear alkanes, based on the total weight of the feed. The cracker feed may contain predominantly propane, predominantly ethane, predominantly butane, or a combination of two or more of these components. These components may be non-recovered components. The cracker feed may predominantly contain propane, or at least 50 mol% propane, or at least 80 mol% propane, or at least 90 mol% propane, or at least 93 mol% propane, or at least 95 mol% propane (including any recycle stream mixed with the fresh feed). The cracker feed may contain HD5 quality propane as the virgin or fresh feed. The cracker may contain greater than 50 mol% ethane, or at least 80 mol% ethane, or at least 90 mol% ethane, or at least 95 mol% ethane. These components may be non-recovered components.

[0278] In one embodiment or in combination with any of the embodiments described herein, the cracker feed stream may contain predominantly C5-C 22 Hydrocarbon compositions. As used herein, "predominantly C5-C 22 hydrocarbons" refers to a stream or composition containing at least 50 weight percent of a C5-C 22 hydrocarbon component. Examples include gasoline, naphtha, middle distillates, diesel, kerosene. In one embodiment or in combination with any of the embodiments described herein, the cracker feed stream or composition may contain at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.%, and / or not more than 100, or not more than 99, or not more than 95, or not more than 92, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, in each case for C5-C 22 or C5-C20 The hydrocarbon weight percentage, based on the total weight of the stream or composition. In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed may have at least 0.5, or at least 1, or at least 2, or at least 5 C 15 and heavier (C 15+ ) content, in each case by weight percentage, and / or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 18, or not more than 15, or not more than 12, or not more than 10, or not more than 5, or not more than 3, in each case by weight percentage, based on the total weight of the feed.

[0279] The cracker feed may have a boiling point curve defined by one or more of its 10%, its 50%, and its 90% boiling points, the boiling points being obtained by the method described above. Additionally, as used herein, "x% boiling point" means the boiling point at which x weight percentage of the composition boils according to the method described above. In one embodiment or in combination with any of the embodiments mentioned herein, the 90% boiling point of the cracker feed stream or composition may be not more than 360, or not more than 355, or not more than 350, or not more than 345, or not more than 340, or not more than 335, or not more than 330, or not more than 325, or not more than 320, or not more than 315, or not more than 300, or not more than 295, or not more than 290, or not more than 285, or not more than 280, or not more than 275, or not more than 270, or not more than 265, or not more than 260, or not more than 255, or not more than 250, or not more than 245, or not more than 240, or not more than 235, or not more than 230, or not more than 225, or not more than 220, or not more than 215, in each case in °C, and / or at least 200, or at least 205, or at least 210, or at least 215, or at least 220, or at least 225, or at least 230 °C, in each case in °C.

[0280] In one embodiment or in combination with any of the embodiments mentioned herein, the 10% boiling point of the cracker feed stream or composition may be at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150 or at least 155, in each case in °C, and / or not more than 250, not more than 240, not more than 230, not more than 220, not more than 210, not more than 200, not more than 190, not more than 180 or not more than 170, in each case in °C.

[0281] In one embodiment or in combination with any embodiment mentioned herein, the 50% boiling point of the cracker feed stream or composition can be at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, or at least 230, in each case in °C, and / or not exceeding 300, not exceeding 290, not exceeding 280, not exceeding 270, not exceeding 260, not exceeding 250, not exceeding 240, not exceeding 230, not exceeding 220, not exceeding 210, not exceeding 200, not exceeding 190, not exceeding 180, not exceeding 170, not exceeding 160, not exceeding 150, or not exceeding 145 °C. The 50% boiling point of the cracker feed stream or composition can be in the range of 65 to 160, 70 to 150, 80 to 145, 85 to 140, 85 to 230, 90 to 220, 95 to 200, 100 to 190, 110 to 180, 200 to 300, 210 to 290, 220 to 280, 230 to 270, in each case in °C.

[0282] In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feedstock or stream or composition can be at least 350 °C, the 10% boiling point can be at least 60 °C; and the 50% boiling point can be in the range of 95 °C to 200 °C. In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feedstock or stream or composition can be at least 150 °C, the 10% boiling point can be at least 60 °C, and the 50% boiling point can be in the range of 80 °C to 145 °C. In one embodiment or in combination with any embodiment herein, the cracker feedstock or stream has a 90% boiling point of at least 350 °C, a 10% boiling point of at least 150 °C, and a 50% boiling point in the range of 220 to 280 °C.

[0283] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil is cracked in a gas furnace. The gas furnace is a furnace having at least one coil that receives (or is operated to receive) a feed that is predominantly in the gas phase (more than 50% by weight of the feed is vapor) at the coil inlet at the convection zone inlet (“gas coil”). In one embodiment or in combination with any embodiment mentioned herein or in combination with any of the embodiments mentioned, the gas coil may receive a feed that is predominantly C2-C4 or predominantly C2-C3 to the inlet of the coil in the convection section, or alternatively, has at least one coil that receives more than 50 wt.% of ethane and / or more than 50% of propane and / or more than 50% of LPG, or in any of these cases, receives at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, based on the weight of the cracker feed to the coil, or alternatively based on the weight of the cracker feed to the convection zone. The gas furnace may have more than one gas coil. In one embodiment or in combination with any embodiment mentioned herein or in combination with any of the embodiments mentioned, at least 25% of the coils in the convection zone or in the convection box of the furnace, or at least 50% of the coils, or at least 60% of the coils, or all of the coils are gas coils. In one embodiment or in combination with any embodiment mentioned herein or in combination with any of the embodiments mentioned, the gas coil receives a vapor phase feed at the coil inlet at the inlet of the convection zone, in which at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is vapor.

[0284] In one embodiment or in combination with any embodiment mentioned herein or in combination with any of the embodiments mentioned, the r-pyrolysis oil is cracked in a cracking furnace. The cracking furnace is a gas furnace. The cracking furnace contains at least one gas coil and at least one liquid coil within the same furnace, or within the same convection zone, or within the same convection box. The liquid coil is a coil that receives a feed that is predominantly in the liquid phase (more than 50% by weight of the feed is liquid) at the coil inlet at the convection zone inlet (“liquid coil”). In one embodiment or in combination with any embodiment mentioned herein or in combination with any of the embodiments mentioned, the liquid coil may receive a feed that is predominantly C 5+ to the inlet of the coil. In one embodiment or in combination with any embodiment mentioned herein or in combination with any of the embodiments mentioned, the liquid coil may receive a feed that is predominantly C6-C 22 or predominantly C7-C 16The feedstock to the inlet of the coil in the convection section, or alternatively, having at least one coil that receives more than 50 wt.% of naphtha, and / or more than 50% of natural gasoline, and / or more than 50% of diesel, and / or more than JP-4, and / or more than 50% of dry cleaning solvent, and / or more than 50% of kerosene, and / or more than 50% of fresh wood tar, and / or more than 50% of JP-8 or Jet-A, and / or more than 50% of heating oil, and / or more than 50% of heavy fuel oil, and / or more than 50% of marine grade C, and / or more than 50% of lubricating oil, or in any of these cases at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 98 wt.%, or at least 99 wt.%, based on the weight of the cracker feed to the liquid coil, or alternatively based on the weight of the cracker feed to the convection zone. In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, at least one coil in the convection zone or in the convection box of the furnace and not more than 75% of the coils, or not more than 50% of the coils, or not more than at least 40% of the coils are liquid coils. In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the liquid coil receives a vapor phase feed at the coil inlet at the inlet of the convection zone, and in the liquid feed at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is liquid.

[0285] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, r-pyrolysis oil is cracked in a hot gas cracker.

[0286] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, r-pyrolysis oil is cracked in a hot steam gas cracker in the presence of steam. Steam cracking refers to the high temperature cracking (decomposition) of hydrocarbons in the presence of steam.

[0287] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the r-composition is directly or indirectly derived from cracking r-pyrolysis oil in a gas furnace. The coils in the gas furnace can consist entirely of gas coils, or the gas furnace can be a cracking furnace.

[0288] When a feed stream containing r-pyrolysis oil is combined with a non-recycle cracker feed, this combination can occur upstream of the cracking furnace or within the cracking furnace or within a single coil or tube. Alternatively, the feed stream containing r-pyrolysis oil and the non-recycle cracker feed can be introduced separately into the furnace and can pass through part or all of the furnace simultaneously and be isolated from each other by passing through separate tubes within the same furnace (e.g., a cracking furnace) to which the feeds are introduced. The manner of introducing the feed stream containing r-pyrolysis oil and the non-recycle cracker feed into the cracking furnace is described in further detail below, according to one embodiment or in combination with any of the embodiments mentioned herein.

[0289] Turning now Figure 5 , a schematic diagram of a cracking furnace suitable for an embodiment or in combination with any of the embodiments mentioned herein is shown.

[0290] In one embodiment or in combination with any of the embodiments mentioned, a method for preparing one or more olefins is provided, comprising: (a) feeding a first cracker feed comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to a cracking furnace; (b) feeding a second cracker feed to the cracking furnace, wherein the second cracker feed does not contain the r-pyrolysis oil or contains less (by weight) of the r-pyrolysis oil than the first cracker feed stream; and (c) cracking the first and second cracker feeds in respective first and second tubes to form an olefin-containing effluent stream.

[0291] The r-pyrolysis oil can be combined with the cracker stream to prepare a combined cracker stream, or, as described above, a first cracker stream. The first cracker stream can be 100% r-pyrolysis oil or a combination of a non-recycle cracker stream and r-pyrolysis oil. The feeds of step (a) and / or step (b) can be r-pyrolysis oil upstream of the convection zone or within the convection zone. The r-pyrolysis oil can be combined with the non-recycle cracker stream to form a combined or first cracker stream and fed to the inlet of the convection zone, or alternatively, the r-pyrolysis oil can be fed separately with the non-recycle cracker stream to the inlet of a coil or distributor to form a first cracker stream at the inlet of the convection zone, or the r-pyrolysis oil can be fed downstream of the inlet of the convection zone to a tube containing the non-recycle cracker feed, but before crossing, to prepare a first cracker stream or a combined cracker stream in the tube or coil. Any of these methods includes feeding the first cracker stream into the furnace.

[0292] The amount of r-pyrolysis oil added to the non-recycle cracker stream to prepare the first cracker stream or the combined cracker stream can be as described above; for example, in an amount of at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95, in each case as a weight percentage, and / or not exceeding 95, 90, 85, 80, 75, 70, 65, 60, 55, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 or 1, in each case as a weight percentage, based on the total weight of the first cracker feed or the combined cracker feed (introduced into the tube or within the tube as described above). Other examples include 5 - 50, 5 - 40, 5 - 35, 5 - 30, 5 - 25, 5 - 20 or 5 - 15 wt.%.

[0293] The first cracker stream is cracked in the first coil or tube. The second cracker stream is cracked in the second coil or tube. The first and second cracker streams and the first and second coils or tubes can be within the same cracker furnace.

[0294] The second cracker stream can be free of r-pyrolysis oil or contain less (by weight) of said r-pyrolysis oil than the first cracker feed stream. Additionally, the second cracker stream can contain only the non-recycle cracker feed in the second coil or tube. The second cracker feed stream can be predominantly C2 to C4, or hydrocarbons (such as non-recycle components), or ethane, propane or butane, in each case in an amount of at least 55, 60, 65, 70, 75, 80, 85 or at least 90 weight percentage, based on the second cracker feed within the second coil or tube. If r-pyrolysis oil is included in the second cracker feed, the amount of such r-pyrolysis oil can be at least 10%, 20, 30, 40, 50, 60, 70, 80, 90, 95, 97 or 99% less by weight than the amount of r-pyrolysis oil in the first cracker feed.

[0295] In one embodiment or in combination with any embodiment described herein or in combination with any recited embodiment, although not shown, an evaporator can be provided to evaporate the condensed feedstock of C2 - C5 hydrocarbons 350 to ensure that the feed to the coil inlet in the convection box 312 or the inlet to the convection zone 310 is predominantly a gas-phase feed.

[0296] Figure 5The cracking furnace shown in [description] includes a convection section or zone 310, a radiation section or zone 320, and an intersection section or zone 330 located between the convection section and the radiation sections 310 and 320. The convection section 310 is part of the furnace 300 that receives heat from hot flue gas and includes a row of tubes or coils 324 through which the cracker stream 350 passes. In the convection section 310, the cracker stream 350 is heated by convection from the hot flue gas passing through it. The radiation section 320 is the section of the furnace 300 that transfers heat to the heater tubes mainly by radiation from high-temperature gases. The radiation section 320 also includes a plurality of burners 326 for introducing heat into the lower part of the furnace. The furnace includes a combustion chamber 322 that surrounds and houses the tubes within the radiation section 320, and the burners are directed into this combustion chamber. The intersection section 330 includes pipes for connecting the convection section 310 and the radiation section 320 and can transfer the heated cracker stream from inside or outside one section within the furnace 300 to the other section.

[0297] When the hot combustion gases rise upward through the furnace body, the gases can pass through the convection section 310 where at least a portion of the waste heat can be recovered and used to heat the cracker stream passing through the convection section 310. In one embodiment or in combination with any of the embodiments mentioned herein, the cracking furnace 300 can have a single convection (preheat) section 310 and a single radiation section 320, while in other embodiments, the furnace can include two or more radiation sections sharing a common convection section. At least one induced draft (I.D.) fan 316 near the furnace body can control the flow of the hot flue gas and the heating distribution through the furnace, and one or more heat exchangers 340 can be used to cool the furnace effluent 370. In one embodiment or in combination with any of the embodiments (not shown) mentioned herein, in addition to or in place of Figure 5 the exchanger shown in [description] (e.g., a transfer line heat exchanger or TLE), liquid quenching can be used to cool the cracked olefin-containing effluent.

[0298] The furnace 300 also includes at least one furnace coil 324 through which the cracker stream passes through the furnace. The furnace coil 324 can be formed of any material that is inert to the cracker stream and suitable for withstanding the high temperature and thermal stress within the furnace. The coil can have any suitable shape and can, for example, have a circular or oval cross-sectional shape.

[0299] The diameter of the coil or the tubes within the coil in the convection section 310 can be at least 1, or at least 1.5, or at least 2, or at least 2.5, or at least 3, or at least 3.5, or at least 4, or at least 4.5, or at least 5, or at least 5.5, or at least 6, or at least 6.5, or at least 7, or at least 7.5, or at least 8, or at least 8.5, or at least 9, or at least 9.5, or at least 10, or at least 10.5, in each case in cm, and / or not exceeding 12, or not exceeding 11.5, or not exceeding 11, or not exceeding 10.5, or not exceeding 10, or not exceeding 9.5, or not exceeding 9, or not exceeding 8.5, or not exceeding 8, or not exceeding 7.5, or not exceeding 7, or not exceeding 6.5, in each case in cm. All or part of one or more coils can be substantially straight, or one or more coils can include helical, twisted, or spiral segments. One or more coils can also have a U-tube or split U-tube design. In one embodiment or in combination with any embodiment mentioned herein, the interior of the tubes can be smooth or substantially smooth, or part (or all) can be rough to minimize coking. Alternatively, or additionally, the interior of the tubes can include inserts or fins and / or surface metal additives to prevent coke buildup.

[0300] In one embodiment or in combination with any embodiment mentioned herein, all or part of one or more furnace coils 324 passing through the convection section 310 can be horizontally oriented, while the furnace coils passing through all or at least part of the radiation section 322 can be vertically oriented. In one embodiment or in combination with any embodiment mentioned herein, a single furnace coil can extend through both the convection section and the radiation section. Alternatively, at least one coil can be split into two or more tubes at one or more points within the furnace such that the cracker stream can pass in parallel along multiple paths. For example, the cracker stream (including r-pyrolysis oil) 350 can be introduced into multiple coil inlets in the convection zone 310, or into multiple tube inlets in the radiation section 320 or the crossover section 330. When introducing multiple coil or tube inlets simultaneously or almost simultaneously, the amount of r-pyrolysis oil introduced into each coil or tube may not be regulated. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil and / or the cracker stream can be introduced into a common header, which then directs the r-pyrolysis oil to multiple coil or tube inlets.

[0301] A single furnace may have at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8 or more, in each case being coiled tubes. Each coiled tube may be 5 to 100, 10 to 75, or 20 to 50 meters in length and may include at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 10, or at least 12, or at least 14 or more tubes. The tubes of a single coiled tube may be arranged in a number of configurations and, in one embodiment or in combination with any of the embodiments mentioned herein, may be connected by one or more 180° (“U”-shaped) bends. Figure 6 An example of a furnace coil 410 with multiple tubes 420 is shown in

[0302] The olefin plant can have a single cracking furnace, or it can have at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8 or more cracking furnaces operating in parallel. Any one or each furnace can be a gas cracker or a liquid cracker or a cracking furnace. In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the furnace is a gas cracker that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, or at least 90 wt.% of ethane, propane, LPG, or a combination thereof, based on the weight of all cracker feeds to the furnace. In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the furnace is a liquid or naphtha cracker that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.% of liquid hydrocarbons having a carbon number of C5-C22 (when measured at 25 °C and 1 atm), based on the weight of all cracker feeds to the furnace. In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the cracker is a cracking furnace that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, or at least 90 wt.% of ethane, propane, LPG or a combination thereof, and receives a cracker feed stream containing at least 0.5 wt.%, or at least 0.1 wt.%, or at least 1 wt.%, or at least 2 wt.%, or at least 5 wt.%, or at least 7 wt.%, or at least 10 wt.%, or at least 13 wt.%, or at least 15 wt.%, or at least 20 wt.% liquid and / or r-pyrolysis oil (when measured at 25 °C and 1 atm), each based on the weight of all cracker feeds to the furnace.

[0303] Turning now to Figure 7 , several possible locations for introducing a feed stream containing r-pyrolysis oil and a non-recycle cracker feed stream into a cracking furnace are shown.

[0304] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil-containing feed stream 550 can be combined with the non-recycle cracker feed 552 upstream of the convection section to form a combined cracker feed stream 554, which can then be introduced into the convection section 510 of the furnace. Alternatively or additionally, the r-pyrolysis oil-containing feed 550 can be introduced into a first furnace coil, while the non-recycle cracker feed 552 can be introduced into a separate or second furnace coil, within the same furnace or within the same convection zone. Then, these two streams can travel through the convection section 510, the crossover 530, and the radiant section 520 within the radiant box 522 in the convection box 512 in parallel with each other, such that each stream is substantially fluidly isolated from the other stream for most or all of the travel path from the inlet to the outlet of the furnace. The pyrolysis stream introduced into any heating zone within the convection section 510 can flow through the convection section 510 and into the radiant box 522 as an evaporation stream 514b. In other embodiments, the r-pyrolysis oil-containing feed stream 550 can also be introduced into the non-recycle cracker stream 552 as it flows through the furnace coils in the convection section 510 into the crossover section 530 of the furnace to form a combined cracker stream 514a, as also shown in Figure 7 as shown.

[0305] In one embodiment or in combination with any of the embodiments mentioned herein or in conjunction with any of the embodiments mentioned, the r-pyrolysis oil 550 can be introduced into a first furnace coil in a first heating zone or a second heating zone as shown in Figure 7 as shown, or an additional amount can be introduced into a second furnace coil. The r-pyrolysis oil 550 can be introduced into the furnace coils at these locations through nozzles. A convenient way to introduce the r-pyrolysis oil feed is through one or more dilution steam feed nozzles, which are used to feed steam into the coils in the convection zone. The service of one or more dilution steam nozzles can be used to inject the r-pyrolysis oil, or new nozzles can be fastened to the coils dedicated to injecting the r-pyrolysis oil. In one embodiment or in combination with any of the embodiments mentioned herein or in conjunction with any of the embodiments mentioned, both steam and r-pyrolysis oil can be co-fed into the furnace coils through nozzles downstream of the coil inlet and upstream of the crossover, optionally in a first or second heating zone within the convection zone, as shown in Figure 7 as shown.

[0306] When introduced into the furnace and / or when combined with the r-pyrolysis oil-containing feed, the non-recycle cracker feed stream can be mainly liquid and have a vapor fraction of less than 0.25 (by volume) or less than 0.25 (by weight), or it can be mainly vapor and have a vapor fraction of at least 0.75 (by volume) or at least 0.75 (by weight). Similarly, when introduced into the furnace and / or combined with the non-recycle cracker stream, the r-pyrolysis oil-containing feed can be mainly vapor or mainly liquid.

[0307] In one embodiment or in combination with any of the embodiments described herein, at least a portion or all of the r-pyrolysis oil stream or the cracker feed stream may be preheated prior to introduction into the furnace. As Figure 8 shown, the preheating may be carried out with an indirect heat exchanger 618 heated by a heat transfer medium (such as steam, hot condensate or a portion of the olefin-containing effluent) or via a direct fired heat exchanger 618. The preheating step may evaporate all or part of the stream containing r-pyrolysis oil, and may evaporate, for example, at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 99 weight percent of the stream containing r-pyrolysis oil.

[0308] When preheating is carried out, the temperature of the stream containing r-pyrolysis oil may be increased to a temperature within about 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 or 2 °C of the bubble point temperature of the stream containing r-pyrolysis oil. Additionally or alternatively, the preheating may increase the temperature of the stream containing r-pyrolysis oil to a temperature at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 100 °C lower than the coking temperature of the stream. In one embodiment or in combination with any of the embodiments described herein, the preheated r-pyrolysis oil stream may have a temperature of at least 200, 225, 240, 250 or 260 °C, and / or not exceeding 375, 350, 340, 330, 325, 320 or 315 °C, or at least 275, 300, 325, 350, 375 or 400 °C, and / or not exceeding 600, 575, 550, 525, 500 or 475 °C. When an atomized liquid (described below) is injected into the vapor-phase heated cracker stream, the liquid may rapidly evaporate such that, for example, the entire combined cracker stream is vapor (e.g., 100% vapor) within 5, 4, 3, 2 or 1 second after injection.

[0309] In one embodiment or in combination with any of the embodiments described herein, the heated r-pyrolysis oil stream (or the cracker stream containing r-pyrolysis oil and the non-recycled cracker stream) may optionally be passed through a vapor-liquid separator to remove any residual heavy or liquid components (when present). The resulting light fraction may then be introduced into the cracking furnace either alone or in combination with one or more of the other cracker streams described in the various embodiments herein. For example, in one embodiment or in combination with any of the embodiments described herein, the r-pyrolysis oil stream may contain at least 1, 2, 5, 8, 10 or 12 weight percent of C 15 and heavier components. The separation may remove at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 99 weight percent of the heavier components from the r-pyrolysis oil stream.

[0310] Returning to Figure 7, the cracker feed stream (alone or when combined with the r-pyrolysis oil feed stream) can be introduced into the furnace coils at or near the inlet of the convection section. The cracker stream can then pass through at least a portion of the furnace coils in the convection section 510, and dilution steam can be added at some point to control the temperature and cracking severity in the furnace. In one embodiment or in combination with any of the embodiments mentioned herein, the steam can be added upstream of the convection section or at the inlet of the convection section, or it can be added downstream of the inlet of the convection section, in the convection section, in the crossover section, or upstream of the radiant section or at the inlet of the radiant section. Similarly, a stream containing r-pyrolysis oil and a non-recovered cracker stream (alone or in combination with steam) can be introduced into the convection section or upstream of or at the inlet of the convection section, or downstream of the inlet of the convection section - within the convection section, at the crossover, or at the inlet of the radiant section. The steam can be combined with the r-pyrolysis oil stream and / or the cracker stream, and the combined stream can be introduced at one or more of these locations, or the steam and r-pyrolysis oil and / or non-recovered cracker stream can be added separately.

[0311] When combined with steam and fed into or near the crossover section of the furnace, the r-pyrolysis oil and / or cracker stream can have a temperature of 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670 or 680 °C, and / or not exceeding 850, 840, 830, 820, 810, 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655 or 650 °C. The resulting steam and r-pyrolysis oil stream can have a vapor fraction of at least 0.75, 0.80, 0.85, 0.90 or at least 0.95 (by weight), or at least 0.75, 0.80, 0.85, 0.90 and 0.95 (by volume).

[0312] When combined with steam and fed into or near the inlet of the convection section 510, the r-pyrolysis oil and / or cracker stream can have a temperature of at least 30, 35, 40, 45, 50, 55, 60 or 65, and / or not exceeding 100, 90, 80, 70, 60, 50 or 45 °C.

[0313] The amount of steam added can depend on operating conditions, including feed type and desired products, but can be added such that the steam-to-hydrocarbon ratio can be at least 0.10:1, 0.15:1, 0.20:1, 0.25:1, 0.27:1, 0.30:1, 0.32:1, 0.35:1, 0.37:1, 0.40:1, 0.42:1, 0.45:1, 0.47:1, 0.50:1, 0.52:1, 0.55:1, 0.57:1, 0.60:1, 0.62:1, 0.65:1, and / or not exceeding about 1:1, 0.95:1, 0.90:1, 0.85:1, 0.80:1, 0.75:1, 0.72:1, 0.70:1, 0.67:1, 0.65:1, 0.62:1, 0.60:1, 0.57:1, 0.55:1, 0.52:1, 0.50:1, or it can be in the range of 0.1:1 to 1.0:1, 0.15:1 to 0.9:1, 0.2:1 to 0.8:1, 0.3:1 to 0.75:1, or 0.4:1 to 0.6:1. When determining the "steam-to-hydrocarbon" ratio, all hydrocarbon components are included and the ratio is by weight. In one embodiment or in combination with any of the embodiments described herein, steam can be generated using a separate boiler feed water / steam line heated in the convection section of the same furnace ( Figure 7 not shown). When the cracker stream has a vapor fraction of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90, steam can be added to the cracker feed (or any intermediate cracker stream within the furnace).

[0314] When a feed stream containing r-pyrolysis oil is introduced separately from a non-recovered feed stream into a cracking furnace, the molar flow rate of the r-pyrolysis oil and / or the stream containing r-pyrolysis oil can be different from the molar flow rate of the non-recovered feed stream. In one embodiment or in combination with any other mentioned embodiment, a method for preparing one or more olefins is provided, which comprises: (a) feeding a first cracker stream having r-pyrolysis oil to a first tube inlet in a cracking furnace; (b) feeding a second cracker stream containing or mainly containing C2-C4 hydrocarbons to a second tube inlet in the cracking furnace, wherein the second tube is separated from the first tube, and the total molar flow rate of the first cracker stream fed at the first tube inlet is lower than the total molar flow rate of the second cracker stream fed to the second tube inlet calculated without the influence of steam. The feeds in step (a) and step (b) can be to respective coil inlets.

[0315] For example, when the r-pyrolysis oil or the first cracker stream passes through a tube in the cracking furnace, its molar flow rate can be higher than that of the hydrocarbon components (such as C2-C4 or C5-C 22) The flow rate of the component through the other or second tube is at least 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55 or 60% lower. When steam is present in the stream containing r-pyrolysis oil or the first cracker stream and in the second cracker stream or the non-recycle stream, the total molar flow rate of the stream containing r-pyrolysis oil or the first cracker stream (including r-pyrolysis oil and dilution steam) can be at least 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55 or 60% higher than the total molar flow rate of the non-recycle cracker feed or the second cracker stream (where the percentage is calculated as the difference between the two molar flow rates divided by the flow rate of the non-recycle stream) (including hydrocarbons and dilution steam).

[0316] In one embodiment or in combination with any embodiment mentioned herein, the molar flow rate of r-pyrolysis oil in the feed stream containing r-pyrolysis oil (first cracker stream) in the furnace tube can be at least 0.01, 0.02, 0.025, 0.03, 0.035 and / or not more than 0.06, 0.055, 0.05, 0.045 kilomoles per pound per hour lower than the molar flow rate of hydrocarbons (e.g., C2-C4 or C5-C 22 ) in the non-recycle cracker stream (second cracker stream). In one embodiment or in combination with any embodiment mentioned herein, the molar flow rates of r-pyrolysis oil and the cracker feed stream can be substantially similar such that the two molar flow rates are within 0.005, 0.001 or 0.0005 kilomoles per pound per hour of each other. The molar flow rate of r-pyrolysis oil in the furnace tube can be at least 0.0005, 0.001, 0.0025, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15 kilomoles per pound per hour (kmol-lb / hr), and / or not more than 0.25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.08, 0.05, 0.025, 0.01 or 0.008 kilomoles per pound per hour, while the molar flow rate of the hydrocarbon component in one or more other coils can be at least 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, and / or not more than 0.30, 0.29, 0.28, 0.27, 0.26, 0.25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15 kilomoles per pound per hour.

[0317] In one embodiment or in combination with any embodiment mentioned herein, the total molar flow rate of the stream containing r-pyrolysis oil (first cracker stream) can be at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 lower than, and / or not more than 0.30, 0.25, 0.20, 0.15, 0.13, 0.10, 0.09, 0.08, 0.07 or 0.06 kilomoles per pound per hour, or the same as the total molar flow rate of the non-recycle feed stream (second cracker stream). The total molar flow rate of the stream containing r-pyrolysis oil (first cracker stream) can be at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07 higher than, and / or not more than 0.10, 0.09, 0.08, 0.07 or 0.06 kilomoles per pound per hour, and the total molar flow rate of the non-recycle feed stream (second cracker stream) can be at least 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, and / or not more than 0.50, 0.49, 0.48, 0.47, 0.46, 0.45, 0.44, 0.43, 0.42, 0.41, 0.40 kilomoles per pound per hour.

[0318] In one embodiment or in combination with any of the embodiments mentioned herein, the steam-to-hydrocarbon ratio of the r-pyrolysis oil-containing stream or the first cracker stream differs from the steam-to-hydrocarbon ratio of the non-recovery feed stream or the second cracker stream by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80%. The steam-to-hydrocarbon ratio can be higher or lower. For example, the steam-to-hydrocarbon ratio of the r-pyrolysis oil-containing stream or the first cracker stream can differ from the steam-to-hydrocarbon ratio of the non-recovery feed stream or the second cracker stream by at least 0.01, 0.025, 0.05, 0.075, 0.10, 0.125, 0.15, 0.175, or 0.20 and / or not more than 0.3, 0.27, 0.25, 0.22, or 0.20. The steam-to-hydrocarbon ratio of the r-pyrolysis oil-containing stream or the first cracker stream can be at least 0.3, 0.32, 0.35, 0.37, 0.4, 0.42, 0.45, 0.47, 0.5, and / or not more than 0.7, 0.67, 0.65, 0.62, 0.6, 0.57, 0.55, 0.52, or 0.5, and the steam-to-hydrocarbon ratio of the non-recovery cracker feed or the second cracker stream can be at least 0.02, 0.05, 0.07, 0.10, 0.12, 0.15, 0.17, 0.20, 0.25, and / or not more than 0.45, 0.42, 0.40, 0.37, 0.35, 0.32, or 0.30.

[0319] In one embodiment or in combination with any of the embodiments mentioned herein, when a stream is introduced separately and passed through a furnace, the temperature of the r-pyrolysis oil-containing feed stream as it passes through the crossover section in the cracking furnace can be different from the temperature of the non-recovery cracker feed as it passes through the crossover section. For example, when the r-pyrolysis oil stream passes through the crossover section, its temperature can differ from the temperature of the non-recovery hydrocarbon stream (e.g., C2-C4 or C5-C22) passing through the crossover section in another coil by at least 0.01, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75%. The percentage can be calculated based on the temperature of the non-recovery stream according to the following formula:

[0320] [(temperature of the r-pyrolysis oil stream - temperature of the non-recovery cracker stream)] / (temperature of the non-recovery cracker steam), expressed as a percentage.

[0321] The difference can be higher or lower. The average temperature of the stream containing r-pyrolysis oil at the crossover section can be at least 400, 425, 450, 475, 500, 525, 550, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620 or 625 °C, and / or not more than 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525 or 500 °C, while the average temperature of the recycled cracker feed can be at least 401, 426, 451, 476, 501, 526, 551, 560, 565, 570, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620 or 625 °C, and / or not more than 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525 or 500 °C.

[0322] The heated cracker stream, which typically has at least 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670 or 680 °C, and / or not more than 850, 840, 830, 820, 810, 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655 or 650 °C, or a temperature in the range of 500 to 710 °C, 620 to 740 °C, 560 to 670 °C or 510 to 650 °C, can then be transferred from the convection section of the furnace to the radiation section via the crossover section.

[0323] In one embodiment or in combination with any embodiment mentioned herein, the feed stream containing r-pyrolysis oil can be added to the cracker stream at the crossover section. When introduced into the furnace in the crossover section, the r-pyrolysis oil can be at least partially evaporated, for example, by preheating the stream in a direct or indirect heat exchanger. When evaporated or partially evaporated, the stream containing r-pyrolysis oil has a vapor fraction of at least 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 or 0.99 by weight or in one embodiment or in combination with any mentioned embodiment by volume.

[0324] When the stream containing r-pyrolysis oil is atomized before entering the crossover section, one or more atomizing nozzles can be used for atomization. Atomization can be carried out inside or outside the furnace. In one embodiment or in combination with any of the embodiments mentioned herein, an atomizing agent can be added to the stream containing r-pyrolysis oil during or before atomization of the stream. The atomizing agent can include steam, or it can mainly include ethane, propane, or a combination thereof. When used, the atomizing agent can be present in the stream to be atomized (e.g., the composition containing r-pyrolysis oil) in an amount of at least 1, 2, 4, 5, 8, 10, 12, 15, 10, 25, or 30 weight percent, and / or not more than 50, 45, 40, 35, 30, 25, 20, 15, or 10 weight percent.

[0325] The atomized or vaporized r-pyrolysis oil stream can then be injected into or combined with the cracker stream passing through the crossover section. At least a portion of the injection can be carried out using at least one nozzle. At least one nozzle can be used to inject the stream containing r-pyrolysis oil into the cracker feed stream, and the nozzle can be oriented to discharge the atomized stream at an angle within about 45, 50, 35, 30, 25, 20, 15, 10, 5, or 0° with respect to the vertical. The nozzle or nozzles can also be oriented to discharge the atomized stream into the coils in the furnace at an angle within about 30, 25, 20, 15, 10, 8, 5, 2, or 1° parallel or parallel to the axial centerline of the coil at the point of introduction. In the crossover and / or convection section of the furnace, at least two, three, four, five, six, or more nozzles can be used for the step of injecting and atomizing r-pyrolysis oil.

[0326] In one embodiment or in combination with any of the embodiments mentioned herein, the atomized r-pyrolysis oil can be fed alone or in combination with at least a portion of the non-recycle cracker stream into the inlet of one or more coils in the convection section of the furnace. The temperature of such atomization can be at least 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 °C, and / or not more than 120, 110, 100, 90, 95, 80, 85, 70, 65, 60, or 55 °C.

[0327] In one embodiment or in combination with any embodiment mentioned herein, the temperature of the atomized or vaporized stream can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350 °C colder than the temperature of the cracker stream to which it is added, and / or not more than 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 75, 70, 60, 55, 50, 45, 40, 30 or 25 °C. The resulting combined cracker stream comprises a continuous gas phase and a discontinuous liquid phase (or droplets or particles) dispersed therein. The atomized liquid phase may comprise r-pyrolysis oil, while the gas phase may mainly comprise C2-C4 components, ethane, propane or a combination thereof. The combined cracker stream can have a vapor fraction of at least 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 or 0.99 by weight or in one embodiment or in combination with any mentioned embodiment by volume.

[0328] The temperature of the cracker stream passing through the crossover section can be at least 500, 510, 520, 530, 540, 550, 555, 560, 565, 570, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620, 625, 630, 635, 640, 645, 650, 660, 670 or 680 °C, and / or not more than 850, 840, 830, 820, 810, 800, 795, 790, 785, 780, 775, 770, 765, 760, 755, 750, 745, 740, 735, 730, 725, 720, 715, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 645, 640, 635 or 630 °C, or in the range of 620 to 740 °C, 550 to 680 °C, 510 to 630 °C.

[0329] Then, the resulting cracker feed stream enters the radiant section. In one embodiment or in combination with any embodiment mentioned herein, the cracker stream from the convection section (with or without r-pyrolysis oil) can pass through a vapor-liquid separator to separate the stream into a heavy fraction and a light fraction before further cracking the light fractions in the radiant section of the furnace. Figure 8 An example of this situation is shown.

[0330] In one embodiment or in combination with any of the embodiments mentioned herein, the vapor-liquid separator 640 can include a flash drum, while in other embodiments, it can include a fractionation column. When the stream 614 passes through the vapor-liquid separator 640, the gas stream impinges on and flows across the trays, and the liquid from the trays falls to the bottoms stream 642. The vapor-liquid separator can also include a demister or chevron or other device located near the vapor outlet for preventing liquid from being carried from the vapor-liquid separator 640 into the gas outlet.

[0331] Within the convection section 610, the temperature of the cracker stream can be increased by at least 50, 75, 100, 150, 175, 200, 225, 250, 275, or 300 °C, and / or not exceeding about 650, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, or 275 °C, such that the passage of the heated cracker stream exiting the convection section 610 through the vapor-liquid separator 640 can occur at a temperature of at least 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650 °C, and / or not exceeding 800, 775, 750, 725, 700, 675, 650, 625 °C. When there are heavier components, at least a portion or substantially all of the heavier components can be removed as bottoms stream 642 in the heavier components. At least a portion of the light fraction 644 from the separator 640 can be introduced into the crossover section or the radiant zone tubes 624 alone or in combination with one or more other cracker streams, such as a hydrocarbon feed stream mainly of C5-C 22 or a hydrocarbon stream of C2-C4, after separation.

[0332] Reference Figure 5 and 6 , the cracker feed streams (non-recycle cracker feed streams or when combined with the r-pyrolysis oil feed stream) 350 and 650 can be introduced into the furnace coils at or near the inlet of the convection section. The cracker feed streams can then pass through at least a portion of the furnace coils in the convection sections 310 and 610, and dilution steam 360 and 660 can be added at some points to control the temperature and cracking severity in the radiant sections 320 and 620. The amount of steam added can depend on the furnace operating conditions, including the feed type and the desired product distribution, but can be added to achieve a steam-to-hydrocarbon ratio within the range of 0.1 to 1.0, 0.15 to 0.9, 0.2 to 0.8, 0.3 to 0.75, or 0.4 to 0.6 by weight. In one embodiment or in combination with any of the embodiments described herein, the steam can be used in the same furnace ( Figure 5Generated by a separate boiler feed water / steam tube heated in the convection section (not shown). Steam 360 and 660 can be added to the cracker feed (or any intermediate cracker feed stream in the furnace) when the cracker feed stream has a vapor fraction by weight of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90, or in one embodiment or in combination with any of the embodiments mentioned, by volume.

[0333] The heated cracker stream, which typically has at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case in °C, and / or not exceeding 850, or not exceeding 840, or not exceeding 830, or not exceeding 820, or not exceeding 810, or not exceeding 800, or not exceeding 790, or not exceeding 780, or not exceeding 770, or not exceeding 760, or not exceeding 750, or not exceeding 740, or not exceeding 730, or not exceeding 720, or not exceeding 710, or not exceeding 705, or not exceeding 700, or not exceeding 695, or not exceeding 690, or not exceeding 685, or not exceeding 680, or not exceeding 675, or not exceeding 670, or not exceeding 665, or not exceeding 660, or not exceeding 655 °C, or not exceeding 650 °C, in each case in °C, or in the range of 500 to 710 °C, 620 to 740 °C, 560 to 670 °C or 510 to 650 °C, can then pass from the convection section 610 of the furnace through the crossover section 630 to the radiation section 620. In one embodiment or in combination with any of the embodiments mentioned herein, a feed stream 550 containing r-pyrolysis oil can be added to the cracker stream at the crossover section 530, as Figure 6As shown. When introduced into the furnace at the crossover section, the r-pyrolysis oil can be at least partially vaporized or atomized before being combined with the cracker stream at the crossover. The temperature of the cracker stream passing through the crossover 530 or 630 can be at least 400, 425, 450, 475, or at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case in °C, and / or not exceeding 850, or not exceeding 840, or not exceeding 830, or not exceeding 820, or not exceeding 810, or not exceeding 800, or not exceeding 790, or not exceeding 780, or not exceeding 770, or not exceeding 760, or not exceeding 750, or not exceeding 740, or not exceeding 730, or not exceeding 720, or not exceeding 710, or not exceeding 705, or not exceeding 700, or not exceeding 695, or not exceeding 690, or not exceeding 685, or not exceeding 680, or not exceeding 675, or not exceeding 670, or not exceeding 665, or not exceeding 660, or not exceeding 655 °C, or not exceeding 650 °C, in each case in °C, or in the range of 620 to 740 °C, 550 to 680 °C, 510 to 630 °C.

[0334] The resulting cracker feed stream then passes through the radiant section, where the feed stream containing r-pyrolysis oil is thermally cracked to form lighter hydrocarbons, including olefins such as ethylene, propylene, and / or butadiene. The residence time of the cracker feed stream in the radiant section can be at least 0.1, or at least 0.15, or at least 0.2, or at least 0.25, or at least 0.3, or at least 0.35, or at least 0.4, or at least 0.45, in each case in seconds, and / or not more than 2, or not more than 1.75, or not more than 1.5, or not more than 1.25, or not more than 1, or not more than 0.9, or not more than 0.8, or not more than 0.75, or not more than 0.7, or not more than 0.65, or not more than 0.6, or not more than 0.5, in each case in seconds. The temperature at the inlet of the furnace coil is at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case in °C, and / or not more than 850, or not more than 840, or not more than 830, or not more than 820, or not more than 810, or not more than 800, or not more than 790, or not more than 780, or not more than 770, or not more than 760, or not more than 750, or not more than 740, or not more than 730, or not more than 720, or not more than 710, or not more than 705, or not more than 700, or not more than 695, or not more than 690, or not more than 685, or not more than 680, or not more than 675, or not more than 670, or not more than 665, or not more than 660, or not more than 655 °C, or not more than 650 °C, in each case in °C, or in the range of 550 to 710 °C, 560 to 680 °C, or 590 to 650 °C, or 580 to 750 °C, 620 to 720 °C, or 650 to 710 °C.

[0335] The coil outlet temperature can be at least 640, or at least 650, or at least 660, or at least 670, or at least 680, or at least 690, or at least 700, or at least 720, or at least 730, or at least 740, or at least 750, or at least 760, or at least 770, or at least 780, or at least 790, or at least 800, or at least 810, or at least 820, in each case in °C, and / or not exceeding 1000, or not exceeding 990, or not exceeding 980, or not exceeding 970, or not exceeding 960, or not exceeding 950, or not exceeding 940, or not exceeding 930, or not exceeding 920, or not exceeding 910, or not exceeding 900, or not exceeding 890, or not exceeding 880, or not exceeding 875, or not exceeding 870, or not exceeding 860, or not exceeding 850, or not exceeding 840, or not exceeding 830, in each case in °C, in the range of 730 to 900 °C, 750 to 875 °C, or 750 to 850 °C.

[0336] The cracking carried out in the furnace coils can include cracking a cracker feed stream under a set of processing conditions including target values of at least one operating parameter. Examples of suitable operating parameters include but are not limited to maximum cracking temperature, average cracking temperature, average tube outlet temperature, maximum tube outlet temperature, and average residence time. When the cracker stream further includes steam, the operating parameters can include hydrocarbon molar flow rate and total molar flow rate. When two or more cracker streams pass through separate coils in the furnace, one of the coils can be operated under a first set of processing conditions and at least one of the other coils can be operated under a second set of processing conditions. The target value of at least one of the operating parameters from the first set of processing conditions can differ from the target value of the same parameter in the second set by at least 0.01, 0.03, 0.05, 0.1, 0.25, 0.5, 1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95%, and / or not exceeding about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 or 15%. Examples include 0.01 to 30, 0.01 to 20, 0.01 to 15, 0.03 to 15%. The percentage is calculated according to the following formula:

[0337] [(Measured value of the operating parameter) - (Target value of the operating parameter)] / [(Target value of the operating parameter)], expressed as a percentage.

[0338] As used herein, the term "different" means higher or lower.

[0339] The coil outlet temperature can be at least 640, 650, 660, 670, 680, 690, 700, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820 °C, and / or not exceed 1000, 990, 980, 970, 960, 950, 940, 930, 920, 910, 900, 890, 880, 875, 870, 860, 850, 840, 830 °C, within the range of 730 to 900 °C, 760 to 875 °C or 780 to 850 °C.

[0340] In one embodiment or in combination with any embodiment mentioned herein, adding r-pyrolysis oil to the cracker feed stream can cause a change in one or more of the above operating parameters compared to the value of the operating parameter when processing the same cracker feed stream in the absence of r-pyrolysis oil. For example, the value of one or more of the above parameters can differ (e.g., be higher or lower) from the value of the same parameter when processing the same feed stream without r-pyrolysis oil by at least 0.01, 0.03, 0.05, 0.1, 0.25, 0.5, 1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95%. The percentage is calculated according to the following formula:

[0341] [(Measured value of the operating parameter) - (Target value of the operating parameter)] / [(Target value of the operating parameter)], expressed as a percentage.

[0342] An example of an operating parameter that can be adjusted by adding r-pyrolysis oil to the cracker stream is the coil outlet temperature. For example, in one embodiment or in combination with any embodiment mentioned herein, when there is a cracker stream without r-pyrolysis oil, the cracking furnace can be operated to achieve a first coil outlet temperature (COT1). Next, r-pyrolysis oil can be added to the cracker stream via any method mentioned herein, and the combined stream can be cracked to achieve a second coil outlet temperature (COT2) different from COT1.

[0343] In some cases, when the r-pyrolysis oil is heavier than the cracker stream, COT2 can be less than COT1, while in other cases, when the r-pyrolysis oil is lighter than the cracker stream, COT2 can be greater than or equal to COT1. When the r-pyrolysis oil is lighter than the cracker stream, it can have a boiling point at least 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50% higher than the 50% boiling point of the cracker stream, and / or not exceed 80, 75, 70, 65, 60, 55 or 50% of the 50% boiling point of the cracker stream. The percentage is calculated according to the following formula:

[0344] [(50% boiling point of r-pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0345] Alternatively or additionally, the 50% boiling point of the r-pyrolysis oil can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 °C lower than the 50% boiling point of the cracker stream, and / or not more than 300, 275, 250, 225 or 200 °C. The heavier cracker stream can include, for example, vacuum gas oil (VGO), atmospheric gas oil (AGO) or even coker gas oil (CGO) or combinations thereof.

[0346] When the r-pyrolysis oil is lighter than the cracker stream, it can have a 50% boiling point that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50% lower than the 50% boiling point of the cracker stream, and / or not more than 80, 75, 70, 65, 60, 55 or 50% of the 50% boiling point. The percentage is calculated according to the following formula:

[0347] [(50% boiling point of r-pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0348] Additionally or alternatively, the 50% boiling point of the r-pyrolysis oil can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 °C higher than the 50% boiling point of the cracker stream, and / or not more than 300, 275, 250, 225 or 200 °C. The lighter cracker stream can include, for example, LPG, naphtha, kerosene, natural gasoline, straight-run gasoline and combinations thereof.

[0349] In some cases, COT1 may differ (higher or lower) from COT2 by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 °C, and / or not more than about 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70 or 65 °C, or COT1 may differ from COT2 by at least 0.3, 0.6, 1, 2, 5, 10, 15, 20 or 25, and / or not more than 80, 75, 70, 65, 60, 50, 45 or 40% (where the percentage is defined as the difference between COT1 and COT2 divided by COT1, expressed as a percentage). At least one or both of COT1 and COT2 may be at least 730, 750, 77, 800, 825, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, and / or not more than 1200, 1175, 1150, 1140, 1130, 1120, 1110, 1100, 1090, 1080, 1070, 1060, 1050, 1040, 1030, 1020, 1010, 1000, 990, 980, 970, 960 950, 940, 930, 920, 910 or 900 °C.

[0350] In one embodiment or in combination with any embodiment mentioned herein, the mass velocity of the cracker feed stream through at least one or at least two radiant coils (determined across the entire coil, as opposed to the tubes within the coil, for clarity) is in the range of 60 to 165 kilograms per second (kg / s) per square meter (m 2 ) of cross-sectional area (kg / s / m 2 ), 60 to 130 (kg / s / m 2 ), 60 to 110 (kg / s / m 2 ), 70 to 110 (kg / s / m 2 ), or 80 to 100 (kg / s / m 2 ). When steam is present, the mass velocity is based on the total flow rate of hydrocarbon and steam.

[0351] In one embodiment or in combination with any of the embodiments mentioned, a method for preparing one or more olefins is provided, which comprises: (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit; (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and (c) cracking the combined cracker stream at a second coil outlet temperature (COT2) in the cracking unit, wherein the second coil outlet temperature is lower than the first coil outlet temperature, or at least 3 °C lower, or at least 5 °C lower.

[0352] The reason or cause for the temperature drop of the second coil outlet temperature (COT2) is not limited as long as COT2 is lower than the first coil outlet temperature (COT1). In one embodiment or in combination with any of the embodiments mentioned, in one embodiment or in combination with any of the embodiments mentioned, the COT2 temperature on the coil of the r-pyrolysis oil feed can be set to be lower than COT1 ("set" mode), or at a temperature at least 1, 2, 3, 4 or at least 5 °C lower than it, or it can be allowed to change or float without setting the temperature on the coil of the r-pyrolysis oil feed ("free float" mode).

[0353] In the set mode, COT2 can be set to be at least 5 °C lower than COT1. All the coils in the furnace can be feed streams containing r-pyrolysis oil, or at least 1, or at least two coils can be feed streams containing r-pyrolysis oil. In either case, at least one of the coils containing r-pyrolysis oil can be in the set mode. By reducing the cracking severity of the combined cracking stream, when its average number-average molecular weight is higher than the cracker feed stream such as gaseous C2-C4 feed, the lower heat energy required for cracking r-pyrolysis oil can be utilized. Although the cracking severity of the cracker feed (such as C2-C4) can be reduced, thereby increasing the amount of un-converted C2-C4 feed in a single pass, a higher amount of un-converted feed (such as C2-C4 feed) is required to increase the final yield of olefins such as ethylene and / or propylene in multiple passes by recycling the un-converted C2-C4 feed through the furnace. Optionally, other cracker products such as aromatic hydrocarbon and diene content can be reduced.

[0354] In one embodiment or in combination with any of the embodiments mentioned, when the hydrocarbon mass flow rate of the combined cracker stream in at least one coil is equal to or less than the hydrocarbon mass flow rate of the cracker stream in step (a) of the coil, COT2 in the coil can be fixed in a set mode to be lower than COT1, or at least 1, 2, 3, 4 or at least 5 °C lower than it. The hydrocarbon mass flow rate includes all hydrocarbons (cracker feed and r-pyrolysis oil and / or natural gasoline or any other type of hydrocarbon if present) and hydrocarbons other than steam. Fixing COT2 is advantageous when the hydrocarbon mass flow rate of the combined cracker stream in step (b) is equal to or less than the hydrocarbon mass flow rate of the cracker stream in step (a) and the average molecular weight of the pyrolysis oil is higher than the average molecular weight of the cracker stream. At the same hydrocarbon mass flow rate, when the pyrolysis oil has a heavier average molecular weight than the cracker stream, COT2 will tend to increase with the addition of the pyrolysis oil because higher molecular weight molecules require less thermal energy to crack. If it is desired to avoid over-cracking the pyrolysis oil, the reduced COT2 temperature can help reduce by-product formation, and while the single-pass olefin yield is also reduced, the final olefin yield can be satisfactory or increased by recycling the unconverted cracker feed through the furnace.

[0355] In the set mode, the temperature can be fixed or set by adjusting the fuel ratio of the furnace to the burner.

[0356] In one embodiment or in combination with any other embodiment mentioned, COT2 is in a free-floating mode and is the temperature of the coil that supplies the pyrolysis oil and allows COT2 to rise or fall without fixing the pyrolysis oil feed. In this embodiment, not all coils contain r-pyrolysis oil. The thermal energy supplied to the coil containing r-pyrolysis oil can be provided by maintaining a constant temperature or fuel feed rate of the burner on the coil containing the non-recycled cracker feed. Without fixing or setting COT2, when the pyrolysis oil is fed to the cracker stream to form a combined cracker stream with a hydrocarbon mass flow rate higher than the hydrocarbon mass flow rate of the cracker stream in step (a), COT2 can be lower than COT1. Adding the pyrolysis oil to the cracker feed to increase the hydrocarbon mass flow rate of the combined cracker feed reduces COT2 and can exceed the temperature-raising effect of using pyrolysis oil with a higher average molecular weight. These effects can be seen while other cracker conditions remain constant, such as the dilution steam ratio, feed location, composition of the cracker feed and pyrolysis oil, and the fuel feed rate to the burner in the combustion chamber of the furnace on the tubes containing only the cracker feed and no r-pyrolysis oil feed.

[0357] COT2 can be lower than COT1, or at least 1, 2, 3, 4, 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, 50 °C lower, and / or not more than about 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70 or 65 °C lower than COT1.

[0358] Irrespective of the cause or origin of the temperature drop in COT2, the time period of step (a) of the joining is flexible, but ideally, step (a) reaches a steady state before step (b) of the joining. In one embodiment or in combination with any of the embodiments mentioned, step (a) is operated for at least 1 week, or at least 2 weeks, or at least 1 month, or at least 3 months, or at least 6 months, or at least 1 year, or at least 1.5 years, or at least 2 years. Step (a) can be represented by a cracking furnace that never receives a pyrolysis oil feed or a combined feed of pyrolysis oil and pyrolysis oil during operation. Step (b) can be the first time the furnace receives a pyrolysis oil feed or a combined cracking unit feed containing pyrolysis oil. In one embodiment or in combination with any other embodiment mentioned, steps (a) and (b) can be cycled multiple times per year, as measured over a calendar year, such as at least 2x / yr, or at least 3x / yr, or at least 4x / yr, or at least 5x / yr, or at least 6x / yr, or at least 8x / yr, or at least 12x / yr. The feed of the blended pyrolysis oil represents multiple cycles of steps (a) and (b). When the feed supply of the pyrolysis oil is exhausted or shut off, COT1 is allowed to reach a steady state temperature before step (b) of the joining.

[0359] Alternatively, the feed of the pyrolysis oil to the cracking unit feed can be continuous throughout at least 1 calendar year or at least 2 calendar years.

[0360] In one embodiment or in combination with any other embodiment mentioned, the composition of the cracking unit feed used in steps (a) and (b) remains unchanged, allowing regular compositional changes to be observed over the course of a calendar year. In one embodiment or in combination with any other embodiment mentioned, the flow of the cracking unit feed in step (a) is continuous and remains continuous when pyrolysis oil enters the cracking unit feed to prepare the combined cracking unit feed. The cracking unit feeds in steps (a) and (b) can be taken from the same source, such as the same stockpile or pipeline.

[0361] In one embodiment or in combination with any of the embodiments mentioned, COT2 is below or at least 1, 2, 3, 4 or at least 5 °C lower for at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 85%, or at least 90%, or at least 95% of the time when pyrolysis oil is fed to the cracker stream to form a combined cracker stream, the measurement time being when all conditions other than COT are held constant, such as the cracking furnace and pyrolysis oil feed rate, steam ratio, feed location, composition of the cracking furnace feed and pyrolysis oil, etc.

[0362] In one embodiment or in combination with any of the embodiments mentioned, the hydrocarbon mass flow rate of the combined cracker feed can be increased. A method for preparing one or more olefins is now provided by the following steps: (a) cracking a cracker stream at a first hydrocarbon mass flow rate (MF1) in a cracking unit; (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream having a second hydrocarbon mass flow rate (MF2) higher than MF1; and (c) cracking the combined cracker stream at MF2 in the cracking unit to obtain an olefin-containing effluent having a combined yield of ethylene and propylene that is the same as or higher than the yield of ethylene and propylene obtained by cracking only the cracker stream at MF1.

[0363] Yield refers to the production rate of the target compound per unit time, expressed in weight, e.g., kg / hr. Increasing the mass flow rate of the cracker stream by adding r-pyrolysis oil can increase the combined production of ethylene and propylene, thus increasing the production of the furnace. Without being bound by theory, it is believed this is possible because the total reaction energy of adding pyrolysis oil is not endothermic relative to the total reaction energy of reacting with lighter cracker feeds such as propane or ethane. Since the heat flux on the furnace is limited and the total heat of reaction of pyrolysis oil is less endothermic, more limited thermal energy can be obtained per unit time to continue cracking the heavy feed. The MF2 can be increased by at least 1, 2, 3, 4, 5, 7, 10, 10, 13, 15, 18, or 20% by the coils for r-pyrolysis oil feed, or can be increased by at least 1, 2, 3, 5, 7, 10, 10, 13, 15, 18, or 20%, as measured by the furnace production rate, provided that at least one coil processes r-pyrolysis oil. Optionally, the increase in the combined production of ethylene and propylene can be achieved without changing the heat flux in the furnace, or without changing the outlet temperature of the r-pyrolysis oil feed coils, or without changing the fuel feed rate of the burners for the coils that heat only the cracker feed containing non-recycled components, or without changing the fuel feed rate of any burner in the furnace. The higher hydrocarbon mass flow rate of MF2 in the coils containing r-pyrolysis oil can be through one or at least one coil in the furnace, or through two or at least two in the furnace, or 50% or at least 50%, or 75% or at least 75%, or through all coils in the furnace.

[0364] The olefin-containing effluent stream can have a combined production of propylene and ethylene from the combined cracker stream at MF2 that is at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% higher than the production of propylene and ethylene in the effluent stream obtained by cracking the same cracker feed without r-pyrolysis oil, as determined below:

[0365]

[0366] where O mf1 is the combined production of propylene and ethylene content in the cracker effluent at MF1 prepared without using r-pyrolysis oil;

[0367] O mf2 is the combined production of propylene and ethylene content in the cracker effluent at MF2 prepared using r-pyrolysis oil.

[0368] The total production of propylene and ethylene in the combined cracker stream of the olefin-containing effluent stream at MF2, calculated as a percentage, is at least 1, 5, 10, 15, 20% of the increase in mass flow rate between MF2 and MF1, and / or at most 80, 70, 65%. Examples of suitable ranges include 1 to 80, or 1 to 70, or 1 to 65, or 5 to 80, or 5 to 70, or 5 to 65, or 10 to 80, or 10 to 70, or 10 to 65, or 15 to 80, or 15 to 70, or 15 to 65, or 20 to 80, or 20 to 70, or 20 to 65, or 25 to 80, or 25 to 70, or 26 to 65, or 35 to 80, or 35 to 70, or 35 to 65, or 40 to 80, or 40 to 70, or 40 to 65, each expressed as a percentage %. For example, if the percentage difference between MF2 and MF1 is 5% and the total production of propylene and ethylene increases by 2.5%, the increase in olefins as a function of the increase in mass flow rate is 50% (2.5% / 5% × 100). This can be determined as:

[0369]

[0370] where ΔO% is the percentage increase between the combined production of propylene and ethylene in the cracker effluent at MF1 prepared without using r-pyrolysis oil and MF2 prepared using r-pyrolysis oil (using the formula above); and

[0371] ΔMF% is the percentage increase of MF2 compared to MF1.

[0372] Optionally, the olefin-containing effluent stream may have a total wt.% of propylene and ethylene from the combined cracker stream at MF2 that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% higher than the wt.% of propylene and ethylene in the effluent stream obtained by cracking the same cracker feed without r-pyrolysis oil, as determined as follows:

[0373]

[0374] where E mf1 is the combined wt.% of propylene and ethylene in the cracker effluent at MF1 prepared without using r-pyrolysis oil;

[0375] E mf2 is the combined wt.% of propylene and ethylene in the cracker effluent at MF2 prepared using r-pyrolysis oil.

[0376] There is also provided a method for preparing one or more olefins, the method comprising: (a) cracking a cracker stream in a cracking furnace to provide a first olefin-containing effluent exiting the cracking furnace at a first coil outlet temperature (COT1); (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and (c) cracking the combined cracker stream in the cracking unit to provide a second olefin-containing effluent exiting the cracking furnace at a second coil outlet temperature (COT2), wherein when the r-pyrolysis oil is heavier than the cracker stream, COT2 is equal to or less than COT1, and wherein when the r-pyrolysis oil is lighter than the cracker stream, COT2 is greater than or equal to COT1.

[0377] In this method, the above embodiments are also applicable to COT2 that is lower than COT1. COT2 can be in a set mode or a free-floating mode. In one embodiment or in combination with any other mentioned embodiment, COT2 is in a free-floating mode, and the hydrocarbon mass flow rate of the combined cracker stream in step (b) is higher than the hydrocarbon mass flow rate of the cracker stream in step (a). In one embodiment or in combination with any mentioned embodiment, COT2 is in a set mode.

[0378] In one embodiment or in combination with any mentioned embodiment, there is provided a method for preparing one or more olefins by: (a) cracking a cracker stream in a cracking unit at a first coil outlet temperature (COT1); (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and (c) cracking the combined cracker stream in the cracking unit at a second coil outlet temperature (COT2), wherein the second coil outlet temperature is higher than the first coil outlet temperature.

[0379] COT2 can be at least 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, 50 °C higher than COT1, and / or not more than about 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70 or 65 °C higher.

[0380] In one embodiment or in combination with any other recited embodiment, r-pyrolysis oil is added to at least one coil, or at least two coils, or at least 50%, or at least 75%, or all of the inlets of the coils to form at least one combined cracker stream, or at least two combined cracker streams, or at least the same number of combined cracker streams as the coils receiving the r-pyrolysis oil feed. At least one or at least two combined cracker streams, or at least all of the r-pyrolysis oil feed coils may have a COT2 that is higher than their respective COT1. In one embodiment or in combination with any recited embodiment, at least one or at least two coils, or at least 50%, or at least 75% of the coils within the cracking furnace contain only non-recycle component cracker feed, wherein at least one coil within the cracking furnace is fed with r-pyrolysis oil, and at least some of the coils or the plurality of coils fed with r-pyrolysis oil have a COT2 that is higher than their respective COT1.

[0381] In one embodiment or in combination with any recited embodiment, the hydrocarbon mass flow rate of the combined stream in step (b) is substantially equal to or lower than the hydrocarbon mass flow rate of the cracker stream in step (a). Substantially the same means a difference of no more than 2%, or no more than 1%, or no more than 0.25%. When the hydrocarbon mass flow rate of the combined cracker stream in step (b) is substantially equal to or lower than the hydrocarbon mass flow rate of the cracker stream (a), and COT2 is allowed to operate in a free-floating mode (where at least 1 tube contains a non-recycle component cracker stream), the COT2 on the coils containing r-pyrolysis oil can rise relative to COT1. This is the case even though pyrolysis oil with a larger number average molecular weight compared to the cracker stream requires less energy to crack. Without being bound by theory, it is believed that one factor or combination of factors contributes to the temperature rise, including the following:

[0382] (i) Less thermal energy is required to crack the pyrolysis oil in the combined stream.

[0383] (ii) Exothermic reactions occur in the cracking products of the pyrolysis oil, such as Diels-Alder reactions.

[0384] This effect can be seen when other process variables are constant, such as the combustion chamber fuel rate, dilution steam ratio, feed location, and cracker feed composition.

[0385] In one embodiment or in combination with any recited embodiment, COT2 can be set or fixed to a temperature higher than COT1 (set mode). This is more applicable when the hydrocarbon mass flow rate of the combined cracker stream is higher than the hydrocarbon mass flow rate of the cracker stream, otherwise this will lower COT2. A higher second coil outlet temperature (COT2) can contribute to an increase in the severity and a decrease in the yield of unreacted lighter cracker feeds (such as C2-C4 feeds), which can contribute to a fractionation tower with limited downstream capacity.

[0386] In one embodiment or in combination with any of the embodiments mentioned, regardless of whether COT2 is higher or lower than COT1, when compared between COT2 and COT1, the cracker feed composition is the same. Desirably, the cracker feed composition in step (a) is the same cracker composition as that used to prepare the combined cracker stream in step (b). Optionally, the cracker composition feed in step (a) is continuously fed to the cracker unit, and the pyrolysis oil in step (b) is added to the continuous cracker feed in step (a). Optionally, the feeding of pyrolysis oil to the cracker feed is continuous for at least 1 day, or at least 2 days, or at least 3 days, or at least 1 week, or at least 2 weeks, or at least 1 month, or at least 3 months, or at least 6 months or at least 1 year.

[0387] In any of the embodiments mentioned, increasing or decreasing the amount of cracker feed in step (b) can be at least 2%, or at least 5%, or at least 8%, or at least 10%. In one embodiment or in combination with any of the embodiments mentioned, decreasing the amount of cracker feed in step (b) can be corresponding to the amount of pyrolysis oil added by weight. In one embodiment or in combination with any of the embodiments mentioned, the mass flow rate of the combined cracker feed is at least 1%, or at least 5%, or at least 8%, or at least 10% higher than the hydrocarbon mass flow rate of the cracker feed in step (a).

[0388] In any or all of the embodiments mentioned, if any one of the coils in the furnace satisfies the relationship, but can also be present in multiple tubes, depending on how the pyrolysis oil is fed and distributed, then the cracker feed or combined cracker feed mass flow rate and COT relationship and measurement are satisfied.

[0389] In one embodiment or in combination with any of the embodiments mentioned herein, the burner in the radiant section provides an average heat flux into the coil of 60 to 160 kW / m 2 , or 70 to 145 kW / m 2 , or 75 to 130 kW / m 2 . The highest (hottest) coil surface temperature is in the range of 1035 to 1150 °C, or 1060 to 1180 °C. The pressure at the inlet of the furnace coil in the radiant section is in the range of 1.5 to 8 bar absolute (bara) or 2.5 to 7 bar, while the outlet pressure of the furnace coil in the radiant section is in the range of 1.03 to 2.75 bar, or 1.03 to 2.06 bar. The pressure drop across the two ends of the furnace coil in the radiant section can be 1.5 to 5 bar, or 1.75 to 3.5 bar, or 1.5 to 3 bar, or 1.5 to 3.5 bar.

[0390] In one embodiment or in combination with any embodiment mentioned herein, the yield of olefins - ethylene, propylene, butadiene, or combinations thereof - can be at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, in each case as a percentage. As used herein, the term "yield" means product mass / feedstock mass × 100%. The olefin - containing effluent stream contains at least about 30, or at least 40, or at least 50, or at least 60, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case as a weight percentage of ethylene, propylene, or ethylene and propylene, based on the total weight of the effluent stream.

[0391] In one embodiment or in combination with one or more embodiments mentioned herein, the olefin - containing effluent stream 670 can contain C2 - C4 olefins, or propylene, or ethylene, or C4 olefins, in an amount of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 weight, based on the weight of the olefin - containing effluent. The stream can predominantly contain ethylene, predominantly contain propylene, or predominantly contain ethylene and propylene, based on the olefins in the olefin - containing effluent, or based on the weight of C1 - C5 hydrocarbons in the olefin - containing effluent, or based on the weight of the olefin - containing effluent stream. The weight ratio of ethylene to propylene in the olefin - containing effluent stream can be at least about 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1, and / or not more than 3:1, 2.9:1, 2.8:1, 2.7:1, 2.5:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.7:1, 1.5:1, or 1.25:1. In one embodiment or in combination with one or more embodiments mentioned herein, the olefin - containing effluent stream can have a propylene:ethylene ratio that is higher than the propylene:ethylene ratio of an effluent stream obtained by cracking the same cracker feed but without the same dilution steam ratio, feed location, cracker feed composition (different from the r - pyrolysis oil), and having the coil fed with r - pyrolysis oil in a floating mode, or if all coils in the furnace are fed with r - pyrolysis oil, at the same temperature prior to feeding the r - pyrolysis oil. As described above, this is possible when r - pyrolysis oil is added relative to the original feed of the cracker stream, when the mass flow rate of the cracker feed remains substantially the same, resulting in a higher hydrocarbon mass flow rate of the combined cracker stream.

[0392] The olefin-containing effluent stream may have a propylene:ethylene ratio that is at least 1%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 10%, or at least 12%, or at least 15%, or at least 17%, or at least 20% higher than the propylene:ethylene ratio of the effluent stream obtained by cracking the same cracker feedstock without r-pyrolysis oil. Alternatively additionally, the propylene:ethylene ratio of the olefin-containing effluent stream may be at most 50%, or at most 45%, or at most 40%, or at most 35%, or at most 25%, or at most 20% higher than the propylene:ethylene ratio of the effluent stream obtained by cracking the same cracker feedstock without r-pyrolysis oil, in each case measured as:

[0393]

[0394] where E is the propylene:ethylene ratio in the cracker effluent produced without using r-pyrolysis oil, in wt.%;

[0395] E r is the propylene:ethylene ratio in the cracker effluent produced with r-pyrolysis oil, in wt.%.

[0396] In one embodiment or in combination with any of the embodiments mentioned herein, the amounts of ethylene and propylene in the cracked olefin-containing effluent stream may remain substantially the same or increase relative to the effluent stream without r-pyrolysis oil. Surprisingly, liquid r-pyrolysis oil can be fed to a gas-feed furnace that accepts and cracks a mainly C2-C4 composition and obtains an olefin-containing effluent stream that can, in some cases, remain substantially the same or be improved relative to the C2-C4 cracker feedstock without r-pyrolysis oil. The high molecular weight of r-pyrolysis oil may contribute mainly to the formation of aromatic hydrocarbons and only a small amount participates in the formation of olefins (especially ethylene and propylene). However, we have found that at the same hydrocarbon mass flow rate, when r-pyrolysis oil is added to the cracker feedstock to form a combined cracker feedstock, the combined weight percentage, and even the yield, of ethylene and propylene does not decrease significantly relative to the cracker feedstock without r-pyrolysis oil and, in many cases, remains the same or may increase. The olefin-containing effluent stream may have a total wt.% of propylene and ethylene that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% higher than the propylene and ethylene content of the effluent stream obtained by cracking the same cracker feedstock without r-pyrolysis oil, as determined below:

[0397]

[0398] where E is the combined wt.% of propylene and ethylene in the cracker effluent produced without using r-pyrolysis oil;

[0399] Er is the combined wt.% of propylene and ethylene in the cracker effluent produced using r-pyrolysis oil.

[0400] In one embodiment or in combination with one or more embodiments described herein, when the dilution steam ratio (weight ratio of steam:hydrocarbon) is higher than 0.3, or higher than 0.35, or at least 0.4, the wt.% of propylene in the olefin-containing effluent stream can be increased. When the dilution steam ratio is at least 0.3, or at least 0.35, or at least 0.4, the increase in propylene wt.% can be up to 0.25 wt.%, or up to 0.4 wt.%, or up to 0.5 wt.%, or up to 0.7 wt.%, or up to 1 wt.%, or up to 1.5 wt.%, or up to 2 wt.%, where the increase is measured as the simple difference in propylene wt.% between an olefin-containing effluent stream prepared using r-pyrolysis oil with a dilution steam ratio of 0.2 and an olefin-containing effluent stream prepared using r-pyrolysis oil with a dilution steam ratio of at least 0.3, all other conditions being the same.

[0401] When the dilution steam ratio is increased as described above, the propylene:ethylene ratio can also increase, or can be at least 1%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 10%, or at least 12%, or at least 15%, or at least 17%, or at least 20% higher than the propylene:ethylene ratio of an olefin-containing effluent stream produced using r-pyrolysis oil with a dilution steam ratio of 0.2.

[0402] In one embodiment or in combination with one or more embodiments described herein, when the dilution steam ratio is increased, the olefin-containing effluent stream can have a reduced wt.% of methane, when measured relative to the olefin-containing effluent stream at a dilution steam ratio of 0.2. The wt.% of methane in the olefin-containing effluent stream can be reduced by at least 0.25 wt.%, or at least 0.5 wt.%, or at least 0.75 wt.%, or at least 1 wt.%, or at least 1.25 wt.%, or at least 1.5 wt.% as measured by the absolute difference in wt.% between the olefin-containing effluent stream at a dilution steam ratio of 0.2 and higher dilution steam ratio values.

[0403] In one embodiment or in combination with one or more embodiments described herein, when measured relative to a cracker feedstock that does not contain r-pyrolysis oil and all other conditions are the same (including hydrocarbon mass flow rate), the amount of unreacted products in the olefin-containing effluent is reduced. For example, the amount of propane and / or ethane can be reduced by adding r-pyrolysis oil. This can be beneficial in reducing the mass flow rate of the recovery loop, thereby (a) reducing the low-temperature energy cost and / or (b) potentially increasing the capacity of the equipment if the equipment is already capacity-constrained. Additionally, if the propylene fractionator has reached its capacity limit, it can eliminate the bottleneck of the propylene fractionator. The amount of unreacted products in the olefin-containing effluent can be reduced by at least 2%, or at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15%, or at least 18%, or at least 20%.

[0404] In one embodiment or in combination with one or more embodiments described herein, when measured relative to a cracker feedstock that does not contain r-pyrolysis oil, the amount of unreacted products (e.g., the combined amount of propane and ethane) in the olefin-containing effluent is reduced while the combined production of ethylene and propylene does not decrease and even improves. Optionally, all other conditions are the same, including hydrocarbon mass flow rate and temperature, where the fuel feed rate to the heating burner to the non-recovery component cracker feed coil remains constant, or optionally when the fuel feed rate to all coils in the furnace remains constant. Alternatively, the same relationship can hold on a wt.% basis rather than a production basis.

[0405] For example, the total amount of propane and ethane (either or both in production or wt.%) in the olefin-containing effluent can be reduced by at least 2%, or at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15%, or at least 18%, or at least 20%, and in each case at most 40% or at most 35% or at most 30%, and in each case the total amount of ethylene and propylene does not decrease and can even be accompanied by an increase in the total amount of ethylene and propylene. For example, the amount of propane in the olefin-containing effluent can be reduced by at least 2%, or at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15%, or at least 18%, or at least 20%, and in each case at most 40% or at most 35% or at most 30%, and in each case the total amount of ethylene and propylene does not decrease and can even be accompanied by an increase in the total amount of ethylene and propylene. In any of these embodiments, the cracker feedstock (different from r-pyrolysis oil and as fed to the inlet of the convection zone) can be predominantly propane on a molar basis, or at least 90 mol% propane, or at least 95 mol% propane, or at least 96 mol% propane, or at least 98 mol% propane; or the fresh feed of the cracker feedstock can be at least HD5 quality propane.

[0406] In one embodiment or in combination with one or more embodiments described herein, the propane:(ethylene and propylene) ratio in the olefin-containing effluent decreases as r-pyrolysis oil is added to the cracker feed, as measured in wt.% or monthly production when compared to the same cracker feed without pyrolysis oil and all other conditions are the same. The propane:(ethylene and propylene) ratio in the olefin-containing effluent can be no more than 0.50:1, or less than 0.50:1, or no more than 0.48:1, or no more than 0.46:1, or no more than 0.43:1, or no more than 0.40:1, or no more than 0.38:1, or no more than 0.35:1, or no more than 0.33:1, or no more than 0.30:1. A low ratio indicates that a high amount of ethylene + propylene can be achieved or maintained while correspondingly reducing unreacted products such as propane.

[0407] In one embodiment or in combination with one or more embodiments described herein, when r-pyrolysis oil and steam are fed downstream of the inlet of the convection box, or when one or both of r-pyrolysis oil and steam are fed at an intersection location, the C in the olefin-containing effluent 6+ The amount of product can be increased if such product is desired, for example for a BTX stream to prepare its derivatives. When r-pyrolysis oil and steam are fed downstream of the convection box inlet, when measured relative to feeding r-pyrolysis oil at the convection box inlet, the C in the olefin-containing effluent 6+ The amount of product can be increased by 5%, or 10%, or 15%, or 20%, or 30%, all other conditions being the same. The increase % can be calculated as:

[0408]

[0409] where E i is the C in the olefin-containing cracker effluent prepared by introducing r-pyrolysis oil at the inlet of the convection box 6+ content;

[0410] E d is the C in the olefin-containing cracker effluent prepared by introducing pyrolysis oil and steam downstream of the convection box inlet 6+ content.

[0411] In one embodiment or in combination with any of the embodiments described herein, the cracked olefin-containing effluent stream may contain relatively small amounts of aromatic hydrocarbons and other heavy components. For example, the olefin-containing effluent stream may contain at least 0.5, 1, 2, or 2.5 weight percent, and / or no more than about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 weight percent of aromatic hydrocarbons, based on the total weight of the stream. We have found that the level of C6+ species in the olefin-containing effluent can be no more than 5 wt.%, or no more than 4 wt.%, or no more than 3.5 wt.%, or no more than 3 wt.%, or no more than 2.8 wt.%, or no more than 2.5 wt.%. C 6+ species include all aromatic hydrocarbons, as well as all alkanes and cyclic compounds having 6 or more carbon atoms. As used throughout the text, the amount of aromatic hydrocarbons mentioned may be represented by the amount of C 6+ species, since the amount of aromatic hydrocarbons does not exceed the amount of C 6+ species.

[0412] The olefin-containing effluent may have an olefin to aromatic hydrocarbon weight ratio of at least 2:1, 3.1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, or 30:1, and / or no more than 100:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1, 35:1, 30:1, 25:1, 20:1, 15:1, 10:1, or 5:1. As used herein, "olefin to aromatic hydrocarbon" is the ratio of the total weight of C2 and C3 olefins as previously defined to the total weight of aromatic hydrocarbons. In one embodiment or in combination with any of the embodiments mentioned herein, the effluent stream may have an olefin to aromatic hydrocarbon of at least 2.5:1, 2.75:1, 3.5:1, 4.5:1, 5.5:1, 6.5:1, 7.5:1, 8.5:1, 9.5:1, 10.5:1, 11.5:1, 12.5:1, or 13:5:1.

[0413] The olefin-containing effluent may have olefin:C 6+The ratio (by weight) is at least 8.5:1, or at least 9.5:1, or at least 10:1, or at least 10.5:1, or at least 12:1, or at least 13:1, or at least 15:1, or at least 17:1, or at least 19:1, or at least 20:1, or at least 25:1, or at least 28:1, or at least 30:1. Additionally or alternatively, the olefin-containing effluent may have an olefin:C 6+ The ratio is at most 40:1, or at most 35:1, or at most 30:1, or at most 25:1, or at most 23:1. As used herein, "olefin to aromatic hydrocarbon" is the ratio of the total weight of C2 and C3 olefins to the total weight of aromatic hydrocarbons as defined above.

[0414] Additionally or alternatively, the olefin-containing effluent stream may have an olefin to C 6+ The ratio is at least about 1.5:1, 1.75:1, 2:1, 2.25:1, 2.5:1, 2.75:1, 3:1, 3.25:1, 3.5:1, 3.75:1, 4:1, 4.25:1, 4.5:1, 4.75:1, 5:1, 5.25:1, 5.5:1, 5.75:1, 6:1, 6.25:1, 6.5:1, 6.75:1, 7:1, 7.25:1, 7.5:1, 7.75:1, 8:1, 8.25:1, 8.5:1, 8.75:1, 9:1, 9.5:1, 10:1, 10.5:1, 12:1, 13:1, 15:1, 17:1, 19:1, 20:1, 25:1, 28:1 or 30:1.

[0415] In one embodiment or in combination with any embodiment mentioned herein, the olefin:aromatic hydrocarbon decreases as the amount of r-pyrolysis oil added to the cracker feed increases. Since r-pyrolysis oil cracks at a lower temperature, it will crack earlier than propane or ethane and thus has more time to react to produce other products, such as aromatic hydrocarbons. Although the aromatic hydrocarbon content in the olefin-containing effluent increases as the pyrolysis oil amount increases, as described above, the amount of aromatic hydrocarbons produced is significantly low.

[0416] The olefin-containing composition may also include trace amounts of aromatic hydrocarbons. For example, the composition may have a benzene content of at least 0.25, 0.3, 0.4, 0.5 weight percent, and / or not more than about 2, 1.7, 1.6, 1.5 weight percent. Additionally or alternatively, the composition may have a toluene content of at least 0.005, 0.010, 0.015 or 0.020 and / or not more than 0.5, 0.4, 0.3 or 0.2 weight percent. Both percentages are based on the total weight of the composition. Alternatively or additionally, the benzene content of the effluent may be at least 0.2, 0.3, 0.4, 0.5 or 0.55 weight percent, and / or not more than about 2, 1.9, 1.8, 1.7 or 1.6 weight percent, and / or the toluene content may be at least 0.01, 0.05 or 0.10 weight percent, and / or not more than 0.5, 0.4, 0.3 or 0.2 weight percent.

[0417] In one embodiment or in combination with any of the embodiments mentioned herein, the olefin-containing effluent withdrawn from a cracking furnace that has cracked a composition containing r-pyrolysis oil may contain increased amounts of one or more compounds or by-products that are not present in the olefin-containing effluent stream formed by processing a conventional cracker feed. For example, the cracker effluent formed by cracking r-pyrolysis oil (r-olefins) may include increased amounts of 1,3-butadiene, 1,3-cyclopentadiene, dicyclopentadiene, or combinations of these components. In one embodiment or in combination with any of the embodiments mentioned herein, the total amount (by weight) of these components may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85% higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without r-pyrolysis oil treatment. The total amount (by weight) of 1,3-butadiene may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85% higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without r-pyrolysis oil treatment. The total amount (by weight) of 1,3-cyclopentadiene may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85% higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without r-pyrolysis oil treatment. The total amount (by weight) of dicyclopentadiene may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85% higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without r-pyrolysis oil treatment. The percentage difference is calculated by dividing the difference in the weight percentages of one or more of the above components between the r-pyrolysis oil and the conventional stream by the amount of the component in the conventional stream (in weight percent), or:

[0418]

[0419] where E is the wt.% of the components in the cracker effluent made without using r-pyrolysis oil;

[0420] E r is the wt.% of the components in the cracker effluent made with r-pyrolysis oil.

[0421] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream may contain acetylene. The amount of acetylene may be at least 2000 ppm, at least 5000 ppm, at least 8000 ppm, or at least 10,000 ppm, based on the total weight of the effluent stream from the furnace. It may also be no more than 50,000 ppm, no more than 40,000 ppm, no more than 30,000 ppm, or no more than 25,000 ppm, or no more than 10,000 ppm, or no more than 6,000 ppm, or no more than 5000 ppm.

[0422] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream may contain methylacetylene and propadiene (MAPD). The amount of MAPD may be at least 2 ppm, at least 5 ppm, at least 10 ppm, at least 20 ppm, at least 50 ppm, at least 100 ppm, at least 500 ppm, at least 1000 ppm, at least 5000 ppm, or at least 10,000 ppm, based on the total weight of the effluent stream. It may also be no more than 50,000 ppm, no more than 40,000 ppm, or no more than 30,000 ppm, or no more than 10,000 ppm, or no more than 6,000 ppm, or no more than 5,000 ppm.

[0423] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream may contain little or no carbon dioxide. The olefin-containing effluent stream may have an amount of carbon dioxide in wt.%, which does not exceed the amount of carbon dioxide in the effluent stream obtained by cracking the same cracker feed but without r-pyrolysis oil under equivalent conditions, or the amount is not higher than 5% of the amount of carbon dioxide in wt.%, or not higher than 2%, or the same amount as the comparative effluent stream without r-pyrolysis oil. Alternatively or additionally, the olefin-containing effluent stream may have an amount of carbon dioxide not exceeding 1000 ppm, or not exceeding 500 ppm, or not exceeding 100 ppm, or not exceeding 80 ppm, or not exceeding 50 ppm, or not exceeding 25 ppm, or not exceeding 10 ppm, or not exceeding 5 ppm.

[0424] Now turning to Figure 9, which shows a block diagram illustrating the main components of a furnace effluent treatment section.

[0425] As Figure 9 shown, the olefin-containing effluent stream from the cracking furnace 700, which includes recycle components, is rapidly cooled (e.g., quenched) in a transfer line exchanger ("TLE") 680, as Figure 8 shown, to prevent the formation of a large amount of undesired by-products and to minimize fouling in downstream equipment, and also to generate steam. In one embodiment or in combination with any embodiment mentioned herein, the temperature of the effluent containing the r-composition from the furnace can be reduced by 35 to 485 °C, 35 to 375 °C, or 90 to 550 °C to a temperature of 500 to 760 °C. The cooling step is carried out immediately after the effluent stream leaves the furnace, e.g., within 1 to 30, 5 to 20, or 5 to 15 milliseconds. In one embodiment or in combination with any embodiment mentioned herein, the quenching step is carried out in a quench zone 710 by indirect heat exchange with high-pressure water or steam in a heat exchanger (sometimes referred to as a transfer line exchanger, as Figure 5 shown as TLE 340 in Figure 8 and shown as TLE 680 in Figure 9 ), while in other embodiments, the quenching step is carried out by direct contact of the effluent with a quench liquid (as Figure 9 generally shown in

[0426] ). The temperature of the quench liquid can be at least 65, or at least 80, or at least 90, or at least 100, in each case in °C, and / or not more than 210, or not more than 180, or not more than 165, or not more than 150, or not more than 135, in each case in °C. When using a quench liquid, the contact can be carried out in a quench tower, and a liquid stream containing gasoline and other hydrocarbon components of a similar boiling range can be removed from the quench tower. In some cases, when the cracker feed is mainly liquid, a quench liquid can be used, and when the cracker feed is mainly vapor, a heat exchanger can be used.

[0426] The resulting cooled effluent stream is then subjected to vapor-liquid separation, and the vapor is compressed in a compression zone 720, e.g., compressed in a gas compressor having, for example, 1 to 5 compression stages, with optional interstage cooling and liquid removal. The gas flow pressure at the outlet of the first set of compression stages is in the range of 7 to 20 barg, 8.5 - 18 psig (0.6 to 1.3 barg), or 9.5 to 14 barg.

[0427] The resulting compressed stream is then treated in an acid gas removal zone 722 to remove acid gases, including CO, CO2, and H2S, by contact with an acid gas removal agent. Examples of acid gas removal agents can include, but are not limited to, caustic amines and various types of amines. In one embodiment or in combination with any embodiment mentioned herein, a single contactor can be used, while in other embodiments, a two-column absorber-stripper configuration can be employed.

[0428] Then, the processed and compressed olefin-containing stream can be further compressed via a compressor in another compression zone 724, with optional interstage cooling and liquid separation. The resulting compressed stream has a pressure of 20 to 50 barg, 25 to 45 barg, or 30 to 40 barg. Any suitable dehumidification method can be used, including, for example, molecular sieves or other similar methods to dry the gas in the drying zone 726. Then, the resulting stream 730 can be sent to the fractionation section, where the olefins and other components can be separated into various high-purity products or intermediate streams.

[0429] Now turning to Figure 10 , a schematic diagram of the main steps of the fractionation section is provided. In one embodiment or in combination with any of the embodiments mentioned herein, the initial column of the fractionation system may not be the demethanizer 810, but may be a deethanizer 820, a debutanizer 840, or any other type of column. As used herein, the term "demethanizer" refers to a column whose light key is methane. Similarly, "deethanizer" and "debutanizer" refer to columns having ethane and propane, respectively, as the light key components.

[0430] As Figure 10As shown, the feed stream 870 from the quench section can be introduced into a demethanizer (or other) 810, where methane and lighter (CO, CO2, H2) components 812 are separated from ethane and heavier components 814. The demethanizer operates at a temperature of at least -145, or at least -142, or at least -140, or at least -135, in each case in °C, and / or not exceeding -120, -125, -130, -135 °C. Then the bottoms stream 814 from the demethanizer is introduced into a deethanizer 820, where C2 and lighter components 816 are separated from C3 and heavier components 818 by fractionation, and the bottoms stream comprises at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%, in each case as a percentage, of the total amount of ethane and heavier comp...

Claims

1. A method for preparing pyrolysis oil, the method comprising: (a) introducing a pyrolysis feed and a reducing gas stream into a pyrolysis unit, wherein the pyrolysis feed comprises at least one recycled waste; and (b) pyrolyzing at least a portion of the pyrolysis feed to form a pyrolysis effluent comprising pyrolysis oil, wherein the pyrolysis oil (i) comprises less than 15 wt% of an aromatic hydrocarbon component; (ii) comprises at least 25 wt% of an alkane component; (iii) comprises at least 10 wt% of an olefin component; and (iv) Exhibiting a density of less than 0.9 g / cm³ at 15°C 3 . wherein the pyrolysis oil is capable of co-cracking with non-recycled C2-C4 hydrocarbons in a hot gas cracker to obtain an olefin-containing effluent, wherein the olefins mainly comprise ethylene and / or propylene, wherein the cracker is a gas furnace, and wherein the cracker feed stream comprises at least 5 wt% but not more than 40 wt% of pyrolysis oil and at least 60 wt% of C2-C4 hydrocarbons based on the total weight of the cracker feed stream; and wherein the pyrolysis oil is not hydrotreated prior to cracking and does not undergo a separation process for separating heavy hydrocarbon fractions from lighter hydrocarbon fractions relative to each other, wherein the C8+ content of the pyrolysis oil is at least 15 weight percent, based on the total weight of the pyrolysis oil.

2. The method according to claim 1, wherein the recycled waste comprises post-consumer waste and / or post-industrial waste.

3. The method according to claim 2, wherein the post-consumer waste comprises waste plastics, waste rubbers, textiles, modified cellulose, wet-laid products, or combinations thereof.

4. The method according to claim 2, wherein the pyrolysis feed comprises at least 30 wt% of at least one post-consumer waste.

5. The method according to claim 1, wherein the recycled waste comprises at least one recycled waste plastic.

6. The method according to claim 5, wherein the pyrolysis feed comprises at least 30 wt% of at least one recycled waste plastic.

7. The method according to claim 1, wherein the reducing gas stream comprises hydrogen, carbon monoxide, or combinations thereof.

8. The method according to claim 1, wherein the pyrolysis oil comprises less than 15 wt% of an aromatic hydrocarbon component.

9. The method according to claim 1 or 8, wherein the pyrolysis oil comprises at least 25 wt% of an alkane component.

10. The method according to claim 1 or 9, wherein the pyrolysis oil exhibits a density of less than 0.85 g / cm 3 at 15 °C.

11. The method according to claim 1, wherein the reducing gas stream comprises at least 2 wt% of at least one reducing gas.

12. The method according to claim 1, wherein the reducing gas stream comprises at least 40 wt% of hydrogen.

13. The method according to claim 12, wherein the reducing gas stream comprises less than 99 wt% of hydrogen.

14. The method according to claim 1, wherein the pyrolysis step (b) occurs in the absence of a pyrolysis catalyst.

15. The method according to claim 1, wherein the pyrolysis step (b) occurs in the absence of a catalytic cracking catalyst and / or a hydrocracking catalyst.

16. The method according to claim 1, wherein the pyrolysis step (b) occurs in the presence of a hydrogenation catalyst.

17. The method according to claim 1, wherein the reducing gas stream effectively removes at least 10% by weight of nitrogen and / or chlorine initially present in the recycled waste.

18. A method for preparing pyrolysis oil, the method comprising: (a) introducing a pyrolysis feed and a steam-containing stream into a pyrolysis unit, wherein the pyrolysis feed comprises at least one recycled waste; and (b) pyrolyzing at least a portion of the pyrolysis feed to form a pyrolysis effluent comprising pyrolysis oil, wherein the pyrolysis oil (i) comprises less than 25% by weight of an aromatic hydrocarbon component; (ii) comprises at least 25% by weight of an alkane component; (iii) comprises at least 10% by weight of an olefin component; and (iv) exhibiting a density of less than 0.9 g / cm³ at 15°C 3 ; wherein the pyrolysis oil is capable of co-pyrolyzing with non-recycled C2-C4 hydrocarbons in a hot gas cracker to obtain an olefin-containing effluent, wherein the olefins mainly comprise ethylene and / or propylene, wherein the cracker is a gas furnace, wherein the cracker feed stream comprises at least 5 wt% but not more than 40 wt% of pyrolysis oil and at least 60 wt% of C2-C4 hydrocarbons based on the total weight of the cracker feed stream; and wherein the pyrolysis oil is not hydrotreated prior to cracking and does not undergo a separation process for separating heavy hydrocarbon fractions from lighter hydrocarbon fractions relative to each other, wherein the C8+ content of the pyrolysis oil is at least 15 weight percent, based on the total weight of the pyrolysis oil.

19. The method according to claim 18, wherein the recycled waste comprises post-consumer waste and / or post-industrial waste.

20. The method according to claim 19, wherein the post-consumer waste comprises waste plastics, waste rubber, textiles, modified cellulose, wet-laid products, or combinations thereof.

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