Recycled Oxodiol

Abstract

Recycled component oxodiol and method for preparing recycled component oxodiol, wherein the recycled component is directly or indirectly derived from the cracking of recycled component pyrolysis oil and / or recycled component pyrolysis gas. The cracking of the pyrolysis oil can be carried out in a gas furnace or a cracking furnace.

Description

Background Art

[0001] Waste materials, especially non-biodegradable ones, can have a negative impact on the environment when disposed of in landfills after a single use. Therefore, from an environmental point of view, it is desirable to recycle as much waste material as possible. However, from an economic point of view, recycling waste materials can be challenging.

[0002] In order to maximize recycling efficiency, it is desirable for large-scale production facilities to be able to process feedstocks with recycled content derived from a variety of waste materials. Some recycling efforts involve complex and detailed separation of waste streams, which results in increased costs to obtain a stream of recycled waste content. It is desirable to establish recycled content without having to be sorted into a single type of plastic or waste material, or which can tolerate a variety of impurities in the waste stream.

[0003] In some cases, it may be difficult to dedicate a product with recycled content to a specific customer or downstream synthesis process for use in making derivatives of a product, particularly if the recycled content product is a gas or is difficult to separate. It may be difficult to separate and allocate a dedicated portion of a gas made exclusively from recycled content feedstock because the gas infrastructure is continuous flow and often mixes gas streams from a variety of sources.

[0004] Furthermore, it may be desirable to move away from reliance on natural gas, ethane or propane as the sole source for producing products such as ethylene and propylene and their downstream derivatives.

[0005] It would also be desirable to synthesize compounds such as oxo diols using existing equipment and processes without the need to invest in additional and expensive equipment in order to establish a recovery component in the manufacture of the compounds.

[0006] Oxo glycols, such as 2,2-dimethyl-1,3-propanediol (also known as "neopentyl glycol" or "NPG"), are important products in organic synthesis. Aldehydes formed by hydroformylation of olefins using synthesis gas can be further reacted in the presence of a catalyst and optionally hydrogenated to form oxo glycols. These glycols can be used to synthesize other chemical components, as well as paints, lubricants, coatings, and plasticizers. These glycols are also used as monomers to form polymers such as polyesters, and when used in this way, impart desirable properties to the polymers, such as improved stability and melt characteristics.

[0007] It is desirable to be able to determine the amount and timing of establishing a recycled component in a compound such as oxo diol. In addition, it may be desirable to provide oxo diol with more or less recycled components or no recycled components at certain times or for different batches. This flexibility in the process without the need to add a large amount of assets is desirable. Summary of the invention

[0008] There is now provided a process for obtaining a recycled component oxo diol composition, a process for reacting a recycled component olefin or aldehyde or applying a recycled component value to prepare a recycled component oxo diol, uses thereof, compositions thereof and systems thereof, each as further described in the claims and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 is a schematic diagram of a process for preparing one or more recycled content compositions into an r-composition using a recycled content pyrolysis oil composition (r-pyrolysis oil).

[0010] Figure 2 is a schematic representation of an exemplary pyrolysis system for at least partially converting one or more recycled wastes, particularly recycled plastic wastes, into various useful r-products.

[0011] Figure 3 is a schematic diagram of a pyrolysis process to produce an olefin-containing product.

[0012] Figure 4 is a block flow diagram showing the steps associated with the cracking furnace and separation zone of a system for producing an r-composition obtained from cracking r-pyrolysis oil and non-recovered cracker feed.

[0013] Figure 5 is a schematic diagram of a cracking furnace suitable for receiving r-pyrolysis oil.

[0014] Figure 6 A furnace coil configuration with multiple tubes is shown.

[0015] Figure 7 Various feed positions of r-pyrolysis oil into the cracking furnace are shown.

[0016] Figure 8 A cracking furnace with a vapor liquid separator is shown.

[0017] Fig. 9 is a block diagram showing the process of recovering constituent furnace effluent.

[0018] Fig.10 A fractionation scheme of the separation section is shown, including a demethanizer, a deethanizer, a depropanizer and a fractionation column to separate and isolate the main r-compositions, including r-propylene, r-ethylene, r-butene, etc.

[0019] Fig.11 A laboratory scale cracking unit design is shown.

[0020] Fig.12 Design features of a plant-based trial for feeding r-pyrolysis oil to a gas-fed cracking furnace are described.

[0021] Fig.13 is a boiling point 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.

[0022] Fig.14 is the boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0023] Fig.15 is the boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0024] Fig.16 is a boiling point graph of r-pyrolysis oil distilled in the laboratory and obtained by chromatography.

[0025] Fig.17 is a boiling point graph of laboratory distilled r-pyrolysis oil that boils at least 90% to 350°C, 50% between 90°C and 200°C, and at least 10% to 60°C.

[0026] Fig.18 is a boiling point graph of laboratory distilled r-pyrolysis oil that boils at least 90% to 150°C, 50% between 80°C and 145°C, and at least 10% to 60°C.

[0027] Fig.19 is a boiling point graph of r-pyrolysis oil distilled in the laboratory that boils at least 90% to 350°C, at least 10% to 150°C, and 50% between 220°C and 280°C.

[0028] Fig. 20 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with 90% boiling between 250-300°C.

[0029] Fig.21 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with 50% boiling between 60-80°C.

[0030] Fig. 22 is a boiling point graph of a laboratory distilled r-pyrolysis oil having a 34.7% aromatic content.

[0031] Fig.23 is a boiling point graph of r-pyrolysis oil, where the initial boiling point is about 40°C.

[0032] Fig.24 is a graph of the carbon distribution of the pyrolysis oil used in the plant trials.

[0033] Fig.25 is a graph of the carbon distribution of the pyrolysis oil used in the plant trials.

[0034] Fig.26 is a schematic diagram of a system suitable for forming recycled component neopentyl glycol (r-NPG). DETAILED DESCRIPTION

[0035] The words "containing" and "including" are synonymous with comprising. When indicating a numerical sequence, it should be understood that each number is modified to be the same as the first or last number in the numerical sequence or sentence, for example, each number is "at least" or "up to" or "not more than" as the case may be; and each number is in an "or" relationship. For example, "at least 10, 20, 30, 40, 50, 75wt%..." means the same as "at least 10wt%, or at least 20wt%, or at least 30wt%, or at least 40wt%, or at least 50wt%, or at least 75wt%", etc.; and "not more than 90wt%, 85, 70, 60..." means the same as "not more than 90wt%, or not more than 85wt%, or not more than 70wt%", etc.; and "at least 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by weight..." means the same as "to "at least 1wt%, or at least 2wt%, or at least 3wt%..." and the like are the same; and "at least 5, 10, 15, 20 and / or no more than 99, 95, 90 weight percent" means the same as "at least 5wt%, or at least 10wt%, or at least 15wt%, or at least 20wt%, and / or no more than 99wt%, or no more than 95wt%, or no more than 90 weight percent..." and the like; 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..." and the like.

[0036] In some aspects, a process for preparing recovered oxo diol ("r-OG") is provided, the process beginning with feeding a recovered component olefin composition to a reactor, at least a portion of which is derived directly or indirectly from pyrolysis recovery waste, reacting the olefins with synthesis gas to produce recovered component aldehydes ("r-AD"), and then reacting at least a portion of the r-AD in the presence of a catalyst (optionally subjecting the r-AD to catalytic hydrogenation) to provide an effluent comprising r-oxo diol.

[0037] Pyrolysis / cracking systems and methods

[0038] Unless otherwise indicated, 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 that does not contain r-pyrolysis oil. The hydrocarbon mass flow rates, MF1 and MF2, are in thousands of pounds per hour (klb / hr) unless otherwise indicated as molar flow rates.

[0039] As used herein, "including" and "comprising" are open ended and synonymous with "comprising."

[0040] The term "recycled content" is used herein as a noun to i) refer to a physical component (e.g., a compound, molecule, or atom), at least a portion of which is derived directly or indirectly from recycled waste, or ii) as an adjective modifying a specific composition (e.g., a compound, polymer, feedstock, product, or stream), at least a portion of which is derived directly or indirectly from recycled waste.

[0041] As used herein, "recycled content composition," "recycled composition," and "r-composition" refer to a composition having recycled content.

[0042] The term "pyrolysis recovery component" is used herein as a noun, i) to refer to a physical component (e.g., a compound, molecule, or atom) at least a portion of which is derived directly or indirectly from the pyrolysis of recovery waste, or ii) as an adjective modifying a specific composition (e.g., a feedstock, a product, or a stream) at least a portion of which is derived directly or indirectly from the pyrolysis of recovery waste. For example, the pyrolysis recovery component can be derived directly or indirectly from the cracking of the recovery component pyrolysis oil, the recovery component pyrolysis gas, or the recovery component pyrolysis oil, such as by a thermal steam cracker or a fluid catalytic cracker.

[0043] As used herein, "pyrolysis recycled content composition", "pyrolysis recycled composition" and "pr-composition" refer to a composition (e.g., compound, polymer, feedstock, product or stream) having pyrolysis recycled content. The pr-composition is a subset of the r-composition, wherein at least a portion of the recycled content of the r-composition is derived directly or indirectly from the pyrolysis of recycled waste.

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

[0045] 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 recycled waste has at least one physical component traceable to the pyrolysis of recycled waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from the pyrolysis of recycled waste has a recycled component quota associated therewith and may or may not contain a physical component traceable to the pyrolysis of recycled waste.

[0046] 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.

[0047] As used herein, "recovered content pyrolysis oil," "recovered pyrolysis oil," "pyrolysis recovered content pyrolysis oil," and "r-pyrolysis oil" refer to a pyrolysis oil at least a portion of which is obtained from pyrolysis and has a recovered content.

[0048] As used herein, "pyrolysis gas" and "pygas" refer to a composition of matter that is a gas when measured at 25°C and 1 atm and at least a portion of which is obtained from pyrolysis.

[0049] As used herein, "recycled content pyrolysis gas," "recycled pyrolysis gas," "pyrolysis content pyrolysis gas," and "r-pyrolysis gas" refer to pyrolysis gas that is at least partially obtained from pyrolysis and has recycled content.

[0050] As used herein, "Et" is an ethylene composition (eg, feedstock, product, or stream) and "Pr" is a propylene composition (eg, feedstock, product, or stream).

[0051] As used herein, "recycled content ethylene", "r-ethylene" and "r-Et" refer to Et with recycled content; "recycled content propylene", "r-propylene" and "r-Pr" refer to Pr with recycled content.

[0052] As used herein, "pyrolysis recovered ethylene" and "pr-Et" refer to r-Et with pyrolysis recovered components; "pyrolysis recovered propylene" and "pr-Pr" refer to r-Pr with pyrolysis recovered components.

[0053] As used herein, "AD" is an aldehyde composition (eg, feedstock, product, or stream).

[0054] As used herein, "recovered content aldehyde" and "r-AD" refer to AD having a recovered content.

[0055] As used herein, "pyrolysis component aldehyde" and "pr-AD" refer to r-AD having a pyrolysis recovered component.

[0056] As used herein, "OG" is an oxo diol composition, such as neopentyl glycol (eg, feedstock, product, or stream).

[0057] As used herein, "recycled content OG" and "r-OG" refer to OG having recycled content.

[0058] As used herein, "pyrolyzed component OG" and "pr-OG" refer to r-OG having a pyrolysis-recovered component.

[0059] As used throughout, the "generic" description of a compound, composition, or stream does not require the presence of its "species", but does not exclude and may include its "species". For example, "OG" or "any OG" may include oxodiols prepared by any method, and may or may not include recycled components, and may or may not be prepared from non-recycled component raw materials or from recycled component raw materials, and may or may not include r-OG or pr-OG. Similarly, r-OG may include or may not include pr-OG, although reference to r-OG does require it to have recycled components. In another example, "Et" or "any Et" may 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 include or may not include pr-Et, although reference to r-Et does require it to have recycled components. This will apply to Pr, r-Pr, and Pr-Pr in a similar manner.

[0060] "Pyrolysis recovered content" is a specific subset / type (species) of "recovered content" (genus). Wherever "recovered content" and "r-" are used herein, such use should be interpreted as explicitly disclosing and providing claim support for "pyrolysis recovered content" and "pr-", even if not explicitly stated as such. For example, whenever the term "recovered content oxo diol" or "r-OG" is used herein, it should be interpreted as also explicitly disclosing and providing claim support for "pyrolysis recovered content oxo diol" and "pr-OG".

[0061] As used throughout, whenever reference is made to cracking of r-pyrolysis oil, such cracking may be carried out by a thermal cracker or a thermal steam cracker in a liquid feed furnace or in a gas feed furnace or in any cracking process. In one embodiment or in combination with any of the embodiments mentioned, the cracking is not catalytic or is carried out in the absence of an added catalyst, or is not a fluid catalytic cracking process.

[0062] As used throughout, whenever reference is made to pyrolysis to recover waste or r-pyrolysis oil, all embodiments also include: (i) the option of cracking the effluent of the pyrolysis to recover the waste or cracking the r-pyrolysis oil and / or (ii) the option of using the cracked effluent or r-pyrolysis oil as feed to a gas feed furnace or tubes of a gas furnace / cracker.

[0063] As used throughout, a "family of entities" means at least one person or entity that directly or indirectly controls, is controlled by, or is under common control with another person or entity, where control means ownership of at least 50% of the voting stock, or shared management, common use of facilities, equipment, and employees, or family interests. As used throughout, references to persons or entities provide claim support to, and include, any person or entity in the family of entities.

[0064] In one embodiment or in combination with any other mentioned embodiment, reference to r-olefins (e.g., r-Et or r-Pr) also includes: pr-Et or pr-Pr, or pr-Et or pr-Pr obtained directly or indirectly from the cracking of r-pyrolysis oil or from r-pyrolysis gas; and r-OG also includes: pr-OG, or pr-OG obtained directly or indirectly from the cracking of r-pyrolysis oil or from r-pyrolysis gas.

[0065] In one embodiment or in combination with any of the embodiments mentioned, a method for preparing an r-OG composition by reacting AD (e.g., an AD composition) with hydrogen is provided. AD can be r-AD or pr-AD or dr-AD. In one embodiment, the method for preparing r-OG starts with feeding r-AD to a reactor for preparing OG. In an embodiment, the AD composition can be prepared by reacting synthesis gas (CO and hydrogen) with an olefin (e.g., Et or Pr). The olefin can be an r-olefin or a pr-olefin or a dr-olefin. In one embodiment, AD is r-AD prepared by feeding an r-olefin (e.g., r-Et or r-Pr) to a reactor for preparing AD.

[0066] Figure 1 is a schematic diagram illustrating an embodiment of a process for preparing one or more recycled component compositions (e.g., ethylene, propylene, butadiene, hydrogen and / or pyrolysis gasoline) (r-composition) using a recycled component pyrolysis oil composition (r-pyrolysis oil) or in combination with any embodiment mentioned herein.

[0067] like Figure 1 As shown in , the recycled waste can be subjected to pyrolysis in a pyrolysis unit 10 to produce a pyrolysis product / effluent containing a recycled component pyrolysis oil composition (r-pyrolysis oil). The r-pyrolysis oil can be fed to a cracker 20 together with a non-recycled cracker feed (e.g., propane, ethane and / or natural gasoline). A recycled component cracking effluent (r-cracked effluent) can be produced from the cracker and then separated in a separation train 30. In one embodiment, or in combination with any of the embodiments mentioned herein, the r-composition can be separated and recovered from the r-cracked effluent. The r-propylene stream can contain primarily propylene, while the r-ethylene stream can contain primarily ethylene.

[0068] As used herein, a furnace includes a convection zone and a radiant zone. The convection zone includes tubes and / or coils inside the convection box, which may also continue outside the convection box downstream of the coil inlet at the inlet of the convection box. For example, Figure 5 As shown, the convection zone 310 includes coils and tubes within the convection box 312, and may optionally extend outside the convection box 312 or interconnect with a duct 314 outside the convection box 312 and return to the convection box 312. The radiant zone 320 includes radiant coils / tubes 324 and a burner 326. The convection zone 310 and the radiant zone 320 may 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 shown in FIG. Figure 5 As shown, the convection box 312 is integrated with the combustion chamber 322 .

[0069] Unless otherwise indicated, all component amounts provided herein (eg, for feeds, materials, streams, compositions, and products) are expressed on a dry basis.

[0070] As used herein, "r-pyoil" or "r-pyrolysis oil" are interchangeable and refer to a composition of matter that is liquid when measured at 25°C and 1 atmosphere, at least a portion of which is obtained from pyrolysis, and which has recycled content. In embodiments, at least a portion of the composition is obtained from pyrolysis of recycled waste (e.g., waste plastic or waste streams).

[0071] In an embodiment, "r-ethylene" can be a composition comprising: (a) ethylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) ethylene having a recovery content value derived from at least a portion of the ethylene; "r-propylene" can be a composition comprising (a) propylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) propylene having a recovery content value or quota applied to at least a portion of the propylene.

[0072] References to "r-ethylene molecules" are to ethylene molecules that are derived directly or indirectly from recycled waste, and references to "pr-ethylene molecules" are to ethylene molecules that are derived directly or indirectly from r-pyrolysis effluents (e.g., r-pyrolysis oil and / or r-pyrolysis gas).

[0073] As used herein, "Site" means the largest contiguous geographic boundary owned by an OG manufacturer, or by an individual or entity within its family of entities, or a combination of individuals or entities, wherein the geographic boundary contains one or more manufacturing facilities, at least one of which is an OG manufacturing facility.

[0074] As used herein, the term "predominantly" means greater than 50 wt%, unless expressed as a mole percent, in which case it means greater than 50 mol%. For example, a stream, composition, feedstock, or product that is primarily propane is a stream, composition, feedstock, or product that contains greater than 50 wt% propane, or if expressed as a mol%, refers to a product that contains greater than 50 mol% propane.

[0075] As used herein, a composition "directly derived from" cracked r-pyrolysis oil has at least one physical component traceable to an r-composition at least a portion of which was obtained by or in conjunction with cracked r-pyrolysis oil, while a composition "indirectly derived from" cracked r-pyrolysis oil has a recovered ingredient quota associated therewith and may or may not contain physical components traceable to an r-composition at least a portion of which was obtained by or in conjunction with cracked r-pyrolysis oil.

[0076] As used herein, "recycled content value" and "r-value" are units of measurement that represent the amount of material that is derived from recycled waste. The r-value can be derived from any type of recycled waste processed in any type of process.

[0077] As used herein, the terms "pyrolysis recovery content value" and "pr-value" refer to a unit of measurement representing the amount of material derived 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 includes but does not require a pr-value.

[0078] The specific recovery component value (r-value or pr-value) can be represented by mass or percentage or any other measurement unit, and can be determined according to the standard system for tracking, distributing and / or crediting recovery components between various compositions. The recovery component value can be deducted from the recovery component inventory and applied to the product or composition, so that the recovery component is attributed to the product or composition. Unless otherwise specified, the recovery component value is not necessarily derived from manufacturing or cracking r-pyrolysis oil. In one embodiment or in combination with any mentioned embodiment, at least a portion of the r-pyrolysis oil from which a quota is obtained is also cracked in the cracking furnace as described in one or more embodiments throughout this paper.

[0079] In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the recycled content quota or quota or recycled content value deposited into the recycled content 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 are obtained from r-pyrolysis oil:

[0080] a. Quota, or

[0081] b. The amount of recycled content deposited, or

[0082] c. The recycled content value in the recycled content inventory, or

[0083] d. The recycled content value applied to a composition to make a recycled content product, intermediate or article (recycled PIA).

[0084] A recycled PIA is a product, intermediate or article that may include a compound with an associated recycled component value, or a composition containing a compound or polymer, and / or an article. A PIA does not have a recycled component value associated with it. PIAs include, but are not limited to, aldehydes, or OGs such as neopentyl glycol.

[0085] As used herein, "recycle content allotment" or "quota" refers to the following recycled content value:

[0086] a. from an original composition (e.g., a compound, polymer, feedstock, product, or stream) that is at least partially derived from recycled waste, or has recycled content value (at least a portion of which is derived from recycled waste, optionally from r-pyrolysis oil) to a receiving composition (receiving a quota of a composition (e.g., a compound, polymer, feedstock, product, or stream) that is at least partially derived from recycled waste, or has recycled content value (at least a portion of which is derived from recycled waste, optionally from r-pyrolysis oil), the receiving composition may or may not have a physical component that is traceable to a composition that is at least partially derived from recycled waste; or

[0087] b. Depositing into a recycling stock from a raw composition (e.g., a compound, polymer, feedstock, product, or stream), at least a portion of which is obtained from or has a recycled content value or pr-value, at least a portion of which is derived from recycled waste.

[0088] As used herein, "pyrolysis recovery component quota" and "pyrolysis quota" or "pr-quota" refer to the pyrolysis recovery component value as follows:

[0089] a. From an original composition (e.g., a compound, polymer, feedstock, product, or stream) that is at least partially obtained from the pyrolysis of recycled waste, or has recycled content value (at least a portion of which is derived from the pyrolysis of recycled waste) to a receiving composition (e.g., a compound, polymer, feedstock, product, article, or stream), the original composition being at least partially obtained from the pyrolysis of recycled waste, or having recycled content value (at least a portion of which is derived from the pyrolysis of recycled waste), the receiving composition may or may not have a physical component that is traceable to a composition at least a portion of which is obtained from the pyrolysis of recycled waste; or

[0090] b. Depositing into a recycling stock from a raw composition (e.g., a compound, polymer, feedstock, product, or stream), at least a portion of which was obtained from or has a recycled component value, at least a portion of which is derived from the pyrolysis of recycled waste.

[0091] A pyrolysis recovery component quota is a specific type of recovery component quota associated with the pyrolysis of the recovery waste. Thus, the term recovery component quota includes the pyrolysis recovery component quota.

[0092] In one embodiment or in combination with any of the mentioned embodiments, the pyrolysis recovery component quota or pyrolysis quota may have the following recovery component values:

[0093] a. from an original composition (e.g., a compound, polymer, feedstock, product or stream or PIA) at least a portion of which is obtained from cracking (e.g., liquid or gaseous thermal steam cracking) r-pyrolysis oil, or from recycled waste used to prepare cracked r-pyrolysis oil, or from r-pyrolysis oil that is or will be cracked or has a recycled component value and at least a portion of the recycled component value is derived from cracking (e.g., liquid or gaseous thermal steam cracking), to a receiving composition (e.g., a compound, polymer, feedstock, product or stream or PIA) that may or may not have a physical component that is traceable to a composition at least a portion of which is obtained from cracking r-pyrolysis oil; or

[0094] b. deposited into a recovered content inventory and obtained from a composition (e.g., a compound, polymer, feedstock, product, or stream), at least a portion of which was obtained from or has a recovered content value, at least a portion of which was derived from the cracking (e.g., liquid or gas thermal steam cracking) of an r-pyrolysis oil (regardless of whether the r-pyrolysis oil was cracked at the time the allowance was deposited into the recovered content inventory, provided that the r-pyrolysis oil from which the allowance was withdrawn was ultimately cracked).

[0095] A quota can be an allotment or a credit.

[0096] The recycled content quota can include a recycled content allocation or a recycled content credit obtained through the transfer or use of raw materials. In one embodiment or in combination with any of the mentioned embodiments, the composition receiving the recycled content quota can be a non-recycled composition, thereby converting the non-recycled composition into an r-composition.

[0097] As used herein, "non-recycled" refers to a composition (eg, compound, polymer, feedstock, product, or stream) that is not derived directly or indirectly from recycled waste.

[0098] As used herein, "non-recycled feed" in the context of a feed to a cracker or furnace refers to a feed that is not obtained from a recycled waste stream. Once the non-recycled feed obtains a recycled component quota (e.g., through a recycled component credit or recycled component allocation), the non-recycled feed becomes a recycled component feed, composition, or recycled PIA.

[0099] As used herein, the term "recovery component allocation" refers to a type of recovery component quota, wherein the entity or individual supplying the composition sells or transfers the composition to the receiving individual or entity, and the individual or entity preparing the composition has a quota, at least a portion of which can be related to the composition sold or transferred to the receiving individual or entity by the supplying individual or entity. The supplying entity or individual can be controlled by the same entity or individual (one or more), or by a family of entities, or by different families of entities. In an embodiment, the recovery component allocation travels with the composition and the downstream derivatives of the composition. In an embodiment, the allocation can be deposited in the recovery component stock, and taken out from the recovery component stock as the allocation, and applied to the composition to prepare the r-composition or recycle PIA.

[0100] As used herein, "recovered content credit" and "credit" refer to a type of recovered content quota in which the quota is not limited to being associated with compositions made from cracked r-pyrolysis oil or its downstream derivatives, but rather has the flexibility to be obtained from r-pyrolysis oil and (i) applied to compositions or PIAs made from processes other than cracking feedstocks in a furnace, or (ii) applied to downstream derivatives of compositions made from processes other than cracking feedstocks in a furnace through one or more intermediate feedstocks, or (iii) can be sold or transferred to a person or entity other than the quota owner, or (iv) can be sold or transferred by a person other than the supplier of the composition transferred to the receiving entity or person. For example, a quota can be a credit when it is taken from r-pyrolysis oil and applied by the quota owner to a BTX composition or fraction thereof that is manufactured by the owner or within its family of entities and is obtained through the refining and fractionation of petroleum rather than through cracker effluent products; or it can be a credit 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 components of the third party.

[0101] The Credit may be sold or transferred or used, or may be sold or transferred or used, in any of the following ways:

[0102] a. There is no sale of the composition, or

[0103] b. There is a sale or transfer of the Composition, but the Quota is not linked to the sale or transfer of the Composition, or

[0104] c. is deposited into or withdrawn from a recycled content stock that does not track molecules of recycled content raw materials to molecules of a resulting composition (made with the recycled content raw materials), or the recycled content stock has such tracking capabilities, but the recycled content stock does not track a specific quota such as applied to the composition.

[0105] In one embodiment or in combination with any of the embodiments mentioned, a quota may be deposited into a recycled content inventory and a credit or allocation may be extracted from the inventory and applied to a composition. This would be the case where a first composition is prepared by pyrolysis of recycled waste, or by cracking of r-pyrolysis oil or r-pyrolysis oil, or by any other method of preparing the first composition from recycled waste, an allocation associated with such a first composition is deposited into a recycled content inventory and the recycled content value is deducted from the recycled content 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 feedstock, to generate a quota. In this system, there is no need to trace back to the cracking of pyrolysis oil or to the source of reactants for any atom contained in the olefin-containing effluent, but rather any reactant prepared by any method may be used and a recycled content allocation associated with such reactant may be associated.

[0106] In one embodiment or in combination with any of the mentioned embodiments, the composition of the receiving quota is used as a feedstock to prepare a downstream derivative of the composition, and such composition is a product of cracking a cracker feedstock in a cracking furnace. In one embodiment or in combination with any of the mentioned embodiments, a process is provided, wherein:

[0107] a. Obtaining r-pyrolysis oil,

[0108] b. The recovered content value (or quota) is obtained from the r-pyrolysis oil, and

[0109] i. is deposited into the recycled content stock, a quota (or credit) is taken from the recycled content stock and applied to any composition to obtain an r-composition, or

[0110] ii. directly applied to any composition without being deposited into the recycled content stock to obtain an r-composition; and

[0111] c. cracking at least a portion of the r-pyrolysis oil in a cracking furnace, optionally according to any of the designs or processes described herein; and

[0112] d. Optionally, at least a portion of the composition in step b originates from cracking of a cracker feed in a cracking furnace, optionally the composition has been obtained by any of the feedstocks comprising r-pyrolysis oil and the methods described herein.

[0113] Steps b. and c. do not have to occur at the same time. 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 a period of time between the time an entity or person receives the r-pyrolysis oil and generates a quota (which may occur upon receipt or possession of the r-pyrolysis oil or deposit into inventory) and the actual processing of the r-pyrolysis oil in the cracking furnace.

[0114] As used herein, "recycle content inventory" and "inventory" mean a group or collection of quotas (allotments or credits) from which the deposits and deductions of quotas under any unit can be tracked. The inventory can be in any form (electronic or paper), using any one or more software programs, or using various modules or applications (which track deposits and deductions together as a whole). Desirably, the total amount of recycled content removed (or applied to the composition) does not exceed the total amount of recycled content quotas deposited in the recycled content inventory (from any source, not only from the cracking of r-pyrolysis oil). However, if a deficit in recycled content value is achieved, the recycled content inventory is rebalanced to achieve zero or positive available recycled content value. The timing of rebalancing can be determined and managed according to the rules of a specific certification system adopted by the olefin-containing effluent manufacturer or a member of its family of entities, or alternatively, rebalanced within one (1) year, or six (6) months, or three (3) months, or one (1) month of achieving a deficit. The timing of depositing the quota into the recycling component inventory, applying the quota (or credit) to the composition to prepare the r-composition and cracking the r-pyrolysis oil need not be simultaneous or in any particular order. In one embodiment or in combination with any of the mentioned embodiments, the step of cracking a specific volume of r-pyrolysis oil occurs after the recycling component value or quota from the volume of r-pyrolysis oil is deposited into the recycling component inventory. In addition, the quota or recycling component value taken out from the recycling component inventory does not need to be traceable to r-pyrolysis oil or cracked r-pyrolysis oil, but can be obtained from any waste recycling stream and any method for processing the recycling waste stream. Desirably, at least a portion of the recycling component value in the recycling component 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, optionally, at least a portion of the volume of r-pyrolysis oil (the recycling component value from this volume is deposited into the recycling component inventory) is also processed by any one or more of the cracking processes described herein.

[0115] Determining whether an r-composition is directly or indirectly derived from recycled waste is not based on the presence or absence of intermediate steps or entities in the supply chain, but rather on whether at least a portion of the r-composition (fed to a reactor used to make a final product such as AD or OG) can be traced back to an r-composition prepared from recycled waste.

[0116] The determination of 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 or absence of intermediate steps or entities in the supply chain, but rather on whether at least a portion of the pr-composition fed to the reactor used to prepare the final product, such as OG, can be traced back to a pr-composition prepared from the pyrolysis of recycled waste.

[0117] As described above, a final product is considered to be directly derived from cracked r-pyrolysis oil or from recycled waste if at least a portion of the reactant feedstock (which is used to prepare the product) can be traced back to at least a portion of the atoms or molecules constituting the r-composition (which is produced from recycled waste, or from the cracking of r-pyrolysis oil fed to a cracking furnace, or as an effluent from a cracking furnace), optionally via one or more intermediate steps or entities.

[0118] The r-composition as an effluent may be in a crude form that requires refining to isolate a specific r-composition. The r-composition manufacturer may sell such r-composition to an intermediate entity, typically after refining and / or purifying and compressing to produce a desired grade of a specific r-composition, which then sells the r-composition or one or more derivatives thereof to another intermediate entity that prepares an intermediate product, or directly to a product manufacturer. Any number of intermediates and intermediate derivatives may be prepared before the final product is prepared.

[0119] The actual volume of r-composition, whether condensed as a liquid, supercritical or stored as a gas, may remain in the facility where it was prepared, or may be transported to a different location, or - prior to use by an intermediary or product manufacturer - held in an off-site storage facility. For tracking purposes, once an r-composition made 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 is mixed with non-recycled ethylene), for example in a storage tank, salt dome or cavern, then the entire tank, dome or cavern becomes a source of r-composition, and for tracking purposes, withdrawals from such storage facilities are withdrawals from a source of r-composition until such time as the entire volume or inventory of the storage facility is turned over, or withdrawn, and / or replaced with non-recycled composition after the feeding of r-composition to the tank is stopped. Likewise, this also applies to any downstream storage facility used to store derivatives of r-composition (e.g., r-Et or r-Pr and pr-Et or pr-Pr compositions).

[0120] An r-composition is considered to be indirectly derived from recycled waste or pyrolysis of recycled waste or cracking of r-pyrolysis oil if the r-composition is associated with a recycled content quota and may or may not contain physical components that are traceable to the r-composition (where at least a portion of the r-composition is obtained from recycled waste / pyrolysis of recycled waste / 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 through a system of credits such as credits that are transferred to the product manufacturer regardless of where or from whom the r-composition, or derivatives thereof, or reactant feedstocks for making the product is purchased or transferred, or (ii) a supplier of the r-composition or derivatives thereof ("supplier") operates within a quota framework that allows a recycled content value or pr-value to be associated or applied to a portion or all of an olefin-containing effluent, or compounds in an olefin-containing effluent, or derivatives thereof, to produce the r-composition, and allows the transfer of the recycled content value or quota to the product manufacturer or any intermediary that obtains a supply of the r-composition from the supplier. In this system, there is no need to trace the source of the olefin volume back to the manufacturer of the r-composition (recycled waste from pyrolysis), but any olefin composition produced by any process can be used and a recovery component quota can be associated with the olefin composition, or r-AD or r-OG does not need to trace the source of the r-olefin or r-AD or r-OG feedstock to the composition obtained from cracked r-pyrolysis oil or pyrolysis recycled waste, respectively, but any olefin (ethylene or propylene) or AD obtained from any source can be used as a feedstock to produce AD ​​or OG, respectively, and a recovery component quota can be associated with such AD or OG to produce r-AD or r-OG.

[0121] Examples of how olefin compositions used to make AD (and ultimately OG) can be recycled include:

[0122] (i) a cracking facility in which the r-olefins (e.g., r-ethylene) produced in the facility (by cracking r-pyrolysis oil or obtained from r-pyrolysis gas) can be in fluid communication with an olefin-derived petrochemical (e.g., AD or OG) forming facility (which can be a storage vessel to the olefin-derived petrochemical facility, or directly to an olefin-derived petrochemical forming reactor) through interconnected pipelines, optionally through one or more storage vessels and valves or interlocks, continuously or intermittently and directly or indirectly through intermediate facilities, and the r-olefin (e.g., r-ethylene) feedstock is withdrawn through the interconnected pipelines at both:

[0123] a. withdrawn from a cracker facility during the production of the r-olefin or thereafter at the time when the r-olefin (e.g., r-ethylene) is piped to an olefin-derived petrochemical product (e.g., AD or OG) forming facility, or

[0124] b. withdrawn from one or more storage tanks at any time, provided that at least one storage tank is fed with r-olefins (e.g., r-ethylene), and for a long period of time, until the entire volume of the one or more storage tanks is replaced by a feed that does not contain r-olefins (e.g., r-ethylene); or

[0125] (ii) delivering the olefin (e.g., ethylene) from a storage vessel, vault, or facility containing or being fed with the r-olefin (e.g., r-ethylene) either in an isotainer by truck or rail or ship or by means other than pipeline until the entire volume of the vessel, vault, or facility has been replaced by olefin feedstock that does not contain the r-olefin (e.g., r-ethylene); or

[0126] (iii) a manufacturer of an olefin-derived petrochemical product (e.g., AD or OG) certifies, represents, or advertises to its consumers or the public that its olefin-derived petrochemical product contains recycled content or is derived from a feedstock containing or obtained from recycled content, where such recycled content is claimed to be based in whole or in part on the acquisition of r-olefins (e.g., an ethylene feedstock associated with an allotted amount of ethylene (produced from cracked r-pyrolysis oil or obtained from r-pyrolysis gas)); or

[0127] (iv) Manufacturers of olefin-derived petrochemicals (e.g. AD or OG) have obtained:

[0128] a. Amount of olefins (e.g., ethylene or propylene) produced from r-pyrolysis oil - as certified, represented, or advertised, or

[0129] b. has transferred credits or allocations to manufacturers of olefin-derived petrochemical products (e.g., AD or OG) in conjunction with the supply of olefins that are sufficient to allow the manufacturer of the olefin-derived petrochemical product (e.g., AD or OG) to meet the certification requirements or make representations or advertisements thereof, or

[0130] c. Olefins having an associated recovery content value, wherein such recovery content value is olefins obtained from r-pyrolysis oil or cracked r-pyrolysis oil, or obtained from cracked r-pyrolysis oil, or obtained from r-pyrolysis gas by one or more entities independent of middlemen.

[0131] As discussed above, the recycled content can be a pyrolysis recycled content that is derived directly or indirectly from the pyrolysis of recycled waste (e.g., from cracking r-pyrolysis oil or from r-pyrolysis gas).

[0132] In one embodiment or in combination with any of the embodiments mentioned, the input or generation of the recycled component (recycled component raw material or quota) can be to or at a first site, and the recycled component value from the input is transferred to a second site and applied to one or more compositions prepared at the second site. The recycled component value can be applied to the composition symmetrically or asymmetrically at the second site. The recycled component value of "derived from cracked r-pyrolysis oil" or "obtained from cracked r-pyrolysis oil" or the recycled component value derived from cracked r-pyrolysis oil directly or indirectly does not imply the timing of when the recycled component value or quota is taken, captured, deposited in the recycled component inventory or transferred. The timing of depositing the quota or recycled component value in the recycled component inventory or realizing, identifying, capturing or transferring it is flexible and can occur as early as the following timing: receiving r-pyrolysis oil to a site within the entity family that owns it, processing r-pyrolysis oil, or moving r-pyrolysis oil to inventory by an entity or individual, or moving r-pyrolysis oil within the entity family that owns or operates a cracking facility. Thus, a quota or recovered component value on a volume of r-pyrolysis oil may be obtained, captured, deposited into inventory or transferred to a product without the volume being fed to a cracking furnace and cracked. The quota may also be obtained during the feeding of r-pyrolysis oil to a cracker, during cracking or when preparing an r-composition. When r-pyrolysis oil is owned, possessed or received and deposited into a recovered component inventory, the quota taken is a quota associated with, obtained from or derived from cracked r-pyrolysis oil, even if the r-pyrolysis oil has not been cracked when the quota is taken or deposited, provided that the r-pyrolysis oil is cracked at some point in the future.

[0133] In one embodiment or in combination with any of the mentioned embodiments, the olefin-containing effluent manufacturer generates a quota from r-pyrolysis oil, and:

[0134] a. applying the quota to any PIA made directly or indirectly (e.g. via a reaction scheme with several intermediates) from cracked r-pyrolysis oil; or

[0135] b. applying the quota to any PIA not produced directly or indirectly from cracked r-pyrolysis oil, such as where the PIA has already been produced and stored in a stockpile or is produced in the future; or

[0136] c. is deposited into the stock, deducting from the stock any quotas applied to the PIA; and the quotas deposited may or may not be associated with a specific quota applied to the PIA; or

[0137] d. is deposited into inventory and stored for later use.

[0138] In one embodiment or in combination with any of the embodiments mentioned, the recycled content information about the recycled PIA can be communicated to a third party, wherein such recycled content information is based on or derived from at least a portion of the allocated amount or credit. The third party can be a customer of an olefin-containing effluent manufacturer or a recycled PIA manufacturer, or can be any other individual or entity or government organization except an entity that owns any of them. The transmission can be electronic, by document, by advertisement or any other communication means.

[0139] In one embodiment or in combination with any of the mentioned embodiments, there is provided a system or package comprising:

[0140] a. Reclaim PIA, and

[0141] b. an identifier, such as a credit, label or certificate associated with said PIA, wherein the identifier is an indication that the PIA has or is derived from recycled content (it does not necessarily identify the source of the recycled content or allowance),

[0142] Provided that the recovered PIA thus produced has a quota, or is produced from the reactants, at least in part, associated with the r-pyrolysis oil.

[0143] As used throughout, the step of deducting quota from the inventory of recycled components does not need to be applied to the recycled PIA product. Deduction does not mean that the quantity disappears or is removed from the inventory log. Deduction can be an adjustment entry, a take-out, an addition as a debit entry, or any other algorithm, which is based on the amount of recycled components associated with the product and one or the accumulated deposit quota amount in the inventory to adjust input and output. For example, 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 that automates deductions and entries / additions and / or applies or is assigned to a product information board. The step of applying quota to PIA (wherein such quota is deducted from the inventory) does not need to physically apply quota to the recycled PIA product or to any document issued in association with the recycled PIA product sold. For example, a recycled PIA manufacturer can ship recycled PIA products to customers, and satisfy the "application" of quota to recycled PIA products by transmitting recycled component credits electronically to customers.

[0144] Also provided is a use of r-pyrolysis oil, the use comprising converting the r-pyrolysis oil in a gas cracking furnace to produce an olefin-containing effluent. Also provided is a use of r-pyrolysis oil, comprising converting reactants in a synthesis process to produce PIA, and applying at least a portion of a quota to the PIA, wherein the quota is associated with the r-pyrolysis oil or its source is a quota stock, wherein at least one credit into the stock is associated with the r-pyrolysis oil.

[0145] In one embodiment or in combination with any of the mentioned embodiments, there is also provided a recovered PIA obtained by any of the methods described above.

[0146] In one embodiment, the process for preparing the recycled PIA can be an integrated process. One such example is a process for preparing the recycled PIA by the following steps:

[0147] a. cracking r-pyrolysis oil to produce an olefin-containing effluent; and

[0148] b. separating the compounds in the olefin-containing effluent to obtain separated compounds; and

[0149] c. reacting any reactants in a synthesis process to prepare PIA;

[0150] d. depositing the quota into the quota stock, the quota being derived from r-pyrolysis oil; and

[0151] e. Apply any allowance from the stock to the PIA, thereby obtaining a recycled PIA.

[0152] In one embodiment or in combination with any of the embodiments mentioned, two or more facilities can be integrated and prepared to recover PIA. The facilities for preparing recovered PIA or olefin-containing effluents can be independent facilities or facilities integrated with each other. For example, a system for producing and consuming reactants can be established as follows:

[0153] a. providing an olefin-containing effluent manufacturing facility configured to produce reactants;

[0154] b. providing a PIA manufacturing facility having a reactor configured to receive reactants from the olefin-containing effluent manufacturing facility; and

[0155] c. a supply system providing fluid communication between the two facilities and capable of supplying reactants from the olefin-containing effluent production facility to the PIA production facility,

[0156] Where the olefins-containing effluent manufacturing facility generates the quota or participates in a process that generates the quota and cracks r-pyrolysis oil, and:

[0157] (i) applying the share to the reactants or to the PIA, or

[0158] (ii) depositing the quota into a quota stock and optionally withdrawing a share from the stock and applying it to the reactants or to the PIA.

[0159] A recovered PIA manufacturing facility may prepare recovered PIA by accepting any reactants from an olefin-containing effluent manufacturing facility and applying the recovered components to the recovered PIA made from the reactants by deducting allowances from their inventory and applying them to the PIA.

[0160] In one embodiment or in combination with any of the mentioned embodiments, there is also provided a system for producing recycled PIA as follows:

[0161] a. providing an olefin-containing effluent manufacturing facility configured to produce an output composition comprising an olefin-containing effluent;

[0162] b. providing a reactant manufacturing facility configured to receive the compound separated from the olefin-containing effluent and to produce one or more downstream products of the compound through a reaction scheme to produce an output composition comprising the reactant;

[0163] c. providing a PIA manufacturing facility having a reactor configured to receive reactants and produce an output composition comprising PIA;

[0164] d. A supply system providing fluid communication between at least two of these facilities and capable of supplying the output composition of one manufacturing facility to another one or more of said manufacturing facilities.

[0165] A PIA manufacturing facility can prepare recycled PIA. In this system, an olefin-containing effluent manufacturing facility can have its output fluidly connected to a reactant composition manufacturing facility, and conversely, a reactant compound or composition manufacturing facility can have its output fluidly connected to a PIA manufacturing facility. Alternatively, the manufacturing facilities of a) and b) can be fluidly connected separately, or only b) and c) can be fluidly connected. In the latter case, the PIA manufacturing facility can prepare recycled PIA by deducting quotas from the inventory of recycled components and applying them to PIA. The quotas obtained and stored in the inventory can be obtained by any of the methods described above,

[0166] Fluid communication can be gaseous or liquid or both. Fluid communication does not need to be continuous, and can be interrupted by storage tank, valve or other purification or treatment facilities, as long as fluid can be transported to subsequent facilities from manufacturing facilities by interconnected pipeline network and do not use truck, train, ship or airplane. In addition, facilities can share the same site, or in other words, a site can include two or more facilities. In addition, facilities can also share storage tank sites or storage tanks for auxiliary chemicals, or can also share utilities, steam or other heat sources, etc., but because their unit operations are separated, they are also considered to be discrete facilities. Facilities are usually defined by device boundary line (battery limit).

[0167] In one embodiment or in combination with any of the mentioned embodiments, the integrated process comprises at least two facilities co-located within 5 miles, or within 3 miles, or within 2 miles, or within 1 mile of each other (as a straight line measurement). In one embodiment or in combination with any of the mentioned embodiments, at least two facilities are owned by the same family of entities.

[0168] A ring manufacturing process is also provided, the process comprising:

[0169] 1. Provide r-pyrolysis oil, and

[0170] 2. cracking the r-pyrolysis oil to produce an olefin-containing effluent, and

[0171] (i) reacting compounds separated from the olefin-containing effluent to produce recovered PIA, or

[0172] (ii) combining a recovery component quota obtained from said r-pyrolysis oil with PIA prepared from compounds separated from a non-recovered olefin-containing effluent to produce a recovered PIA; and

[0173] 3. Removing at least a portion of any of the recycled PIA or any other product, compound or polymer produced from the recycled PIA as a feedstock to produce the r-pyrolysis oil.

[0174] In the process described above, a fully circular or closed loop process is provided, wherein the recovered PIA can be recycled multiple times.

[0175] Examples of articles included in the PIA are fibers, yarns, tows, continuous filaments, staple fibers, rovings, fabrics, textiles, foils, films (eg, polyolefin films), sheets, composite sheets, plastic containers, and consumer articles.

[0176] In one embodiment or in combination with any of the mentioned embodiments, the recovered PIA is of the same family or class of polymers or articles as the polymers or articles used to prepare the r-pyrolysis oil.

[0177] 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). A recycled waste stream is a flow or accumulation of recycled waste from industrial and consumer sources that is at least partially recycled.

[0178] Recycled waste streams include materials, products, and articles (collectively referred to as "materials" when used alone). Recycled waste materials can be solid or liquid. Examples of solid recycled waste streams include plastics, rubber (including tires), textiles, wood, biowaste, modified cellulose, wet laid products, and any other material capable of pyrolysis. Examples of liquid waste streams include industrial sludge, oils (including those derived from plants and petroleum), recovered lubricating oils, or vegetable or animal oils, and any other chemical streams from industrial plants.

[0179] In one embodiment, or in combination with any of the embodiments mentioned, the recycled waste stream that is pyrolyzed comprises a stream that contains at least in part post-industrial material, or post-consumer material, or both post-industrial material and post-consumer material. In one embodiment, or in combination with any of the embodiments mentioned, post-consumer material is material that has been used at least once for its intended application for any duration regardless of wear and tear, or material that has been sold to an end-use consumer, or material that has been discarded into a recycling bin by any person or entity other than the manufacturer or business that manufactures or sells the material.

[0180] In one embodiment, or in combination with any of the embodiments mentioned, post-industrial materials are materials that have been generated and have not yet been used in their intended application, or sold to an end-use customer, or discarded by the manufacturer or any other entity involved in the sale of the material. Examples of post-industrial materials include reprocessing, regrind, waste materials, offcuts, non-specified materials, and finished materials that have been transferred from a manufacturer to any downstream customer (e.g., manufacturer to wholesaler to distributor) but have not yet been used or sold to an end-use customer.

[0181] The form of the recycled waste stream that can be fed to the pyrolysis unit is not limited and can include any form of article, product, material or part thereof. A portion of the article can take the form of a sheet, extruded profile, molded article, film, laminate, foam sheet, fragment, flake, granule, fiber, agglomerate, briquette, powder, fragment, strip, or any shaped piece having various shapes, or any other form other than the original form of the article, and suitable for feeding to the pyrolysis unit.

[0182] In one embodiment, or in combination with any of the embodiments mentioned, the waste material is reduced in size. The reduction can be performed by any means, including shredding, shredding, harrowing, grinding, pulverizing, cutting the material, molding, compressing or dissolving in a solvent.

[0183] The recycled waste plastics can be separated as one type of polymer stream, or can be a stream of mixed recycled waste plastics. Plastics can be any organic synthetic polymer that is solid at 25°C and 1 atm. 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), polyvinyl chloride esters, cellulose and its derivatives (e.g., cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate; regenerated cellulose 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, urea-based polymers, and melamine-containing polymers.

[0184] Suitable recycled waste plastics also include any of those with 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, 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 with 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 pyrolyzed recycled waste stream contains less than 10wt%, or no more than 5wt%, or no more than 3wt%, or no more than 2wt%, or no more than 1wt%, or no more than 0.5wt%, or no more than 0.2wt%, or no more than 0.1wt%, or no more than 0.05wt% of No. 3 plastic (polyvinyl chloride), or alternatively No. 3 and No. 6 plastics, or alternatively No. 3, 6 and No. 7 plastics.

[0185] Examples of recycled rubber include natural and synthetic rubber. The form of the rubber is not limited, including tires.

[0186] Examples of recycled waste wood include softwood and hardwood, chipped wood, pulp or finished products. A large amount of waste wood comes from industry, construction or demolition.

[0187] Examples of recycled biorecycled waste include household biorecycled waste (eg food), green or garden biorecycled waste, and biorecycled waste from the industrial food processing industry.

[0188] Examples of recycled textiles include: natural and / or synthetic fibers, rovings, yarns, nonwoven webs, cloths, fabrics, and products made from or containing any of the above. Textiles can be woven, knitted, knotted, stitched, tufted, pressed together, such as in a felting operation, embroidered, lace, crocheted, braided or nonwoven webs and materials. Textiles include: fabrics and fibers separated from textiles or other products containing fibers, waste materials or substandard fibers or yarns or textiles, or any other loose fiber and yarn sources. Textiles also include: staple fibers, continuous fibers, threads, tows, twisted and / or spun yarns, grey fabrics made from yarns, finished textiles made from wet-processed grey fabrics, and garments made from finished textiles or any other textiles. Textiles include clothing, interior furnishings, and industrial-type textiles.

[0189] 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, cold-weather 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 furniture coverings, carpets and cushions, curtains, bedding such as sheets, pillowcases, duvets, quilts, mattress covers; linens, tablecloths, towels and blankets. Examples of industrial textiles include transportation (car, plane, train, bus) seats, floor mats, trunk liners and headliners; outdoor furniture and cushions, tents, backpacks, luggage, ropes, conveyor belts, calendar roller felts, polishing cloths, rags, soil erosion textiles and geotextiles, agricultural mats and screens, personal protective equipment, bulletproof vests, medical bandages, sutures, tapes, etc.

[0190] The nonwoven web of recovery can also be a dry-laid nonwoven web. The example of suitable products that can be formed by the dry-laid nonwoven web as described herein can include: for personal, consumer, industry, 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 towels and tampons, adult incontinence pads, underwear or underpants and pet training pads. Other examples include a variety of different dry or wet wipes, including those wipes used for consumers (such as personal care or family) and industry (such as food service, health care or professional). Nonwoven webs can also be used as pillows, mattresses and furniture decorations, for the cotton wool of bedding and quilt covers. In the medical and industrial fields, the nonwoven web of the present invention can be used for medical and industrial masks, protective clothing, hats and shoe covers, disposable sheets, surgical gowns, curtains, bandages and medical dressings. In addition, nonwoven webs 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 coverings and sheets. Nonwoven webs can also be used for other consumer end uses, such as packaging, heat insulation or sound insulation and various types of clothing for carpet backing, consumer products, industrial products and agricultural products. Dry-laid nonwoven webs can also be used for a variety of filtering applications, including transportation (for example, automobile or aviation), business, residential, industrial or other professional applications. Example can include filter elements for consumer or industrial air or liquid filters (for example, gasoline, oil, water), including nanofiber webs for microfiltration and end uses such as tea bags, coffee filters and dryer sheets. In addition, nonwoven webs can be used to form a variety of components for automobiles, including but not limited to brake pads, trunk pads, carpet tufting and bottom fillers.

[0191] The recycled textiles may 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 fibers and one type of synthetic fibers, one type of natural fibers and two or more types of synthetic fibers, two or more types of natural fibers and one type of synthetic fibers, and two or more types of natural fibers and two or more types of synthetic fibers.

[0192] Examples of wet-laid products that are recycled include: paperboard, office paper, newsprint and magazines, printing and writing paper, toilet paper, tissue / towel paper, packaging / containerboard, specialty papers, apparel, bleached paperboard, corrugated base, wet-laid molded products, unbleached kraft paper, decorative laminates, bond paper and currency, oversized graphics, specialty products and food and beverage products.

[0193] Examples of modified cellulose include cellulose acetate, cellulose diacetate, cellulose triacetate, regenerated cellulose such as viscose, rayon and Lyocel TM Products in any form, such as tow bands, staple fibers, continuous fibers, films, sheets, molded or stamped products, and contained in or on any articles, such as cigarette filter rods, ophthalmic products, screwdriver handles, optical films and coatings.

[0194] Examples of recycled vegetable or animal oils include oils recycled from animal processing facilities and recycled waste from restaurants.

[0195] The sources of post-consumer or post-industrial recycled waste from which recycling is obtained are not limited and may include recycled waste present in and / or separated from the municipal solid waste stream ("MSW"). For example, the MSW stream may be processed and sorted into a number of discrete components, including textiles, fibers, paper, wood, glass, metals, etc. Other sources of textiles include those obtained by collection agencies, or by textile brand owners or alliances or organizations, or for or on behalf of the above organizations, or by brokers, or from post-industrial sources, such as waste materials 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.

[0196] In one embodiment, or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit may contain 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 weight percent of at least one, or at least two, or at least three, or at least four, or at least five, or at least six different kinds of recycled waste. Reference to "kind" is determined by resin ID code 1-7. In one embodiment, or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit contains less 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 weight percent of polyvinyl chloride and / or polyethylene terephthalate 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.

[0197] Figure 2 An exemplary pyrolysis system 110 is described that 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 2 The pyrolysis system shown in is merely one 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 desirable to effectively and efficiently pyrolyze recycled waste, particularly recycled plastic waste, into a variety of desired end products. Figure 2 An exemplary pyrolysis system is shown in FIG.

[0198] like Figure 2 As 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 source 112 may be, for example, a hopper, a storage bin, a rail car, 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 described herein, the waste plastics supplied by the plastic source 112 may be in the form of solid particles, such as chips, flakes, or powder. Although in Figure 2 Not depicted in the drawings, the pyrolysis system 110 may also include additional sources of other types of recycled waste, which may be used to provide other feed types to the system 110 .

[0199] 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, polyamide, poly(methyl methacrylate), polytetrafluoroethylene, or a combination 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 a combination thereof. As used herein, "post-consumer" refers to non-virgin plastics that have been previously introduced into the consumer market.

[0200] In one embodiment or in combination with any of the embodiments mentioned herein, a feed containing waste plastic can be supplied from a plastic source 112. In one embodiment or in combination with any of the embodiments mentioned herein, the feed containing waste plastic can comprise, consist essentially of, or consist of high density polyethylene, low density polyethylene, polypropylene, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyethylene terephthalate, polyamide, poly(methyl methacrylate), polytetrafluoroethylene, or a combination thereof.

[0201] In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastics may contain at least one, two, three or four different types of waste plastics in each case 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 weight percent. In one embodiment or in combination with any embodiment mentioned herein, the plastic waste may contain polyvinyl chloride and / or polyethylene terephthalate in each case at 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 weight percent. In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastics may contain at least one, two or three plasticized plastics. Reference to "type" is determined by resin ID code 1-7.

[0202] like Figure 2As shown, the solid waste plastic feed from the plastic source 112 can be supplied to the feedstock pretreatment unit 114. In the feedstock pretreatment unit 114, the introduced waste plastic can undergo a number of pretreatments to promote the subsequent pyrolysis reaction. Such pretreatments may include, for example, washing, mechanical agitation, flotation, diameter 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 diameter reduction 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 plastic by at least 10%, or at least 25%, or at least 50%, or at least 75%.

[0203] 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 of the embodiments mentioned herein, the plastic feed system 116 can include a screw feeder, a hopper, a pneumatic conveying system, a mechanical metal bar or chain, or a combination thereof.

[0204] When in the pyrolysis reactor 118, at least a portion of the plastic feed can be subjected to a pyrolysis reaction that 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, or a membrane reactor, or a combination of these reactors.

[0205] Generally, pyrolysis is a process that involves both chemical and thermal decomposition of the incoming feed. Although all pyrolysis processes can generally be characterized by a reaction environment that is substantially free of oxygen, the pyrolysis process can be further defined by, for example, the pyrolysis reaction temperature within the reactor, the residence time in the pyrolysis reactor, the type of reactor, the pressure within the pyrolysis reactor, and the presence or absence of a pyrolysis catalyst.

[0206] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction can include heating and converting the plastic feedstock in an atmosphere that is substantially free of oxygen or in an atmosphere that contains less oxygen relative to ambient air. In one embodiment or in combination with any of the embodiments mentioned herein, the atmosphere within the pyrolysis reactor 118 can contain oxygen in an amount 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.

[0207] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process can be carried out in the presence of an inert gas such as nitrogen, carbon dioxide and / or steam. 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.

[0208] In one embodiment or in combination with any embodiment mentioned herein, the temperature in the pyrolysis reactor 118 can be adjusted to promote 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 can 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 can 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 can 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.

[0209] 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, 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.

[0210] 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 18 can be maintained at about atmospheric pressure or in a 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.

[0211] In one embodiment or in combination with any of the embodiments mentioned herein, a pyrolysis catalyst can be introduced into the plastic feed prior to introduction into the pyrolysis reactor 118 and / or directly introduced into the pyrolysis reactor 118 to produce r-catalyzed pyrolysis oil, or r-pyrolysis oil prepared by a catalytic pyrolysis process. In one embodiment or in combination with any embodiment mentioned herein, or in combination with any embodiment mentioned herein, the catalyst may comprise: (i) a solid acid such as a zeolite (e.g., ZSM-5, mordenite, beta, ferrierite and / or zeolite-Y); (ii) a superacid such as sulfonated, phosphated or fluorinated forms of zirconium oxide, titania, alumina, silica-alumina, and / or clay; (iii) a solid base such as a metal oxide, mixed metal oxide, metal hydroxide and / or metal carbonate, 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) a homogeneous catalyst such as a Lewis acid, a metal tetrachloroaluminate or an organic ionic liquid; (viii) activated carbon; or (ix) a combination thereof.

[0212] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 occurs in the substantial absence of a catalyst, particularly the catalysts described above. In such an embodiment, non-catalytic, heat-retaining inert additives, such as sand, may still be introduced into the pyrolysis reactor 118 to facilitate heat transfer within the reactor 118.

[0213] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 can occur at a temperature in the range of 350 to 550° C., at a pressure in the range of 0.1 to 60 bar, and at a residence time of 0.2 seconds to 4 hours or 0.5 hours to 3 hours in the substantial absence of a pyrolysis catalyst.

[0214] Reference again Figure 2 , the pyrolysis effluent 120 leaving the pyrolysis reactor 118 generally includes pyrolysis gases, pyrolysis vapors, and residual solids. As used herein, the vapors produced during the pyrolysis reaction may be interchangeably referred to as "pyrolysis oils," which refers to the vapors when condensed into their liquid state. In one embodiment or in combination with any of the embodiments mentioned herein, the solids in the pyrolysis effluent 20 may include particles of char, ash, unconverted plastic solids, other unconverted solids from the feedstock, and / or spent catalyst (if a catalyst is used).

[0215] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain 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 weight percent of pyrolysis vapor in each case, which may subsequently be condensed into a resulting pyrolysis oil (e.g., r-pyrolysis oil). Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain no more than 99, 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, 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 weight percent of pyrolysis vapor in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can contain 20-99 wt%, 40-90 wt%, or 55-90 wt% pyrolysis vapor.

[0216] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can contain 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 weight percent of pyrolysis gas (e.g., r-pyrolysis gas) in each case. 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 can contain 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 each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can contain 1-90 wt%, or 5-60 wt%, or 10-60 wt%, or 10-30 wt%, or 5-30 wt% pyrolysis gases.

[0217] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can contain 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, in each case.

[0218] In one embodiment or in any combination of the embodiments mentioned, a cracker feedstock composition comprising pyrolysis oil (r-pyrolysis oil) is provided, and the r-pyrolysis oil composition contains a recycled component catalytic pyrolysis oil (r-catalytic pyrolysis oil, r-catalytic pyoil) and a recycled component thermal pyrolysis oil (r-thermal pyrolysis oil, r-thermal pyoil). R-thermal pyrolysis oil is a pyrolysis oil prepared without adding a pyrolysis catalyst. The cracker feedstock may include at least 5wt%, 10wt%, 15wt% or 20wt% of r-catalytic pyrolysis oil, which may be optionally hydrotreated. The r-pyrolysis oil containing t-thermal pyrolysis oil and r-catalytic pyrolysis oil may be cracked according to any process described herein to provide an olefin-containing effluent stream. The r-catalytic pyrolysis oil may be blended with the r-thermal pyrolysis oil to form a blended stream cracked in a cracker unit. Alternatively, the blended stream may contain no more than 10 wt%, 5 wt%, 3 wt%, 2 wt%, 1 wt% of unhydrotreated r-catalytic pyrolysis oil.

[0219] In one embodiment or in combination with any of the mentioned embodiments, the r-pyrolysis oil is free of r-catalytic pyrolysis oil.

[0220] like Figure 2 As shown, the conversion effluent 120 from the pyrolysis reactor 118 can be introduced into a 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 conversion effluent 120. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the solid particles 24 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. The solids can be removed from the regenerator 126 via line 145 and discharged from the system.

[0221] Back to Figure 2, the remaining gas and vapor conversion products 130 from the solid separator 122 can be introduced into a fractionation tower 132. In the fractionation tower 132, at least a portion of the pyrolysis oil vapor can be separated from the cracked gas to form a cracked gas product stream 134 and a pyrolysis oil vapor stream 136. Suitable systems for use as the fractionation tower 132 may include, for example, a distillation tower, a membrane separation unit, a quench tower, a condenser, or any other known separation unit 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 an optional regenerator 126 for additional processing.

[0222] In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the pyrolysis oil vapor stream 136 may 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 may include any suitable quenching system known in the art, such as a quench tower. The resulting liquid pyrolysis oil stream 140 may 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 treatment, such as hydroprocessing and / or hydrogenation, before being used in any downstream application described herein.

[0223] 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 hydroprocessing unit 142 for further refining. The hydroprocessing unit 142 may include a hydrocracker, a catalytic cracker operated using a hydrogen feed stream, a hydroprocessing unit, and / or a hydrogenation unit. In the hydroprocessing 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 byproducts from the pyrolysis oil. The resulting hydrotreated pyrolysis oil vapor stream 144 can be removed and introduced into a quenching 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 hydroprocessing is performed in the liquid phase pyrolysis oil. In this embodiment, post-hydrogenation or post-hydroprocessing does not require a quenching step.

[0224] 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 although all of the following characteristics and properties can be listed individually, it is contemplated that each of the following characteristics and / or properties of the pyrolysis oil or pyrolysis gas are not mutually exclusive and can be combined and exist in any combination.

[0225] Pyrolysis oil can contain mainly hydrocarbons having 4 to 30 carbon atoms per molecule (e.g., C4 to C30 hydrocarbons). As used herein, the term "Cx" or "Cx hydrocarbons" refers to hydrocarbon compounds having x total carbons per molecule, and includes all olefins, paraffins, aromatic hydrocarbons, and isomers having this number of carbon atoms. For example, each of normal, iso- and tert-butane and butene and butadiene molecules will fall within the general description "C4".

[0226] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the cracking furnace may have a C4-C50 weight percent 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. 30 Hydrocarbon content, based on the weight of the pyrolysis oil.

[0227] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the furnace may comprise primarily C5-C 25 、C5-C 22 or C5-C 20 hydrocarbons, or may contain 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 weight percent of C5-C 25 、C5-C 22 or C5-C 20 Hydrocarbons, based on the weight of the pyrolysis oil.

[0228] The gas furnace can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock, thereby avoiding the necessity of subjecting the pyrolysis oil feedstock to separation techniques to deliver smaller or lighter hydrocarbon fractions to the cracking furnace. In one embodiment or in any of the mentioned embodiments, after delivery from the pyrolysis manufacturer, the pyrolysis oil does not undergo a separation process for separating the heavy hydrocarbon fractions from the lighter hydrocarbon fractions relative to each other before feeding the pyrolysis oil to the cracking furnace. Feeding the pyrolysis oil to the gas furnace allows the use of pyrolysis oil containing heavy tails or higher carbon numbers equal to or higher than 12. In one embodiment or in any of the mentioned embodiments, the pyrolysis oil fed to the cracking furnace is C5 to C 25 A hydrocarbon stream containing at least 1 wt%, 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 a hydrocarbon stream in C 12 To C 25(including the end value), or in the range of C 14 To C 25 (including the end value), or in the range of C 16 To C 25 Hydrocarbons within the range of 20 Å to 50 Å (including the end value).

[0229] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have 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 weight percent of C6 to C 12 Hydrocarbon content, 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-C12 hydrocarbon content of no more than 98.5, 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. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a C6-C12 hydrocarbon content of 10-95 wt%, 20-80 wt%, or 35-80 wt%.

[0230] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a C 2+ 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, in each case by weight. 13 To C 23 Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a C content of 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, in each case by weight. 13 To C 23 In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have 1-80 wt%, 5-65 wt%, or 10-60 wt% C 13 To C 23 Hydrocarbon content.

[0231] 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 fed to the cracking furnace that receives a predominantly C2-C4 feedstock prior to feeding the pyrolysis oil (and references to r-pyrolysis oil or pyrolysis oil throughout include any of these embodiments), may have at least 1, or at least 2, or at least 3, or at least 4, or at least 5 weight percent of C2-C4 in each case. 24+ Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a C content of 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. 24+ Hydrocarbon content, in each case as a percentage by weight. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have 1-15 wt%, 3-15 wt%, 2-5 wt% or 5-10 wt% C 24+ Hydrocarbon content.

[0232] The pyrolysis oil may also include various amounts of olefins, aromatics, and other compounds. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil contains at least 1, or at least 2, or at least 5, or at least 10, or at least 15, or at least 20 weight percent olefins and / or aromatics in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may contain 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, or no more than 10, or no more than 5, or no more than 2, or no more than 1 weight percent olefins and / or aromatics in each case.

[0233] In one embodiment or in combination with any of the embodiments mentioned herein, the aromatic hydrocarbon content of the pyrolysis oil may be no more than 25, or no more than 20, or no more than 15, or no more than 14, or no more than 13, or no more than 12, or no more than 11, 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, or no more than 2, or no more than 1, in each case by weight. In one embodiment or in combination with any of the embodiments mentioned, the aromatic hydrocarbon content of the pyrolysis oil is no more than 15, or no more than 10, or no more than 8, or no more than 6, in each case by weight.

[0234] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a cycloalkane 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 by weight. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a cycloalkane content of 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 10, or no more than 5, or no more than 2, or no more than 1, or no more than 0.5, or undetectable amounts, in each case by weight. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a cycloalkane content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or undetectable amounts. Alternatively, the pyrolysis oil may contain 1-50 wt%, 5-50 wt%, or 10-45 wt% cycloparaffins, especially if the r-pyrolysis oil is subjected to a hydrotreating process.

[0235] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a paraffin 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 of the embodiments mentioned herein, the pyrolysis oil may have a paraffin content of 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 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a paraffin content of 25-90 wt%, 35-90 wt%, or 40-80 wt%, or 40-70 wt%, or 40-65 wt%.

[0236] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an n-paraffin 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 an n-paraffin content of 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 weight percent in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an n-paraffin content of 25-90 wt%, 35-90 wt%, or 40-70 wt%, or 40-65 wt%, or 50-80 wt%.

[0237] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin 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 can have a paraffin to olefin 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 embodiment mentioned herein, the pyrolysis oil can have a paraffin 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.

[0238] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a normal paraffin to isoparaffin 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 embodiment mentioned herein, the pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of no more than 100:1, 7, or no more than 5:1, 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 embodiment mentioned herein, the pyrolysis oil can have a normal-to-isoparaffin weight ratio in the range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0239] It should be noted that all of the above hydrocarbon weight percentages can be determined using gas chromatography-mass spectrometry (GC-MS).

[0240] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may exhibit at least 0.6 g / cm 3 , or at least 0.65g / cm 3 , or at least 0.7g / cm 3 Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may exhibit a density of no more than 1 g / cm at 15°C. 3 , or not more than 0.95g / cm 3 , or not more than 0.9g / cm 3 , or not more than 0.85g / cm 3 In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil exhibits a density of 0.6 to 1 g / cm at 15°C. 3 , 0.65 to 0.95 g / cm 3 or 0.7 to 0.9 g / cm 3 .

[0241] In one embodiment or in combination with any of the embodiments 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 of the embodiments 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 of the embodiments mentioned herein, the pyrolysis oil exhibits an API gravity of between 28 and 50, between 29 and 58, or between 30 and 44 at 15°C.

[0242] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can 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 can be measured according to ASTM D-2887 or the procedure described in the working examples. If the value is obtained in any method, the mid-boiling point with the value is met. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a medium 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, 1°C, or no more than 55°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 values ​​can be measured according to ASTM D-2887 or the procedure described in the working examples. If this value is obtained in any method, the medium boiling point with the value is satisfied. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a medium boiling point in the range of 75 to 250°C, 90 to 225°C, or 115 to 190°C. As used herein, "medium boiling point" refers to the median boiling point temperature of the pyrolysis oil when 50 wt% of the pyrolysis oil boils above the medium boiling point and 50 wt% of the pyrolysis oil boils below the medium boiling point.

[0243] 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 a final 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 having the stated value is satisfied.

[0244] Turning to the pyrolysis gases, the pyrolysis gases may have a methane content of at least 1 wt%, or at least 2 wt%, or at least 5 wt%, or at least 10 wt%, or at least 11 wt%, or at least 12 wt%, or at least 13 wt%, or at least 14 wt%, or at least 15 wt%, or at least 16 wt%, or at least 17 wt%, or at least 18 wt%, or at least 19 wt%, or at least 20 wt%. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gases may have a methane content of 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 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gases may have a methane content of 1-50 wt%, 5-50 wt%, or 15-45 wt%.

[0245] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may 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 may have a C3 hydrocarbon content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30 weight percent in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C3 hydrocarbon content of 1-50 wt%, 5-50 wt%, or 20-50 wt%.

[0246] 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 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 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 1-50 wt%, 5-50 wt%, or 20-50 wt%.

[0247] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil of the present invention can be a recycled content pyrolysis oil composition (r-pyrolysis oil).

[0248] 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 may undergo one or more processing steps before being introduced into a downstream unit such as a cracking furnace. Examples of suitable processing steps may include, but are not limited to, separation of less desirable components (e.g., nitrogen-containing compounds, oxygen-containing compounds, and / or olefins and aromatics), distillation to provide a specific pyrolysis oil composition, and preheating.

[0249] Now turn to Figure 3 , showing a schematic diagram of a processing zone for pyrolysis oil, according to one embodiment or in combination with any embodiment mentioned herein.

[0250] like Figure 3 As shown in the processing zone 220 shown in , at least a portion of the r-pyrolysis oil 252 made from the recycled waste stream 250 in the pyrolysis system 210 can be passed through the processing zone 220, such as a separator, which can separate the r-pyrolysis oil into a light pyrolysis oil fraction 254 and a heavy pyrolysis oil fraction 256. The separator 220 used for this separation can be of any suitable type, including a single-stage vapor liquid separator or "flash" tower, or a multi-stage distillation tower. The vessel may or may not include internal components, and may or may not use reflux and / or boiling flow.

[0251] In one embodiment or in combination with any of the embodiments mentioned herein, the C4 to C7 content of the heavy fraction or the C 8+The content may be at least 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt% or 85 wt%. The light fraction may 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- In some embodiments, the separator can concentrate the desired components into the heavy fraction, so that the heavy fraction can have a C4 to C7 content or C8 content higher than the pyrolysis oil taken from the pyrolysis zone. 8+ The C4 to C7 content or C4 to C7 content of at least 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 70%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, 120%, 125%, 130%, 135%, 140%, 145% or 150% greater 8+ Content. Figure 3 As shown, at least a portion of the heavy fraction may be sent to a cracking furnace 230 to be cracked as an r-pyrolysis oil composition or as a portion of a pyrolysis oil composition to form an olefin-containing effluent 258, as discussed in further detail below.

[0252] In one embodiment or in combination with any embodiment 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 embodiment 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.

[0253] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can be combined with a non-recovered 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 concentration of less desirable compounds (e.g., impurities such as oxygenates, aromatics, or other compounds described herein), the r-pyrolysis oil can be combined with the cracker feed 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 compound 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-recovered cracker feed 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 a target value for the one or more compounds to determine a difference, and then determining the amount of non-recovered hydrocarbons to add to the r-pyrolysis oil stream based on the difference. The amount of r-pyrolysis oil and non-recovered hydrocarbons can be within one or more ranges described herein.

[0254] At least a portion of the r-ethylene may be derived directly or indirectly from the cracking of r-pyrolysis oil. The process for obtaining r-olefins from cracking (r-pyrolysis oil) may be as follows and as Figure 4 As described in.

[0255] Steering Figure 4 , which is a flow chart showing the steps associated with the cracking furnace 20 and the separation zone 30 of a system for producing an r-composition obtained by cracking r-pyrolysis oil. Figure 4 As shown, a feed stream containing r-pyrolysis oil (a feed stream containing r-pyrolysis oil) can be introduced into the cracking furnace 20 alone or in combination with a non-recovery cracker feed stream. The pyrolysis unit that produces r-pyrolysis oil can be located at the same location as the production facility. In other embodiments, the r-pyrolysis oil can originate from a remote pyrolysis unit and be transported to the production facility.

[0256] In one embodiment or in combination with any embodiment mentioned herein, the feed stream containing r-pyrolysis oil can contain the following amount of r-pyrolysis oil: 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. 8, or at least 99, or at least or 100, in each case as weight percent; and / 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, 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, in each case as weight percent, based on the total weight of the feed stream containing r-pyrolysis oil.

[0257] In one embodiment or combination with any embodiment mentioned herein, at least 1 wt%, or at least 5 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%, or at least 70 wt%, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at least 97 wt%, or at least 98 wt%. In one embodiment or in combination with any of the embodiments mentioned herein, at least a portion of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock containing plastic waste. Desirably, at least 90, or at least 95, or at least 97, or at least 98, or at least 99, or at least or 100, in each case by weight, of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock comprising plastic waste, or a feedstock comprising at least 50 wt% plastic waste, or a feedstock comprising at least 80 wt% plastic waste, or a feedstock comprising at least 90 wt% plastic waste, or a feedstock comprising at least 95 wt% plastic waste.

[0258] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have any one or combination of the compositional characteristics described above for the pyrolysis oil.

[0259] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may comprise at least 55 wt%, or at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at least 95 wt% of C4-C 30 Hydrocarbons, 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 may mainly contain C5-C 25 、C5-C 22 or C5-C 20 hydrocarbons, or may contain at least 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt% or 95 wt% of C5-C 25 、C5-C 22 or C5-C 20 hydrocarbon.

[0260] In one embodiment or, or in combination with any of the embodiments mentioned, the r-pyrolysis oil composition may comprise C4-C 12 Aliphatic compounds (branched or unbranched alkanes and alkenes, including dienes and alicyclic 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.

[0261] In one embodiment, or in combination with any of the embodiments mentioned, the r-pyrolysis oil composition may include C 13 -C 22 Aliphatic compounds (branched or unbranched alkanes and alkenes, including diolefins and alicyclic 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.

[0262] In one embodiment, the two aliphatic hydrocarbons (branched or unbranched alkanes and alkenes, and alicyclic compounds) with the highest concentration in the r-pyrolysis oil are in the C5-C 18 , or C5-C 16 , or C5-C 14 , or C5-C 10 , or in the range of C5-C8 (including the end values).

[0263] The r-pyrolysis oil may include one or more of paraffinic, cycloparaffinic or cycloaliphatic hydrocarbons, aromatic hydrocarbons, aromatic-containing hydrocarbons, olefins, oxygen-containing compounds and polymers, heteroatom compounds or polymers, and other compounds or polymers.

[0264] For example, in one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can contain 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 no more than 99, or no more than 97, or no more than 98 weight percent in each case. 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 of paraffins (either straight or branched) based on the total weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin content of 25 to 90, 35 to 90, or 40 to 80, or 40 to 70, or 40 to 65 weight percent, 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 each case as wt % based on the weight of the r-pyrolysis oil composition.

[0265] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include cycloalkanes or cycloaliphatic 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 each case by weight percent, and / 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, or no more than 10, or no more than 5, or no more than 2, or no more than 1, or no more than 0.5, or undetectable amounts, in each case by weight percent. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have a cycloalkanes content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or undetectable amounts. Examples of ranges for the amount of cycloalkanes (or cycloaliphatic 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 each case wt % based on the weight of the r-pyrolysis oil composition.

[0266] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a paraffin 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 r-pyrolysis oil can have a paraffin to olefin 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 embodiment mentioned herein, the r-pyrolysis oil can have a paraffin 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.

[0267] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a normal paraffin to isoparaffin 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 embodiment mentioned herein, the r-pyrolysis oil can have a normal paraffin to isoparaffin 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 embodiment mentioned herein, the r-pyrolysis oil can have a normal-to-isoparaffin weight ratio in the range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0268] In one embodiment, the r-pyrolysis oil contains no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 5, or no more than 2, or no more than 1 weight percent of aromatic hydrocarbons, 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 wt%, or at least 2 wt%, or at least 5 wt%, or at least 8 wt%, or at least 10 wt% of aromatic hydrocarbons, based on the total weight of the r-pyrolysis oil in each case.

[0269] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include an amount of no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 5, or no more than 2, or no more than 1, or no detectable aromatic compounds, in each case by weight, based on the total weight of the r-pyrolysis oil. Aromatic compounds include the above-mentioned aromatic hydrocarbons and any compounds containing aromatic moieties, such as terephthalate residues and fused ring aromatic hydrocarbons, such as naphthalene and tetralin.

[0270] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can contain olefins in the following amounts: 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 olefins in each case by weight, and / or, in each case 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, or no more than 10 weight percent, based on the weight of the r-pyrolysis oil. Olefins include mono-olefins and di-olefins. Examples of suitable ranges include olefins being present in amounts 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.

[0271] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include an amount of zero or at least 0.01, or at least 0.1, or at least 1, or at least 2, or at least 5 weight percent oxygenates or polymers, and / or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 6, or no more than 5, or no more than 3, or no more than 2 weight percent oxygenates or polymers in each case, based on the weight of the r-pyrolysis oil. Oxygenated compounds and polymers are those containing oxygen atoms. Examples of suitable ranges include oxygenates present in an amount in the range of 0-20, or 0-15, or 0-10, or 0.01-10, or 1-10, or 2-10, or 0.01-8, or 0.1-6, or 1-6, or 0.01-5, in each case wt %, based on the weight of the r-pyrolysis oil.

[0272] In one embodiment or in combination with any embodiment mentioned herein, the amount of oxygen atoms in the r-pyrolysis oil may be no more than 10, or no more than 8, or no more than 5, or no more than 4, or no more than 3, or no more than 2.75, or no more than 2.5, or no more than 2.25, or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.1, or no more than 0.05, in each case as wt % based on the weight of the r-pyrolysis oil. Examples of amounts of oxygen in the r-pyrolysis oil may be 0-8, or 0-5, or 0-3, or 0-2.5 or 0-2, or 0.001-5, or 0.001-4, or 0.001-3, or 0.001-2.75, or 0.001-2.5, or 0.001-2, or 0.001-1.5, or 0.001-1, or 0.001-0.5, or 0.001-1, in each case in wt % based on the weight of the r-pyrolysis oil.

[0273] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include a heteroatom compound or polymer in an amount of at least 1 wt%, or at least 2 wt%, or at least 5 wt%, or at least 8 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, and / or, no more than 25 wt%, or no more than 20 wt%, or no more than 15 wt%, or no more than 10 wt%, or no more than 8 wt%, or no more than 6 wt%, or no more than 5 wt%, or no more than 3 wt%, or no more than 2 wt%, based on the weight of the r-pyrolysis oil. A heteroatom compound or polymer is defined in this paragraph as any compound or polymer containing nitrogen, sulfur or phosphorus. Any other atom is not considered a heteroatom to determine the amount of heteroatoms, heterocompounds or heteropolymers present in the r-pyrolysis oil. The r-pyrolysis oil may contain heteroatoms present in an amount of 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 0.075, or not more than 0.05, 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 0.005, or not more than 0.003, or not more than 0.002, in each case in wt % based on the weight of the r-pyrolysis oil.

[0274] In one embodiment or in combination with any embodiment mentioned herein, the solubility of water in r-pyrolysis oil at 1 atm and 25° C. is less than 2 wt %, water, or no more than 1.5, or no more than 1, or no more than 0.5, or no more than 0.1, or no more than 0.075, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, in each case wt % water based on the weight of r-pyrolysis oil. Desirably, the solubility of water in r-pyrolysis oil is no more than 0.1 wt %, based on the weight of r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, r-pyrolysis oil contains no more than 2 wt % water, or no more than 1.5, or no more than 1, or no more than 0.5, desirably or no more than 0.1, or no more than 0.075, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, in each case wt % water based on the weight of r-pyrolysis oil.

[0275] In one embodiment or in combination with any embodiment mentioned herein, the solids content in the r-pyrolysis oil is no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, or no more than 0.001, in each case as wt% solids based on the weight of the r-pyrolysis oil.

[0276] In one embodiment or in combination with any embodiment mentioned herein, the sulfur content of the r-pyrolysis oil is no more than 2.5 wt%, or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.1, or no more than 0.05, desirably or no more than 0.03, or no more than 0.02, or no more than 0.01, or no more than 0.008, or no more than 0.006, or no more than 0.004, or no more than 0.002, or no more than 0.001, in each case as wt% based on the weight of the r-pyrolysis oil.

[0277] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have the following component contents:

[0278] a carbon atom content of 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

[0279] 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 by wt %.

[0280] 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 by weight %.

[0281] In each case based on the weight of the r-pyrolysis oil.

[0282] In one embodiment or in combination with any embodiment mentioned herein, the amount of hydrogen atoms in the r-pyrolysis oil may 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 wt % based on the weight of the r-pyrolysis oil.

[0283] In one embodiment or in combination with any embodiment mentioned herein, the metal content of the r-pyrolysis oil is desirably low, for example no more than 2 wt%, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, in each case as wt% based on the weight of the r-pyrolysis oil.

[0284] In one embodiment or in combination with any embodiment mentioned herein, the alkali and alkaline earth metal or mineral content of the r-pyrolysis oil is desirably low, for example no more than 2 wt%, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, in each case as wt% based on the weight of the r-pyrolysis oil.

[0285] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of paraffins to cycloalkanes 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.

[0286] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of the combination of paraffins and cycloalkanes to aromatic hydrocarbons 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 of the embodiments mentioned herein, the ratio of the combination of paraffins and cycloalkanes to aromatic hydrocarbons in the r-pyrolysis oil may 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.

[0287] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have a boiling point curve defined by one or more of its 10%, its 50% and its 90% boiling points, as defined below. As used herein, "boiling point" refers to the boiling point of the composition measured by ASTM D2887 or according to the procedure described in the working examples. If the value is obtained in any method, the boiling point with the value is satisfied. In addition, as used herein, "x% boiling point" means that according to any of these methods, x% of the composition by weight boils at the boiling point.

[0288] As used throughout, x% boiling at the temperature means that at least x% of the composition boils at the temperature. In one embodiment or combination with any embodiment 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 250. %, or no more than 25 wt%, 20 wt%, 15 wt%, 10 wt%, 5 wt% or 2 wt% of the r-pyrolysis oil may have a boiling point of 300°C or higher.

[0289] Reference again Figure 3, r-pyrolysis oil may be introduced into a cracking furnace or coils or tubes alone (e.g., in an amount comprising at least 85, or at least 90, or at least 95, or at least 99, or 100, in each case wt % based on the weight of the cracker feed streams, of pyrolysis oil) or in combination with one or more non-recovery cracker feed streams. When introduced into a cracking furnace, coils or tubes with a non-recovery cracker feed stream, the r-pyrolysis oil may be present 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 12, or at least 15, or at least 20, or at least 25, or at least 30, in each case wt %, and / 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, or no more than 10, or no more than 8, or no more than 5, or no more than 2, in each case wt % based on the total weight of the combined streams. Thus, the non-recovery 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, in each case by weight percent, and / or no more than 99, 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, or no more than 55, or no more than 50, or no more than 45, or no more than 40, in each case by weight percent based on the total weight of the combined stream. Unless otherwise indicated herein, the properties of the cracker feed stream described below apply to the non-recovered cracker feed stream before (or in the absence of) being combined with a stream comprising r-pyrolysis oil, as well as to a combined cracker stream comprising both a non-recovered cracker feed and an r-pyrolysis oil feed.

[0290] In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed stream may comprise a composition comprising primarily C2-C4 hydrocarbons, or a composition comprising primarily C5-C 22As used herein, the term "primarily C2-C4 hydrocarbons" refers to a stream or composition containing at least 50 weight percent of C2-C4 hydrocarbon components. 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 embodiment mentioned herein, the cracker feed may contain the following amounts of C2-C4 hydrocarbons or linear alkanes: 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 as wt%, based on the total weight of the feed, and / or no more than 100, or no more than 99, or no more than 95, or no more than 92, 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 as weight percent, based on the total weight of the feed. The cracker feed may comprise mainly propane, mainly ethane, mainly butane or a combination of two or more of these components. These components may be non-recovery components. The cracker feed may comprise mainly 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 recovery stream mixed with fresh feed). The cracker feed may comprise HD5 quality propane as raw or fresh feed. The cracker may comprise 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-recovery components.

[0291] In one embodiment or in combination with any embodiment described herein, the cracker feed stream may comprise a predominantly C5-C 22 As used herein, "primarily C5-C 22 "Hydrocarbon" refers to hydrocarbons containing at least 50 weight percent of C5-C 22 Examples include gasoline, naphtha, middle distillates, diesel, kerosene. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed stream or composition may include the following amounts of C5-C 22 , or C5-C 20Hydrocarbons: 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 no more than 100, or no more than 99, or no more than 95, or no more than 92, 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 as weight percent, based on the total weight of the stream or composition. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed can have a C15 and heavier (C15+) content of at least 0.5, or at least 1, or at least 2, or at least 5, in each case as weight percent, and / 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 18, or no more than 15, or no more than 12, or no more than 10, or no more than 5, or no more than 3, in each case as weight percent, based on the total weight of the feed.

[0292] 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 above method, and further, as used herein, "x% boiling point" means the boiling point at which x weight percent of the composition boils according to the above method. In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feed stream or composition may be no more than 360, or no more than 355, or no more than 350, or no more than 345, or no more than 340, or no more than 335, or no more than 330, or no more than 325, or no more than 320, or no more than 315, 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 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 °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 °C.

[0293] In one embodiment or in combination with any of the embodiments mentioned herein, the 10% boiling point of the cracker feed stream or composition can 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 °C, and / or no more than 250, no more than 240, no more than 230, no more than 220, no more than 210, no more than 200, no more than 190, no more than 180 or no more than 170, in each case °C.

[0294] In one embodiment or in combination with any of the embodiments 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 °C, and / or no more than 300, no more than 290, no more than 280, no more than 270, no more than 260, no more than 250, no more than 240, no more than 230, no more than 220, no more than 210, 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 145 °C. The 50% boiling point of the cracker feed stream or composition may 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 °C.

[0295] In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feed or stream or composition may be at least 350°C, the 10% boiling point may be at least 60°C; and the 50% boiling point may 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 feed or stream or composition may be at least 150°C, the 10% boiling point may be at least 60°C, and the 50% boiling point may be in the range of 80°C to 145°C. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed 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.

[0296] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil is cracked in a gas furnace. A gas furnace is a furnace having at least one coil that receives (or operates to receive) a feed that is primarily in the gas phase (more than 50% of the feed weight is vapor) at the coil inlet at the convection zone inlet ("gas coil"). In one embodiment or in combination with any embodiment mentioned herein, the gas coil may receive a primarily C2-C4 feedstock or a primarily C2-C3 feedstock to the inlet of the coil in the convection section, or alternatively, have at least one coil that receives more than 50 wt% ethane and / or more than 50% propane and / or more than 50% 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. A gas furnace may have more than one gas coil. In one embodiment or in combination with any of the embodiments mentioned herein, 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 of the embodiments mentioned herein, the gas coils receive 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.

[0297] In one embodiment or in combination with any of the embodiments mentioned herein, 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 in the same furnace, or in the same convection zone, or in the same convection box. The liquid coil is a coil that receives a feed that is mainly in liquid phase (more than 50% of the feed weight is liquid) at the coil inlet at the inlet of the convection zone ("liquid coil"). In one embodiment or in combination with any of the embodiments mentioned herein, the liquid coil may receive a feed that is mainly in liquid phase (more than 50% of the feed weight is liquid) at the inlet of the convection section ("liquid coil"). 5+ In one embodiment or in combination with any embodiment mentioned herein, the liquid coil may receive a liquid feedstock of mainly C6-C 22 The raw materials are mainly C7-C 16of feed to the inlet of the coils in the convection section, or alternatively, having at least one coil which receives more than 50 wt % naphtha, and / or more than 50 wt % natural gasoline, and / or more than 50 wt % diesel, and / or more than JP-4, and / or more than 50 wt % dry cleaning solvent, and / or more than 50 wt % kerosene, and / or more than 50 wt % fresh creosote, and / or more than 50 wt % JP-8 or Jet-A, and / or more than 50 wt % heating oil, and / or more than 50 wt % heavy fuel oil, and / or more than 50 wt % marine grade C, and / or more than 50 wt % 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 coils, or alternatively based on the weight of the cracker feed to the convection zone. In one embodiment or in combination with any of the embodiments mentioned herein, at least one coil in the convection zone or in the convection box of the furnace and no more than 75% of the coils, or no more than 50% of the coils, or no more than at least 40% of the coils are liquid coils. In one embodiment or in combination with any of the embodiments mentioned herein, the liquid 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 liquid.

[0298] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil is cracked in a thermal gas cracker.

[0299] In one embodiment or in combination with any of the embodiments mentioned herein, the 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.

[0300] In one embodiment or in combination with any embodiment mentioned herein, the r-composition is derived directly or indirectly from cracking r-pyrolysis oil in a gas furnace.The coils in the gas furnace may consist entirely of gas coils, or the gas furnace may be a cracking furnace.

[0301] When the feed stream containing r-pyrolysis oil is combined with the non-recovery cracker feed, this combination can occur upstream of the cracking furnace or inside the cracking furnace or in a single coil or tube. Alternatively, the feed stream containing r-pyrolysis oil and the non-recovery cracker feed can be introduced into the furnace separately, and can pass through a portion or all of the furnaces at the same time, while being isolated from each other by feeding into separate tubes in the same furnace (e.g., a cracking furnace). According to one embodiment or in combination with any embodiment mentioned herein, the manner in which the feed stream containing r-pyrolysis oil and the non-recovery cracker feed are introduced into the cracking furnace is described in further detail below.

[0302] Now turn to Figure 5 , shows a schematic diagram of a cracking furnace suitable for use in an embodiment or in combination with any embodiment mentioned herein.

[0303] In one embodiment or combination of any of the mentioned embodiments, there is provided a method for preparing one or more olefins, comprising:

[0304] (a) feeding a first cracker feed comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to a cracking furnace;

[0305] (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

[0306] (c) cracking said first and said second cracker feeds in respective first and second tubes to form olefin-containing effluent streams.

[0307] 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-recovery cracker stream and r-pyrolysis oil. The feeding of step (a) and / or step (b) can be carried out upstream of the convection zone or in the convection zone. The r-pyrolysis oil can be combined with the non-recovery 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 to the inlet of the coil or distributor together with the non-recovery cracker stream to form the first cracker stream at the inlet of the convection zone, or the r-pyrolysis oil can be fed into the tube containing the non-recovery cracker feed downstream of the inlet of the convection zone, but before crossing, to prepare the first cracker stream or the combined cracker stream in the tube or coil. Any of these methods includes feeding the first cracker stream into the furnace.

[0308] The amount of r-pyrolysis oil added to the non-recovery 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 weight percent, and / or not more than 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 weight percent, based on the total weight of the first cracker feed or the combined cracker feed (introduced into or within the tube as described above). Other examples include 5-50 wt%, 5-40 wt%, 5-35 wt%, 5-30 wt%, 5-25 wt%, 5-20 wt%, or 5-15 wt%.

[0309] The first cracker stream is cracked in a first coil or tube. The second cracker stream is cracked in a second coil or tube. The first and second cracker streams and the first and second coils or tubes may be in the same cracking furnace.

[0310] The second cracker stream may contain no r-pyrolysis oil or contain less (by weight) of said r-pyrolysis oil than the first cracker feed stream. In addition, the second cracker stream may contain only non-recycled cracker feed in the second coil or tube. The second cracker feed stream may be primarily C2 to C4, or hydrocarbons (e.g., non-recycled components), or ethane, propane or butane, in each case in an amount of at least 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt% or at least 90 wt%, based on the second cracker feed in the second coil or tube. If r-pyrolysis oil is included in the second cracker feed, the amount of such r-pyrolysis oil may 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.

[0311] In one embodiment or in combination with any embodiment described herein, although not shown, an evaporator may be provided to evaporate the condensed feed of C2-C5 hydrocarbons 350 to ensure that the feed to the coil inlet in the convection box 312 or the inlet of the convection zone 310 is primarily a vapor phase feed.

[0312] Figure 5The cracking furnace shown in FIG. 300 includes a convection section or zone 310, a radiation section or zone 320, and a cross section or zone 330 located between the convection section and the radiation sections 310 and 320. The convection section 310 is a portion of the furnace 300 that receives heat from the hot flue gases 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 gases passing therethrough. The radiation section 320 is a section of the furnace 300 that transfers heat to the heater tubes primarily by radiation from the high temperature gases. The radiation section 320 also includes a plurality of burners 326 for introducing heat into the lower portion of the furnace. The furnace includes a combustion chamber 322 that surrounds and accommodates the tubes within the radiation section 320, and the burners are directed into the combustion chamber. The crossover section 330 includes conduits for connecting the convection section 310 and the radiant section 320 and can transfer the heated cracker stream from inside or outside one section to another section within the furnace 300.

[0313] As the hot combustion gases rise upward through the furnace, the gases may pass through a convection section 310, wherein at least a portion of the waste heat may 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 may have a single convection (preheat) section 310 and a single radiant section 320, while in other embodiments, the furnace may include two or more radiant sections that share a common convection section. At least one induced draft (ID) machine 316 near the furnace may control the flow of the hot flue gases and the distribution of heat through the furnace, and one or more heat exchangers 340 may be used to cool the furnace effluent 370. In one embodiment or in combination with any of the embodiments mentioned herein (not shown), in addition to or in lieu of Figure 5 An exchanger such as that shown in FIG. 5 (eg, a transfer line heat exchanger or TLE) may be used to cool the cracked olefin-containing effluent using a liquid quench.

[0314] 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 temperatures and thermal stresses within the furnace. The coil can have any suitable shape and can, for example, have a circular or elliptical cross-sectional shape.

[0315] The diameter of the coils or tubes within the coils 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 cm, and / or no more than 12, or no more than 11.5, or no more than 11, 1, or no more than 0.5, or no more than 10, or no more than 9.5, or no more than 9, or no more than 8.5, or no more than 8, or no more than 7.5, or no more than 7, or no more than 6.5, in each case cm. All or a portion of one or more coils can be substantially straight, or one or more coils can include spirals, twists, 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 tube can be smooth or substantially smooth, or a portion (or all) can be roughened to minimize coking. Alternatively, or in addition, the interior of the tube can include inserts or fins and / or surface metal additives to prevent coke accumulation.

[0316] In one embodiment or in combination with any embodiment mentioned herein, all or a portion of one or more furnace coils 324 passing through the convection section 310 may be oriented horizontally, while all or at least a portion of the furnace coils passing through the radiant section 322 may be oriented vertically. In one embodiment or in combination with any embodiment mentioned herein, a single furnace coil may extend through both the convection section and the radiant section. Alternatively, at least one coil may be divided into two or more tubes at one or more points in the furnace so that the cracker stream may pass in parallel along multiple paths. For example, the cracker stream (including r-pyrolysis oil) 350 may be introduced into multiple coil inlets in the convection zone 310, or into multiple tube inlets in the radiated section 320 or the cross section 330. When multiple coils or tube inlets are introduced simultaneously or nearly simultaneously, the amount of r-pyrolysis oil introduced into each coil or tube may not be adjusted. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil and / or the cracker stream may be introduced into a common header, which then guides the r-pyrolysis oil to multiple coils or tube inlets.

[0317] 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, a coil. Each coil may be 5 to 100, 10 to 75, or 20 to 50 meters long 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 coil may be arranged in many 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 One example of a furnace coil 410 having a plurality of tubes 420 is shown in FIG.

[0318] 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, 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 50wt%, or at least 75wt%, or at least 85wt%, or at least 90wt% 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 of the embodiments mentioned herein, 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 C5-C 22 In one embodiment or in combination with any embodiment mentioned herein, 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% 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.

[0319] Now turn to Figure 7 , showing several possible locations for introducing the feed stream containing r-pyrolysis oil and the non-recovery cracker feed stream into the cracking furnace.

[0320] In one embodiment or in combination with any embodiment mentioned herein, the feed stream 550 containing r-pyrolysis oil can be combined with the non-recovery 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 feed 550 containing r-pyrolysis oil can be introduced into the first furnace coil, while the non-recovery cracker feed 552 is introduced into a separate or second furnace coil, in the same furnace or in the same convection zone. The two streams can then travel parallel to each other through the convection section 510, the crossover 530, and the radiant section 520 in the radiant box 522, so that each stream is substantially fluidly isolated from the other stream over most or all of the path of travel from the inlet to the outlet of the furnace. The pyrolysis stream introduced into any heating zone in the convection section 510 can flow through the convection section 510 and flow into the radiant box 522 as the vaporized stream 514b. In other embodiments, the feed stream 550 containing r-pyrolysis oil may also be introduced into the non-recovery cracker stream 552 as it flows through the furnace coils in the convection section 510 into the cross section 530 of the furnace to form the combined cracker stream 514a, also as shown in FIG. Figure 7 as shown in .

[0321] In one embodiment or in combination with any of the embodiments mentioned herein, the Figure 7 The first heating zone or the second heating zone shown introduces r-pyrolysis oil 550 into the first furnace coil, or an additional amount into the second furnace coil. The r-pyrolysis oil 550 may be introduced into the furnace coils at these locations via nozzles. A convenient method of introducing the r-pyrolysis oil feed is via one or more dilution steam feed nozzles, which are used to feed steam into the coils in the convection zone. The services of one or more dilution steam nozzles may be used to inject r-pyrolysis oil, or new nozzles may be fastened to the coils dedicated to the injection of r-pyrolysis oil. In one embodiment or in combination with any of the embodiments mentioned herein, both steam and r-pyrolysis oil may be co-fed into the furnace coils via nozzles downstream of the coil inlet and upstream of the crossover, optionally in the first or second heating zone within the convection zone, such as Figure 7 shown.

[0322] When introduced into the furnace and / or when combined with a feed containing r-pyrolysis oil, the non-recovery cracker feed stream may be primarily liquid and have a vapor fraction of less than 0.25 (by volume) or less than 0.25 (by weight), or it may be primarily vapor and have a vapor fraction of at least 0.75 (by volume) or at least 0.75 (by weight). Similarly, the feed containing r-pyrolysis oil may be primarily vapor or primarily liquid when introduced into the furnace and / or combined with the non-recovery cracker stream.

[0323] In one embodiment or in combination with any of the embodiments mentioned herein, at least a portion or all of the r-pyrolysis oil stream or cracker feed stream may be preheated prior to introduction into the furnace. Figure 8 As shown, preheating can be performed with an indirect heat exchanger 618 heated by a heat transfer medium (e.g., steam, hot condensate, or a portion of the olefin-containing effluent) or via a directly fired heat exchanger 618. The preheating step can vaporize all or part of the stream comprising r-pyrolysis oil, and can, for example, vaporize at least 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or 99 wt% of the stream comprising r-pyrolysis oil.

[0324] When preheating is performed, the temperature of the stream containing r-pyrolysis oil can 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, preheating can increase the temperature of the stream containing r-pyrolysis oil to a temperature that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 100° C. below the coking temperature of the stream. In one embodiment or in combination with any embodiment mentioned herein, the preheated r-pyrolysis oil stream can have a temperature of at least 200, 225, 240, 250, or 260° C., and / or no more than 375, 350, 340, 330, 325, 320, or 315° C., or at least 275, 300, 325, 350, 375, or 400° C., and / or no more than 600, 575, 550, 525, 500, or 475° C. When an atomized liquid (as described below) is injected into the vapor-phase heated cracker stream, the liquid can evaporate rapidly 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.

[0325] In one embodiment or in combination with any embodiment mentioned herein, the heated r-pyrolysis oil stream (or a cracker stream comprising r-pyrolysis oil and a non-recovery cracker stream) may optionally be passed through a vapor liquid separator to remove any residual heavy components or liquid components (when present). The resulting light fraction may then be introduced into a cracking furnace alone or in combination with one or more other cracker streams described in various embodiments herein. For example, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil stream may comprise at least 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, or 12 wt% C 15 The separation can remove at least 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or 99 wt% of the heavier components from the r-pyrolysis oil stream.

[0326] Back 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 points to control the temperature and cracking severity in the furnace. In one embodiment or in combination with any embodiment mentioned herein, 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 cross 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-recovery cracker stream (alone or in combination with steam) can also be introduced into the convection section or upstream or at the inlet of the convection section, or downstream of the inlet of the convection section - in the convection section, at the cross section, or at the inlet of the radiant section. Steam may be combined with the r-pyrolysis oil stream and / or the cracker stream, and the combined stream may be introduced at one or more of these locations, or steam and the r-pyrolysis oil and / or non-recovery cracker stream may be added separately.

[0327] 70, 760, 750, 740, 730, 720, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, or 650°C when combined with steam and fed into or near a crossover section of a furnace. The resulting steam and r-pyrolysis oil streams may 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.

[0328] When combined with steam and fed into or near the inlet of convection section 510, the r-pyrolysis oil and / or cracker stream may have a temperature of at least 30, 35, 40, 45, 50, 55, 60 or 65, and / or no more than 100, 90, 80, 70, 60, 50 or 45°C.

[0329] The amount of steam added may depend on the operating conditions, including the feed type and the desired product, but may be added to achieve a steam to hydrocarbon ratio of 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 The steam to hydrocarbon ratio may be in the range of no more than 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 may 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 embodiment described herein, steam may be used in the same furnace ( Figure 7Steam may be added to the cracker feed (or any intermediate cracker stream within the furnace) 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.

[0330] When the feed stream containing r-pyrolysis oil is introduced into the cracking furnace separately from the non-recycled feed stream, the molar flow rate of the r-pyrolysis oil and / or the stream containing r-pyrolysis oil may be different from the molar flow rate of the non-recycled feed stream. In one embodiment or in combination with any of the other mentioned embodiments, a method for preparing one or more olefins is provided, which is provided by:

[0331] (a) feeding a first cracker stream having r-pyrolysis oil to a first tube inlet in a cracking furnace;

[0332] (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 separate 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 to the second tube inlet calculated without the influence of steam. The feeds to step (a) and step (b) may be to respective coil inlets.

[0333] For example, when the r-pyrolysis oil or the first cracker stream passes through the tubes in the cracking furnace, its molar flow rate can be higher than the hydrocarbon components (e.g., C2-C4 or C5-C6) in the non-recycled feed stream or the second cracker stream. 22 ) 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 r-pyrolysis oil-containing stream or the first cracker stream and in the second cracker stream or the non-recovery stream, the total molar flow rate of the r-pyrolysis oil-containing stream or the first cracker stream (including r-pyrolysis oil and dilution steam) may 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 (including hydrocarbons and dilution steam) of the non-recovery 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-recovery stream).

[0334] In one embodiment or in combination with any of the embodiments mentioned herein, the molar flow rate of the r-pyrolysis oil in the feed stream containing r-pyrolysis oil in the furnace tubes (the first cracker stream) can be greater than the molar flow rate of the hydrocarbons (e.g., C2-C4 or C5-C6) in the non-recovery cracker stream (the second cracker stream). 22) is at least 0.01, 0.02, 0.025, 0.03, 0.035 and / or no more than 0.06, 0.055, 0.05, 0.045 kmol lb / hr lower than the molar flow rate of the cracker feed stream. In one embodiment or in combination with any embodiment mentioned herein, the molar flow rates of the 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 kmol lb / hr of each other. The molar flow rate of the r-pyrolysis oil in the furnace tubes may 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 kmol-lb / hr, and / or no 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, 0.0 25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.19, 0.21, 0.22, 0.23, 0.24, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65

[0335] In one embodiment or in combination with any embodiment mentioned herein, the total molar flow rate of the stream containing r-pyrolysis oil (the 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 the total molar flow rate of the non-recycled feed stream (the second cracker stream), and / or no more than 0.30, 0.25, 0.20, 0.15, 0.13, 0.10, 0.09, 0.08, 0.07 or 0.06 kilomol pounds per hour, or the same as the total molar flow rate of the non-recycled feed stream (the second cracker stream). The total molar flow rate of the stream containing r-pyrolysis oil (the first cracker stream) may be at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, and / or no more than 0.10, 0.09, 0.08, 0.07, or 0.06 kmol lb / hr higher than the total molar flow rate of the second cracker stream, while the total molar flow rate of the non-recycled feed stream (the second cracker stream) may 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 no more than 0.50, 0.49, 0.48, 0.47, 0.46, 0.45, 0.44, 0.43, 0.42, 0.41, 0.40 kmol lb / hr.

[0336] In one embodiment or in combination with any embodiment mentioned herein, the steam to hydrocarbon ratio of the stream or the first cracker stream containing r-pyrolysis oil differs from the steam to hydrocarbon ratio of the non-recovered 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 stream or the first cracker stream containing r-pyrolysis oil can differ from the steam to hydrocarbon ratio of the non-recovered 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 no 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 no 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 no more than 0.45, 0.42, 0.40, 0.37, 0.35, 0.32 or 0.30.

[0337] In one embodiment or in combination with any of the embodiments mentioned herein, the temperature of the stream containing r-pyrolysis oil 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 when the streams are introduced separately and passed through the furnace. For example, the temperature of the r-pyrolysis oil stream as it passes through the crossover section can be different from the temperature of the non-recovery cracker feed (e.g., C2-C4 or C5-C6) as it passes through the crossover section in another coil. 22 ) differs 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%. This percentage can be calculated based on the temperature of the non-recycled stream according to the following formula:

[0338] [(r - temperature of pyrolysis oil stream - temperature of non-recovery cracker stream)] / (temperature of non-recovery cracker steam), expressed as a percentage.

[0339] The difference may be higher or lower. The average temperature of the stream containing r-pyrolysis oil at the crossover section may 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., instead of recycling The average temperature of the cracker feed may 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 no more than 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525 or 500°C.

[0340] The heated cracker stream typically has a temperature of 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 no 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 radiant section via a cross section.

[0341] In one embodiment or in combination with any of the embodiments mentioned herein, a 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 of the embodiments mentioned, by volume.

[0342] When the stream containing r-pyrolysis oil is atomized before entering the cross section, one or more atomizing nozzles can be used for atomization. Atomization can be carried out in or outside the furnace. In one embodiment or in combination with any embodiment mentioned herein, an atomizing agent can be added to the stream containing r-pyrolysis oil during or before the atomization of the stream containing r-pyrolysis oil. The atomizing agent can include steam, or it can mainly include ethane, propane or a combination thereof. When used, the atomizing agent can be at least 1wt%, 2wt%, 4wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 10wt%, 25wt% or 30wt%, and / or no more than 50wt%, 45wt%, 40wt%, 35wt%, 30wt%, 25wt%, 20wt%, 15wt% or 10wt% in the amount present in the stream to be atomized (e.g., the composition containing r-pyrolysis oil).

[0343] Then the r-pyrolysis oil stream through atomization or gasification can be injected into the cracker stream through the cross section or combined with it.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 of about 45,50,35,30,25,20,15,10,5 or 0 ° with vertical.Nozzle or multiple nozzles can also be oriented to discharge the atomized stream into the coil in the furnace at an angle parallel to or parallel to the axial centerline of the coil at the introduction point.In the cross and / or convection section of the furnace, at least two, three, four, five, six or more nozzles can be used to spray the step of atomizing r-pyrolysis oil.

[0344] In one embodiment or in combination with any embodiment mentioned herein, atomized r-pyrolysis oil can be fed alone or in combination with at least a portion of the non-recovery 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 no more than 120, 110, 100, 90, 95, 80, 85, 70, 65, 60 or 55°C.

[0345] 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. cooler than the temperature of the cracked gas stream to which it is added, and / or no 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. cooler than the temperature of the cracked gas stream to which it is added. 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 comprise primarily C2-C4 components, ethane, propane, or a combination thereof. The combined cracker stream may 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 of the mentioned embodiments, by volume.

[0346] The temperature of the cracker stream passing through the crossover section may 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 no more than 850, 840, 830, 820, 810, 800, 790, 800, 815, 820, 830, 820, 815, 800, 890, 80 ...5, 810, 815, 820, 625, 630, 635, 640, 645, 650, 660, 670 or 680°C. 75, 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.

[0347] The resulting cracker feed stream then enters the radiant section. In one embodiment or in combination with any of the embodiments mentioned herein, the cracker stream from the convection section (with or without r-pyrolysis oil) can be passed through a vapor liquid separator to separate the stream into heavy and light fractions before further cracking the light fractions in the radiant section of the furnace. Figure 8 An example of this is shown in .

[0348] In one embodiment or in combination with any of the embodiments mentioned herein, the vapor liquid separator 640 may include a flash tank, while in other embodiments, it may include a fractionation column. As the stream 614 passes through the vapor liquid separator 640, the gas stream impinges on and flows through the trays, and the liquid from the trays falls to the bottom stream 642. The vapor liquid separator may also include a demister or chevron or other device located near the vapor outlet to prevent liquid from being carried from the vapor liquid separator 640 into the gas outlet.

[0349] 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 no more than about 650, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, or 275°C so that the passage of the heated cracker stream exiting the convection section 610 through the vapor liquid separator 640 can be carried out at a temperature of at least 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650°C, and / or no more than 800, 775, 750, 725, 700, 675, 650, 625°C. When heavier components are present, at least a portion or substantially all of the heavier components may be removed in the heavy components as bottom stream 642. At least a portion of the light fraction 644 from separator 640 may be removed alone or with one or more other cracker streams, such as primarily C5-C 22 The hydrocarbon stream or the combination of C2-C4 hydrocarbon streams is introduced into the cross section or radiation zone pipe 624 after separation.

[0350] refer to Figure 5 and 6 , the cracker feed stream (non-recycled cracker feed stream or when combined with an r-pyrolysis oil feed stream) 350 and 650 can be introduced into the furnace coils at or near the entrance of the convection section. The cracker feed stream 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 in 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 embodiment described herein, steam can be used in the same furnace ( Figure 5Steam 360 and 660 may be added to the cracker feed (or any intermediate cracker feed stream within 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 by volume in one embodiment or in combination with any of the mentioned embodiments.

[0351] The heated cracker stream typically has a temperature of 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 ° C, and / or no more than 850, or no more than 840, or no more than 830, or no more than 820, or no more than 810, or no more than 800, or no more than 790, or no more than 780, or no 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 °C, or in the range of 500 to 710°C, 620 to 740°C, 560 to 670°C, or 510 to 650°C, and then may pass from the convection section 610 of the furnace via the crossover section 630 to the radiant section 620. In one embodiment or in combination with any embodiment mentioned herein, the feed stream 550 containing r-pyrolysis oil may be added to the cracker stream at the crossover section 530, such as Figure 6When introduced into the furnace at the intersection, the r-pyrolysis oil may be at least partially vaporized or atomized before being combined with the cracker stream at the intersection. The temperature of the cracker stream passing through the intersection 530 or 630 may 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 ° C, and / or no more than 850, or no more than 840, or no more than 830, or no more than 820, or no more than 8 10, 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 620 to 740°C, 550 to 680°C, 510 to 630°C,

[0352] The resulting cracker feed stream then passes through a radiant section, wherein the feed stream containing the 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 may 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 seconds, and / or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.9, or no more than 0.8, or no more than 0.75, or no more than 0.7, or no more than 0.65, or no more than 0.6, or no more than 0.5, in each case 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 ° C, and / or does not exceed 850, or does not exceed 840, or does not exceed 830, or does not exceed 820, or does not exceed 810, or does not exceed 800, or does not exceed 890, or does not exceed 880, or does not exceed 890, or does not exceed 810. 770°C, or not more than 760°C, or not more than 750°C, or not more than 740°C, or not more than 730°C, or not more than 720°C, or not more than 710°C, or not more than 705°C, or not more than 700°C, or not more than 695°C, or not more than 690°C, or not more than 685°C, or not more than 680°C, or not more than 675°C, or not more than 670°C, or not more than 665°C, or not more than 660°C, or not more than 655°C, or not more than 650°C, in each case 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.

[0353] The coil outlet temperature may 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 ° C, and / or no more than 1000, or no more than 990, or no more than 980, Or not more than 970, or not more than 960, or not more than 950, or not more than 940, or not more than 930, or not more than 920, or not more than 910, or not more than 900, or not more than 890, or not more than 880, or not more than 875, or not more than 870, or not more than 860, or not more than 850, or not more than 840, or not more than 830, in each case ° C, in the range of 730 to 900 ° C, 750 to 875 ° C, or 750 to 850 ° C.

[0354] The cracking carried out in the furnace coils may include cracking the cracker feed stream under a set of processing conditions including a target value for 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 may include hydrocarbon molar flow rate and total molar flow rate. When two or more cracker streams pass through the separate coils in the furnace, one of the coils may be operated under a first set of processing conditions, and at least one of the other coils may be operated under a second set of processing conditions. At least one target value for an operating parameter from the first set of processing conditions may differ from the target value for the same parameter in the second set of conditions 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, by no more than about 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, or 15%. Examples include 0.01-30%, 0.01-20%, 0.01-15%, 0.03-15%. The percentage is calculated according to the following formula:

[0355] [(measured value of the operating parameter) - (target value of the operating parameter)] / [(target value of the operating parameter)], expressed as a percentage.

[0356] As used herein, the term "different" means higher or lower.

[0357] The coil outlet temperature may be at least 640, 650, 660, 670, 680, 690, 700, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820°C, and / or no more than 1000, 990, 980, 970, 960, 950, 940, 930, 920, 910, 900, 890, 880, 875, 870, 860, 850, 840, 830°C, in the range of 730 to 900°C, 760 to 875°C or 780 to 850°C.

[0358] In one embodiment or in combination with any embodiment mentioned herein, the addition of r-pyrolysis oil to the cracker feed stream can result in a change in one or more of the above operating parameters compared to the value of the operating parameter when the same cracker feed stream is treated 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) 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% from the value of the same parameter when the same feed stream without r-pyrolysis oil is treated. The percentages are calculated according to the following formula:

[0359] [(measured value of the operating parameter) - (target value of the operating parameter)] / [(target value of the operating parameter)], expressed as a percentage.

[0360] 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 of the embodiments 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 of the methods mentioned herein, and the combined stream can be cracked to achieve a second coil outlet temperature (COT2) different from COT1.

[0361] In some cases, when the r-pyrolysis oil is heavier than the cracker stream, COT2 may be less than COT1, while in other cases, when the r-pyrolysis oil is lighter than the cracker stream, COT2 may be greater than or equal to COT1. When the r-pyrolysis oil is lighter than the cracker stream, it may have a 50% boiling point that is higher than the 50% boiling point of the cracker stream by at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, and / or no more than 80%, 75%, 70%, 65%, 60%, 55%, or 50%. The percentages are calculated according to the following formula:

[0362] [(r-50% boiling point of pyrolysis oil in R)-(50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0363] Alternatively or additionally, the 50% boiling point of the r-pyrolysis oil may 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 may include, for example, vacuum gas oil (VGO), atmospheric gas oil (AGO) or even coker gas oil (CGO) or a combination thereof.

[0364] When the r-pyrolysis oil is lighter than the cracker stream, it may 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 no more than 80%, 75%, 70%, 65%, 60%, 55%, or 50%. The percentages are calculated according to the formula:

[0365] [(r - 50% boiling point of pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0366] Additionally or alternatively, the 50% boiling point of the r-pyrolysis oil may 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 may include, for example, LPG, naphtha, kerosene, natural gasoline, straight run gasoline, and combinations thereof.

[0367] In some cases, COT1 may differ from COT2 by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50°C (higher or lower), and / or no 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 no more than 80%, 75%, 70%, 65%, 60%, 50%, 45%, or 40% (percentages herein are 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 no more than 1200, 1175, 1150, 1140, 1130, 1120, 1110, 1100, 1090, 1080, 1070, 1060, 1050, 1040, 1030, 1020, 1010, 1000, 990, 980, 970, 960950, 940, 930, 920, 910 or 900°C.

[0368] 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 (for clarity, as determined across the entire coil as opposed to tubes within the coil) is between 60 and 165 kilograms per second (kg / s) per square meter (m 2 ) 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.

[0369] In one embodiment or in combination with any of the mentioned embodiments, there is provided a process for preparing one or more olefins by:

[0370] (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit;

[0371] (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

[0372] (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.

[0373] The reason or cause of 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 mentioned embodiments, in one embodiment or in combination with any of the other mentioned embodiments, the COT2 temperature on the coil of the r-pyrolysis oil feed can be set to a temperature lower than COT1 ("set" mode), or 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 floating" mode).

[0374] In the setting mode, COT2 can be set to be at least 5°C lower than COT1. All 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 setting 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 thermal energy required for cracking r-pyrolysis oil can be utilized. Although the cracking severity of the cracker feed (e.g., C2-C4) can be reduced, thereby increasing the amount of unconverted C2-C4 feed in a single pass, a higher amount of unconverted feed (e.g., C2-C4 feed) is required to increase the final yield of olefins such as ethylene and / or propylene in multiple passes by recycling the unconverted C2-C4 feed through the furnace. Alternatively, other cracker products, such as aromatic hydrocarbons and diene content, can be reduced.

[0375] In one embodiment or in combination with any of the mentioned embodiments, 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) in said coil, the COT2 in the coil can be fixed in the set mode to be lower than COT1, or at least 1, 2, 3, 4°C 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. It is advantageous to fix COT2 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 of the pyrolysis oil, a reduced COT2 temperature can help reduce by-product formation, and while the single pass olefin yield is also reduced, the final yield of olefins can be satisfactory or increased by recycling unconverted cracker feed through the furnace.

[0376] In set mode, the temperature can be fixed or set by adjusting the furnace to burner fuel ratio.

[0377] In one embodiment or in combination with any of the other mentioned embodiments, COT2 is in free floating mode and is the temperature of the coils of the pyrolysis oil feed due to feeding pyrolysis oil and allowing COT2 to rise or fall without fixing it. In this embodiment, not all coils contain r-pyrolysis oil. The thermal energy provided to the coils containing r-pyrolysis oil can be provided by maintaining a constant temperature of the burners on the coils containing non-recovered cracker feed or the fuel feed rate. Without fixing or setting COT2, when pyrolysis oil is fed to the cracker stream to form a combined cracker stream having a higher hydrocarbon mass flow rate than the hydrocarbon mass flow rate of the cracker stream in step (a), COT2 can be lower than COT1. Adding pyrolysis oil to the cracker feed to increase the hydrocarbon mass flow rate of the combined cracker feed reduces COT2 and can exceed the warming effect of using a higher average molecular weight pyrolysis oil. These effects can be seen while other cracker conditions are kept constant, such as the dilution steam ratio, feed location, composition of cracker feed and pyrolysis oil, and fuel feed rate to the combustor burners in the furnace on tubes containing only cracker feed and no r-pyrolysis oil feed.

[0378] COT2 may 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 no more than about 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70, or 65°C lower than COT1.

[0379] Regardless of the reason or cause of the temperature drop in COT2, the time period for joining step (a) is flexible, but ideally, step (a) reaches a steady state before joining step (b). In one embodiment or in combination with any of the mentioned embodiments, step (a) operates 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 has never received a pyrolysis oil feed or a combination of a pyrolysis oil feed and a pyrolysis oil in operation. Step (b) can be the first time the furnace receives a pyrolysis oil feed or a combined cracker feed containing pyrolysis oil. In one embodiment or in combination with any of the other mentioned embodiments, steps (a) and (b) may be repeated multiple times per 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, as measured on a calendar year. Formulating the feed of pyrolysis oil represents multiple cycles of steps (a) and (b). When the feed supply of pyrolysis oil is exhausted or shut off, COT1 is allowed to reach a steady-state temperature before engaging step (b).

[0380] Alternatively, the feeding of pyrolysis oil to the cracker feed may be continued throughout the course of at least 1 calendar year or at least 2 calendar years.

[0381] In one embodiment or in combination with any of the other mentioned embodiments, the composition of the cracker feed used in steps (a) and (b) remains constant, allowing for regular composition changes to be observed over the course of a calendar year. In one embodiment or in combination with any of the other mentioned embodiments, the flow of the cracker feed in step (a) is continuous and remains continuous as the pyrolysis oil enters the cracker feed to prepare the combined cracker feed. The cracker feeds in steps (a) and (b) may be taken from the same source, such as the same stock or pipeline.

[0382] In one embodiment or in combination with any of the mentioned embodiments, COT2 is below or at least 1, 2, 3, 4°C 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 that the pyrolysis oil is fed to the cracking furnace stream to form the combined cracking furnace stream, the measurement time being when all conditions except COT remain constant, such as cracking furnace and pyrolysis oil feed rates, steam ratio, feed location, composition of cracking furnace feed and pyrolysis oil, etc.

[0383] In one embodiment or in combination with any of the mentioned embodiments, the hydrocarbon mass flow rate of the combined cracker feed can be increased. A method for preparing one or more olefins by the following steps is now provided:

[0384] (a) cracking a cracker stream at a first hydrocarbon mass flow rate (MF1) in a cracking unit;

[0385] (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, the combined cracker stream having a second hydrocarbon mass flow rate (MF2) higher than MF1; and

[0386] (c) cracking the combined cracker stream in the cracking unit at MF2 to obtain an olefin-containing effluent having a combined yield of ethylene and propylene that is the same as or higher than that obtained by cracking only the cracker stream at MF1.

[0387] Yield refers to the production of the target compound per unit time, expressed as 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, thereby increasing the throughput of the furnace. Without being bound by theory, it is believed that this is possible because the total energy of the reaction of adding pyrolysis oil is not endothermic relative to the total energy of the reaction 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 heat energy is available per unit time to continue cracking the heavy feed. MF2 can be increased by at least 1%, 2%, 3%, 4%, 5%, 7%, 10%, 10%, 13%, 15%, 18%, or 20% through the coils of 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 furnace output, provided that at least one coil is processing r-pyrolysis oil. Alternatively, the increase in combined ethylene and propylene production can be achieved without changing the heat flux in the furnace, or without changing the r-pyrolysis oil feed coil outlet temperature, or without changing the fuel feed rate to the burners used to heat the coils containing only non-recycled cracker feed, or without changing the fuel feed rate to 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, or 50% or at least 50%, or 75% or at least 75%, or through all coils in the furnace.

[0388] The olefin-containing effluent stream may have a total yield of propylene and ethylene from the combined cracker streams at MF2 that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% greater than the yield of propylene and ethylene of the effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, as determined by:

[0389]

[0390] Among them, mf1 is the combined production of propylene and ethylene components in the cracker effluent under MF1 produced without using r-pyrolysis oil; and

[0391] O mf2 is the combined production of propylene and ethylene components in the cracker effluent at MF2 made using r-pyrolysis oil.

[0392] The total production of propylene and ethylene in the combined cracker stream at MF2 in the olefin-containing effluent stream is, as a percentage, at least 1%, 5%, 10%, 15%, 20%, and / or up to 80%, 70%, 65% of the increase in mass flow rate between MF2 and MF1. 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%, then the increase in olefins as a function of the increase in mass flow rate is 50% (2.5% / 5% x 100). This can be determined as:

[0393]

[0394] wherein 1% is the percentage increase (using the above formula) between the combined production of propylene and ethylene components in the cracker effluent when MF1 is produced without r-pyrolysis oil and MF2 is produced with r-pyrolysis oil; and

[0395] ΔMF% is the percentage of increase of MF2 compared to MF1.

[0396] Alternatively, the olefin-containing effluent stream may have a total wt% of propylene and ethylene from the combined cracker streams 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 of an effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, as determined by:

[0397]

[0398] Where E mf1 is the combined wt% of propylene and ethylene components in the cracker effluent under MF1 produced without using r-pyrolysis oil; E mf2 is the combined wt% of propylene and ethylene components in the cracker effluent at MF2 made using r-pyrolysis oil.

[0399] Also provided is a method for preparing one or more olefins, the method comprising:

[0400] (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);

[0401] (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

[0402] (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),

[0403] wherein when the r-pyrolysis oil is heavier than the cracker stream, COT2 is equal to or less than COT1,

[0404] Wherein, when the r-pyrolysis oil is lighter than the cracker stream, COT2 is greater than or equal to COT1.

[0405] In this method, the above embodiments are also applicable here for COT2 which is lower than COT1. COT2 can be in set mode or free floating mode. In one embodiment or in combination with any other mentioned embodiment, COT2 is in 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 set mode.

[0406] In one embodiment or in combination with any of the mentioned embodiments, there is provided a process for preparing one or more olefins by:

[0407] (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit;

[0408] (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

[0409] (c) cracking the combined cracker stream at a second coil outlet temperature (COT2) in the cracking unit, wherein the second coil outlet temperature is higher than the first coil outlet temperature.

[0410] COT2 may be at least 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, 50°C higher than COT1, and / or no more than about 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70, or 65°C higher.

[0411] In one embodiment or in combination with any of the other mentioned embodiments, r-pyrolysis oil is added to the inlet of at least one coil, or at least two coils, or at least 50%, or at least 75%, or all 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 coils receiving r-pyrolysis oil feed. At least one, or at least two combined cracker streams, or at least all r-pyrolysis oil feed coils may have a COT2 higher than their respective COT1. In one embodiment or in combination with any of the mentioned embodiments, 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-recycled component cracker feed, wherein at least one coil in the cracking furnace is fed with r-pyrolysis oil, and at least some of the coils or multiple coils fed with r-pyrolysis oil have a COT2 higher than their respective COT1.

[0412] In one embodiment or in combination with any of the mentioned embodiments, 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 no more than 2% difference, or no more than 1% difference, or no more than 0.25% difference. 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 (wherein at least 1 tube contains a non-recovery cracker stream), COT2 on the coil containing r-pyrolysis oil can be increased relative to COT1. This is the case even if the pyrolysis oil having a larger number average molecular weight than 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:

[0413] (i). Lower thermal energy is required to crack the pyrolysis oil in the combined stream.

[0414] (ii) Exothermic reactions occur in the cracking products of the pyrolysis oil, such as the Diels-Alder reaction.

[0415] This effect can be seen when other process variables are constant, such as combustor fuel rate, dilution steam ratio, feed location and cracker feed composition.

[0416] In one embodiment or in combination with any of the mentioned embodiments, COT2 can be set or fixed to a higher temperature (set mode) than COT1. 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, which would otherwise reduce COT2. The higher second coil outlet temperature (COT2) can help with increased severity and reduced yield of unconverted lighter cracker feeds (e.g., C2-C4 feeds), which can help with downstream capacity-constrained fractionators.

[0417] In one embodiment or in combination with any of the embodiments mentioned, no matter COT2 is higher or lower than COT1, when comparing 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 the cracker composition for preparing 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 pyrolysis oil is continuously fed to the feed of the cracker feed 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.

[0418] In any of the mentioned embodiments, the amount of the cracker feed increased or decreased in step (b) may 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 mentioned embodiments, the amount of the cracker feed decreased in step (b) may be an amount corresponding to the addition of pyrolysis oil by weight. In one embodiment or in combination with any of the mentioned embodiments, 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).

[0419] In any or all of the mentioned embodiments, if any one coil in the furnace satisfies the relationship, but it may also exist 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 is satisfied.

[0420] In one embodiment or in combination with any embodiment mentioned herein, the burners in the radiant zone provide an average heat flux into the coil of 60 to 160 kW / m 2 , or 70 to 145kW / m 2 , or 75 to 130kW / 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 pressure (bara), or 2.5 to 7 bar, and 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 furnace coil in the radiant section may 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.

[0421] In one embodiment or in combination with any embodiment mentioned herein, the yield of olefin-ethylene, propylene, butadiene or a combination 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" refers to product mass / raw material mass × 100%. The olefin-containing effluent stream comprises ethylene, propylene, or ethylene and propylene in the following content: 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, based on the total weight of the effluent stream.

[0422] 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 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, or 90 wt%, based on the weight of the olefin-containing effluent. The stream can contain mainly ethylene, mainly propylene, or mainly ethylene and propylene, based on the olefins in the olefin-containing effluent, or based on the weight of the 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 may 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 no 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 the effluent stream obtained by cracking the same cracker feed but without r-pyrolysis oil at the same dilution steam ratio, feed location, cracker feed composition (other than r-pyrolysis oil), and placing the coils fed with r-pyrolysis oil in floating mode, or if all coils in the furnace are fed with r-pyrolysis oil, at the same temperature before feeding r-pyrolysis oil. As described above, this is possible when the mass flow rate of the cracker feed remains substantially the same when r-pyrolysis oil is added relative to the original feed of the cracker streams, resulting in a higher hydrocarbon mass flow rate of the combined cracker streams.

[0423] The olefin-containing effluent stream may have a propylene:ethylene ratio that is at least 1% higher, or at least 2% higher, or at least 3% higher, or at least 4% higher, or at least 5% higher, or at least 7% higher, or at least 10% higher, or at least 12% higher, or at least 15% higher, or at least 17% higher, or at least 20% higher than the propylene:ethylene ratio of the effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil. Alternatively, in addition, the olefin-containing effluent stream may have a propylene:ethylene ratio that is up to 50% higher, or up to 45% higher, or up to 40% higher, or up to 35% higher, or up to 25% higher, or up to 20% higher than the propylene:ethylene ratio of the effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, in each case determined as:

[0424]

[0425] wherein E is the propylene:ethylene ratio in a cracker effluent produced without the use of r-pyrolysis oil, expressed in wt%; and

[0426] Er is the propylene:ethylene ratio in the cracker effluent prepared using r-pyrolysis oil, expressed in wt%.

[0427] In one embodiment or in combination with any embodiment mentioned herein, relative to the effluent stream without r-pyrolysis oil, the amount of ethylene and propylene in the olefin-containing effluent stream of cracking can remain substantially unchanged or increase. Surprisingly, liquid r-pyrolysis oil can be fed to a gas feed furnace, which is received and cracked mainly as a C2-C4 composition and obtains an olefin-containing effluent stream, which can remain substantially unchanged or improved relative to the C2-C4 cracker feed without r-pyrolysis oil in some cases. The high molecular weight of r-pyrolysis oil can mainly contribute to the formation of aromatic hydrocarbons, and only participates in the formation of olefins (especially ethylene and propylene) in a small amount. However, we find that, under the same hydrocarbon mass flow rate, relative to the cracker feed without r-pyrolysis oil, when r-pyrolysis oil is added to the cracker feed to form a combined cracker feed, the combined weight percentage of ethylene and propylene, even the output does not significantly decline, and in many cases remains the same or may increase. The olefin-containing effluent stream may have a combined 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 feed but without the r-pyrolysis oil, as determined by:

[0428]

[0429] wherein E is the combined wt% of the propylene and ethylene components of the cracker effluent produced without using r-pyrolysis oil; and

[0430] Er is the combined wt% of propylene and ethylene components in the cracker effluent produced using r-pyrolysis oil.

[0431] In one embodiment or in combination with one or more embodiments mentioned herein, the wt% of propylene in the olefin-containing effluent stream can be increased 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. When the dilution steam ratio is at least 0.3, or at least 0.35, or at least 0.4, the increase in wt% of propylene 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%, wherein the increase is measured as the simple difference in wt% of propylene between an olefin-containing effluent stream prepared with an r-pyrolysis oil having a dilution steam ratio of 0.2 and an olefin-containing effluent stream prepared with an r-pyrolysis oil having a dilution steam ratio of at least 0.3, all other conditions being the same.

[0432] When the dilution steam ratio is increased as described above, the propylene:ethylene ratio may also increase, or may be at least 1% higher, or at least 2% higher, or at least 3% higher, or at least 4% higher, or at least 5% higher, or at least 7% higher, or at least 10% higher, or at least 12% higher, or at least 15% higher, or at least 17% higher, or at least 20% higher than the propylene:ethylene ratio of an olefin-containing effluent stream produced using r-pyrolysis oil having a dilution steam ratio of 0.2.

[0433] In one embodiment or in combination with one or more embodiments described herein, the olefin-containing effluent stream can have a reduced wt% of methane when the dilution steam ratio increases, 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%, measured as the absolute difference in wt% between the olefin-containing effluent stream at a dilution steam ratio of 0.2 and a higher dilution steam ratio.

[0434] In one embodiment or in combination with one or more embodiments mentioned herein, when measuring relative to the cracker feed without r-pyrolysis oil and all other conditions being identical (comprising hydrocarbon mass flow rate), the amount of unconverted products in the olefin effluent is reduced.For example, the amount of propane and / or ethane can be reduced by adding r-pyrolysis oil.This can be conducive to reducing the mass flow rate of recovery loop, thereby (a) reducing low temperature energy cost and / or (b) if equipment is capacity-limited, then potentially increasing the capacity of equipment.In addition, if propylene fractionator has reached its capacity limit, then it can eliminate the bottleneck of propylene fractionator.The amount of unconverted products in the olefin 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%.

[0435] In one embodiment or in combination with one or more embodiments mentioned herein, when measured relative to a cracker feed without r-pyrolysis oil, the amount of unconverted products (e.g., propane and ethane combined) in the olefin-containing effluent is reduced, while the combined and yield of ethylene and propylene does not decrease and even improves. Optionally, all other conditions are the same, including hydrocarbon mass flow rate and temperature, wherein the fuel feed rate of the heating burner to the non-recovery cracker feed coil remains unchanged, or optionally when the fuel feed rate to all coils in the furnace remains unchanged. Alternatively, the same relationship can be established on a wt% basis rather than on a yield basis.

[0436] For example, the total amount of propane and ethane (either or both of the output 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 up to 40%, or up to 35%, or up to 30%, in each case without a reduction in the total amount of ethylene and propylene, and can even be accompanied by an increase in the total amount of ethylene and propylene. For example, the amount of 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 up to 40%, or up to 35%, or up to 30%, in each case without a reduction in the total amount of ethylene and propylene, and can even be accompanied by an increase in the total amount of ethylene and propylene. In any of these embodiments, the cracker feed (other than r-pyrolysis oil and as fed to the inlet of the convection zone) can be predominantly propane, or at least 90 mol% propane, or at least 95 mol% propane, or at least 96 mol% propane, or at least 98 mol% propane on a molar basis; or the fresh supply of cracker feed can be at least HD5 quality propane.

[0437] In one embodiment or in combination with one or more embodiments mentioned herein, the propane:(ethylene and propylene) ratio in the olefin-containing effluent decreases with the addition of r-pyrolysis oil to the cracker feed, when measured in wt% or monthly production relative to the same cracker feed without pyrolysis oil and all other conditions being the same. The propane:(ethylene and propylene) ratio in the olefin-containing effluent may 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 means that high amounts of ethylene+propylene can be achieved or maintained while correspondingly reducing unconverted products such as propane.

[0438] In one embodiment or in combination with one or more embodiments mentioned herein, when the r-pyrolysis oil and steam are fed downstream of the inlet of the convection box, or when one or both of the r-pyrolysis oil and steam are fed at a crossover position, the C 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, the C in the olefin-containing effluent is about 1.3 % when measured relative to feeding r-pyrolysis oil at the convection box inlet. 6+ The amount of product may be increased by 5%, or 10%, or 15%, or 20%, or 30%, all other conditions being the same. The % increase may be calculated as:

[0439]

[0440] Where E i The C in the olefin-containing cracker effluent prepared by introducing r-pyrolysis oil at the inlet of the convection box 6+ content;

[0441] E d The C in the olefin-containing cracker effluent is obtained by introducing pyrolysis oil and steam downstream of the convection box inlet. 6+ content.

[0442] In one embodiment or in combination with any embodiment described herein, the cracked olefin-containing effluent stream can contain relatively small amounts of aromatic hydrocarbons and other heavy components. For example, the olefin-containing effluent stream can contain at least 0.5 wt%, 1 wt%, 2 wt%, or 2.5 wt%, and / or no more than about 20 wt%, 19 wt%, 18 wt%, 17 wt%, 16 wt%, 15 wt%, 14 wt%, 13 wt%, 12 wt%, 11 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt% of aromatic hydrocarbons, based on the total weight of the stream. We have found that C in the olefin-containing effluent stream can contain relatively small amounts of aromatic hydrocarbons and other heavy components. 6+ The substance level may 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%. 6+ The substances include all aromatic hydrocarbons, as well as all paraffins and cyclic compounds having a carbon number of 6 or more. As used throughout the text, the amount of aromatic hydrocarbons referred to can be determined by C 6+ The amount of substance is expressed because the amount of aromatic hydrocarbons will not exceed C 6+ The amount of substance.

[0443] The olefin-containing effluent may have a 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 1, 7:1, 28:1, 29:1 or 30:1, and / or a weight ratio of olefins to aromatics of 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, "olefins to aromatics" is the ratio of the total weight of C2 and C3 olefins as defined above to the total weight of aromatics. In one embodiment or in combination with any embodiment mentioned herein, the effluent stream can have at least a 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 ratio of olefins to aromatics.

[0444] The olefin-containing effluent may have olefins: C 6+ The olefin-containing effluent may have a ratio (by weight) of 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 ratio of at least 1:1. 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, "olefins to aromatics" is the ratio of the total weight of C2 and C3 olefins to the total weight of aromatics as defined above.

[0445] Additionally or alternatively, the olefin-containing effluent stream may have olefins and 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.

[0446] In one embodiment or in combination with any of the embodiments mentioned herein, the olefin:aromatic ratio decreases with increasing amounts of r-pyrolysis oil added to the cracker feed. Since r-pyrolysis oil cracks at lower temperatures, it will crack earlier than propane or ethane and therefore have more time to react to produce other products, such as aromatics. Although the aromatic content in the olefin-containing effluent increases with increasing amounts of pyrolysis oil, as described above, the amount of aromatics produced is significantly low.

[0447] Olefin-containing compositions can also include trace aromatic hydrocarbons.For example, composition can have at least 0.25wt%, 0.3wt%, 0.4wt%0.5wt%, and / or be no more than about 2wt%, 1.7wt%, 1.6wt%, 1.5wt% benzene content.Additionally or alternatively, composition can have at least 0.005wt%, 0.010wt%, 0.015wt% or 0.020wt% and / or be no more than 0.5wt%, 0.4wt%, 0.3wt% or 0.2wt% toluene content.Two percentages are all based on the gross weight of composition. Alternatively or additionally, the benzene content of the effluent may be at least 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt% or 0.55wt%, and / or no more than about 2wt%, 1.9wt%, 1.8wt%, 1.7wt% or 1.6wt%, and / or the toluene content may be at least 0.01wt%, 0.05wt% or 0.10wt%, and / or no more than 0.5wt%, 0.4wt%, 0.3wt% or 0.2wt%.

[0448] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent taken out from the cracking furnace of the composition comprising r-pyrolysis oil cracked may include an increased amount of one or more compounds or by-products not present in the olefin-containing effluent stream formed by processing conventional cracker feed. For example, the cracker effluent formed by cracking r-pyrolysis oil (r-olefin) may include an increased amount of 1,3-butadiene, 1,3-cyclopentadiene, dicyclopentadiene or a combination of these components. In one embodiment or in combination with any embodiment mentioned herein, the total amount (by weight) of these components may be higher than at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85% under the same conditions and at the same mass feed rate but without the same cracker feed stream of r-pyrolysis oil processing. The total amount of 1,3-butadiene (by weight) 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 the r-pyrolysis oil treatment. The total amount of 1,3-cyclopentadiene (by weight) 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 the r-pyrolysis oil treatment. The total amount of dicyclopentadiene (by weight) 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 the r-pyrolysis oil treatment. The percentage difference is calculated by dividing the difference in weight percentage of one or more of the above components in the r-pyrolysis oil and the conventional stream by the amount of the component in the conventional stream (by weight percentage), or:

[0449]

[0450] wherein E is the wt% of the components in the cracker effluent produced without using r-pyrolysis oil;

[0451] Er is the wt% of components in the cracker effluent made with r-pyrolysis oil.

[0452] 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 2000ppm, at least 5000ppm, at least 8000ppm, or at least 10,000ppm, based on the total weight of the effluent stream from the furnace. It may also be no more than 50,000ppm, no more than 40,000ppm, no more than 30,000ppm, or no more than 25,000ppm, or no more than 10,000ppm, or no more than 6,000ppm, or no more than 5000ppm.

[0453] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream can include methylacetylene and propadiene (MAPD). The amount of MAPD can be at least 2ppm, at least 5ppm, at least 10ppm, at least 20ppm, at least 50ppm, at least 100ppm, at least 500ppm, at least 1000ppm, at least 5000ppm, or at least 10,000ppm, based on the gross weight of the effluent stream. It can also be no more than 50,000ppm, no more than 40,000ppm, or no more than 30,000ppm, or no more than 10,000ppm, or no more than 6,000ppm, or no more than 5,000ppm.

[0454] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream may contain a small amount or no carbon dioxide. The olefin-containing effluent stream may have a carbon dioxide amount in wt%, which is no more than the amount of carbon dioxide in the effluent stream obtained by cracking the same cracker feed under equivalent conditions but without r-pyrolysis oil, or an amount not higher than 5% of the carbon dioxide amount 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 no more than 1000ppm, or no more than 500ppm, or no more than 100ppm, or no more than 80ppm, or no more than 50ppm, or no more than 25ppm, or no more than 10ppm, or no more than 5ppm of carbon dioxide.

[0455] Now go to Fig. 9 , a block diagram illustrating the major elements of the furnace effluent processing section is shown.

[0456] like Fig. 9 As shown, the olefin-containing effluent stream from the cracking furnace 700, which includes the recovered components, is rapidly cooled (e.g., quenched) in a transfer line exchange ("TLE") 680, as shown. Figure 8As shown, to prevent the production of large amounts of undesirable byproducts and to minimize fouling in downstream equipment, as well as to produce steam. In one embodiment or in combination with any of the embodiments 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 performed immediately after the effluent stream leaves the furnace, such as within 1 to 30, 5 to 20, or 5 to 15 milliseconds. In one embodiment or in combination with any of the embodiments mentioned herein, the quenching step is performed in the quench zone 710 by heating the effluent in a heat exchanger (sometimes referred to as a transfer line exchanger, such as Figure 5 The TLE 340 is shown in Figure 8 In some embodiments, the quenching step is performed by indirect heat exchange with high pressure water or steam in the effluent (shown as TLE 680 in FIG. 1 ), while in other embodiments, the quenching step is performed by direct contact of the effluent with a quenching liquid 712 (shown as Fig. 9 ). The temperature of the quench liquid may be at least 65, or at least 80, or at least 90, or at least 100, in each case, ° C, and / or no more than 210, or no more than 180, or no more than 165, or no more than 150, or no more than 135, in each case, ° C. When a quench liquid is used, contacting may be conducted in a quench tower, and a liquid stream comprising gasoline and other similar boiling range hydrocarbon components may be removed from the quench tower. In some cases, a quench liquid may be used when the cracker feed is primarily liquid, and a heat exchanger may be used when the cracker feed is primarily vapor.

[0457] The resulting cooled effluent stream is then subjected to vapor-liquid separation, and the vapor is compressed in compression zone 720, such as in a gas compressor having, for example, 1 to 5 compression stages, with optional interstage cooling and liquid removal. The gas stream pressure at the outlet of the first set of compression stages is in the range of 7 to 20 bar gauge (barg), 8.5-18 psig (0.6 to 1.3 barg), or 9.5 to 14 barg.

[0458] The resulting compressed stream is then treated in an acid gas removal zone 722 to remove acid gases, including CO, CO2, and H2S, by contacting with an acid gas removal agent. Examples of acid gas removal agents may include, but are not limited to, caustic amines and various types of amines. In one embodiment or in combination with any of the embodiments mentioned herein, a single contactor may be used, while in other embodiments, a dual tower absorber-stripper configuration may be employed.

[0459] Then, the treated compressed olefin-containing stream can be further compressed via a compressor in another compression zone 724, optionally with 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 a fractionation section, where olefins and other components can be separated into various high-purity products or intermediate streams.

[0460] Now go to Fig.10 , a schematic diagram of the main steps of the fractionation section is provided. In one embodiment or in combination with any embodiment mentioned herein, the initial tower of the fractionation system may not be a demethanizer 810, but may be a deethanizer 820, a depropanizer 840, or any other type of tower. As used herein, the term "demethanizer" refers to a tower whose light key component is methane. Similarly, "deethanizer" and "depropanizer" refer to towers with ethane and propane as light key components, respectively.

[0461] like Fig.10As shown, the feed stream 870 from the quench stage can be introduced into a demethanizer (or other) 810, wherein methane and lighter (CO, CO2, H2) components 812 are separated from ethane and heavier components 814. The demethanizer is operated at a temperature of at least -145, or at least -142, or at least -140, or at least -135, in each case ° C, and / or no more than -120, -125, -130, -135 ° C. The bottoms stream 814 from the demethanizer is then introduced into a deethanizer 820, wherein C2 and lighter components 816 are separated from C3 and heavier components 818 by fractionation, the bottoms stream comprising 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 components introduced into the column. The deethanizer 820 may be operated at a top temperature of at least -35, or at least -30, or at least -25, or at least -20, in each case, °C, and / or no more than -5, -10, -10, -20 °C, and a top pressure of at least 3, or at least 5, or at least 7, or at least 8, or at least 10, in each case, barg, and / or no more than 20, or no more than 18, or no more than 17, or no more than 15, or no more than 14, or no more than 13, in each case, barg. The deethanizer 820 recovers the following total amount of C2 and lighter components introduced into the tower in the top stream: 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 99, in each case, percent. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 816 removed from the deethanizer comprises ethane and ethylene in amounts of 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 by weight percent, based on the total weight of the overhead stream.

[0462] like Fig.10As shown, the C2 and lighter overhead stream 816 from the deethanizer 820 is further separated in an ethane-ethylene fractionator (ethylene fractionator) 830. In the ethane-ethylene fractionator 830, an ethylene and lighter component stream 822 can be taken from the overhead of the column 830, or as a side stream from the upper 1 / 2 portion of the column, while ethane and any remaining heavier components are removed in a bottoms stream 824. The ethylene fractionation column 830 may be operated at a top temperature of at least -45, or at least -40, or at least -35, or at least -30, or at least -25, or at least -20, in each case ° C, and / or no more than -15, or no more than -20, or no more than -25, in each case ° C, and a top pressure of at least 10, or at least 12, or at least 15, in each case barg, and / or no more than 25, 22, 20 barg. The ethylene-rich top stream 822 may contain ethylene in an amount of 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, in each case weight percent, based on the total weight of the stream, and may be sent to a downstream processing unit for further processing, storage, or sale. The overhead ethylene stream 822 produced during cracking of the cracker feed containing r-pyrolysis oil is an r-ethylene composition or stream. In one embodiment or in combination with any embodiment mentioned herein, the r-ethylene stream can be used to prepare one or more petrochemical products.

[0463] The bottoms stream of the ethane-ethylene fractionator 824 can include 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 98 weight percent ethane in each case, based on the total weight of the bottoms stream. As previously described, all or a portion of the recovered ethane can be recycled to the cracking furnace as additional feedstock, either alone or in combination with a feed stream containing r-pyrolysis oil.

[0464] The liquid bottoms stream 818 from the deethanizer may be enriched in C3 and heavier components and may be separated in the depropanizer 840, such as Fig.10As shown. In the depropanizer 840, C3 and lighter components are removed as an overhead vapor stream 826, while C4 and heavier components can leave the tower in a liquid bottoms stream 828. The depropanizer 840 can be operated at a top temperature and top pressure of at least 20, or at least 35, or at least 40, in each case, ° C, and / or no more than 70, 65, 60, 55 ° C, and a top pressure of at least 10, or at least 12, or at least 15, in each case, barg, and / or no more than 20, or no more than 17, or no more than 15, in each case, barg. The depropanizer 840 recovers the following total amount of C3 and lighter components introduced into the tower in the overhead stream 826: 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 99, in each case, as a percentage. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 826 removed from the depropanizer 840 comprises propane and propylene in amounts of at least 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 98, in each case as weight percent, based on the total weight of the overhead stream 826.

[0465] The overhead stream 826 from the depropanizer 840 is introduced into a propane-propylene fractionator (propylene fractionator) 860, wherein propylene and any lighter components are removed in an overhead stream 832, while propane and any heavier components exit the column in a bottoms stream 834. The propylene fractionator 860 may be operated at an overhead temperature and an overhead pressure of at least 20, or at least 25, or at least 30, or at least 35, in each case, °C, and / or no more than 55, 50, 45, 40 °C, and an overhead pressure of at least 12, or at least 15, or at least 17, or at least 20, in each case, barg, and / or no more than 20, or no more than 17, or no more than 15, or no more than 12, in each case, barg. The overhead stream 860 rich in propylene can contain propylene in an amount of 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, in each case by weight percent, based on the total weight of the stream, and can be sent to a downstream processing unit for further processing, storage or sale. The overhead propylene stream produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-propylene composition or stream. In one embodiment or in combination with any embodiment mentioned herein, the stream can be used to prepare one or more petrochemical products.

[0466] The bottoms stream 834 from the propane-propylene fractionator 860 can include 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 98 weight percent propane, in each case based on the total weight of the bottoms stream 834. As previously described, all or a portion of the recovered propane can be recycled to the cracking furnace as additional feedstock, either alone or in combination with the r-pyrolysis oil.

[0467] Refer again Fig.10 , the bottom stream 828 from the depropanizer 840 can be sent to the debutanizer 850 for separating C4 components, including butenes, butanes and butadiene, from C5+ components. The debutanizer can be operated at a top temperature and a top pressure of at least 20, or at least 25, or at least 30, or at least 35, or at least 40, in each case, ° C, and / or not more than 60, or not more than 65, or not more than 60, or not more than 55, or not more than 50, in each case, ° C, and a top pressure of at least 2, or at least 3, or at least 4, or at least 5, in each case, barg, and / or not more than 8, or not more than 6, or not more than 4, or not more than 2, in each case, barg. The debutanizer recovers the following total amount of C4 and lighter components introduced into the tower in the overhead stream 836: 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 99, in each case as a percentage. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 836 removed from the debutanizer contains the following amount of butadiene: 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 as a weight percentage, based on the total weight of the overhead stream. The overhead stream 836 produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-butadiene composition or stream. The bottom stream 838 from the debutanizer mainly comprises C5 and heavier components in an amount of at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt% or at least 95 wt%, based on the total weight of the stream. The debutanizer bottom stream 838 can be sent for further separation, processing, storage, sale or use.

[0468] The overhead stream 836 or C4 from the debutanizer may be subjected to any conventional separation method such as extraction or distillation processes to recover a more concentrated butadiene stream.

[0469] Preparation and Application of Oxo Diols

[0470] In one embodiment or in combination with any of the mentioned embodiments, there is now provided a method for processing recycled component olefins, including, for example, recycled component propylene, by feeding r-olefins to a reactor in which r-aldehydes are produced, which are then condensed in the presence of a catalyst and optionally hydrogenated to form oxo diols. In some embodiments, the r-aldehydes may include r-butyraldehyde, particularly isobutyraldehyde, which may react with formaldehyde and optionally hydrogen to form oxo diols, including 2,2-dimethyl-1,3-propanediol.

[0471] In one embodiment or in combination with any of the mentioned embodiments, the concentration of r-olefins introduced into the reactor vessel is at least 90 wt%, or at least 95 wt%, or at least 97 wt%, or at least 99 wt%, based on the weight of the olefin composition fed to the aldehyde reactor.

[0472] Similarly, in one embodiment or in combination with any of the mentioned embodiments, the concentration of r-aldehyde introduced into the reactor vessel for reacting the aldehyde to form oxo diol is at least 90 wt%, or at least 95 wt%, or at least 97 wt%, or at least 99 wt%, based on the weight of the aldehyde composition fed to the oxo diol reactor.

[0473] In one embodiment or in combination with any of the mentioned embodiments, the olefins or aldehydes fed to the reaction vessel do not contain recycled components. In another embodiment, at least a portion of the olefin or aldehyde composition fed to the reaction vessel is directly or indirectly derived from the cracking of r-pyrolysis oil or obtained from r-pyrolysis gas. For example, at least 0.005wt%, or at least 0.01wt%, or at least 0.05wt%, or at least 0.1wt%, or at least 0.15wt%, or at least 0.2wt%, or at least 0.25wt%, or at least 0.3wt%, or at least 0.35wt%, or at least 0.4wt%, or at least 0.45wt%, or at least 0.5wt%, or at least 0.6wt%, or at least 0.7wt%, or at least 0.8wt%, or at least 0.9wt%, or at least 1wt%, or at least 2wt%, or at least 3wt%, or at least 4wt%, or at least 5wt%, or at least 6wt%, or at least 7wt%. %, or at least 8wt%, or at least 9wt%, or at least 10wt%, or at least 11wt%, or at least 13wt%, or at least 15wt%, or at least 20wt%, or at least 25wt%, or at least 30wt%, or at least 35wt%, or at least 40wt%, or at least 45wt%, or at least 50wt%, or at least 55wt%, or at least 60wt%, or at least 70wt%, or at least 80wt%, or at least 90wt%, or at least 95wt%, or at least 98wt%, or at least 99wt%, or 100wt% of the olefin composition is r-olefin or pr-olefin or r-aldehyde or pr-aldehyde.

[0474] Additionally or alternatively, at most 100wt%, or at most 98wt%, or at most 95wt%, or at most 90wt%, or at most 80wt%, or at most 75wt%, or at most 70wt%, or at most 60wt%, or at most 50wt%, or at most 40wt%, or at most 30wt%, or at most 20wt%, or at most 10wt%, or at most 8wt%, or at most 5wt%, or at most 4wt%, or at most 3wt%, or at most 2wt%, or at most 1wt%, or At most 0.8 wt%, or at most 0.7 wt%, or at most 0.6 wt%, or at most 0.5 wt%, or at most 0.4 wt%, or at most 0.3 wt%, or at most 0.2 wt%, or at most 0.1 wt%, or at most 0.09 wt%, or at most 0.07 wt%, or at most 0.05 wt%, or at most 0.03 wt%, or at most 0.02 wt%, or at most 0.01 wt% of the olefin composition is pr-olefins, based on the weight of the olefin composition fed to the reaction vessel.

[0475] Alternatively, or in addition, the following amounts of the aldehyde composition are r-aldehyde or pr-aldehyde: at least 0.005 wt%, or at least 0.01 wt%, or at least 0.05 wt%, or at least 0.1 wt%, or at least 0.15 wt%, or at least 0.2 wt%, or at least 0.25 wt%, or at least 0.3 wt%, or at least 0.35 wt%, or at least 0.4 wt%, or at least 0.45 wt%, or at least 0.5 wt%, or at least 0.6 wt%, or at least 0.7 wt%, or at least 0.8 wt%, or at least 0.9 wt%, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5wt%, or at least 6wt%, or at least 7wt%, or at least 8wt%, or at least 9wt%, or at least 10wt%, or at least 11wt%, or at least 13wt%, or at least 15wt%, or at least 20wt%, or at least 25wt%, or at least 30wt%, or at least 35wt%, or at least 40wt%, or at least 45wt%, or at least 50wt%, or at least 55wt%, or at least 60wt%, or at least 70wt%, or at least 80wt%, or at least 90wt%, or at least 95wt%, or at least 98wt%, or at least 99wt%, or 100wt%.

[0476] Additionally, or alternatively, based on the weight of the composition fed to the reaction vessel, the following amount of the aldehyde composition is r-aldehyde or pr-aldehyde: at most 100 wt%, or at most 98 wt%, or at most 95 wt%, or at most 90 wt%, or at most 80 wt%, or at most 75 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 20 wt%, or at most 10 wt%, or at most 8 wt%, or at most 5 wt%, Or at most 4wt%, or at most 3wt%, or at most 2wt%, or at most 1wt%, or at most 0.8wt%, or at most 0.7wt%, or at most 0.6wt%, or at most 0.5wt%, or at most 0.4wt%, or at most 0.3wt%, or at most 0.2wt%, or at most 0.1wt%, or at most 0.09wt%, or at most 0.07wt%, or at most 0.05wt%, or at most 0.03wt%, or at most 0.02wt%, or at most 0.01wt%.

[0477] In each case, the amounts recited apply not only to the olefin or aldehyde fed to the reactor, but may alternatively or additionally apply to the pr-olefin or pr-aldehyde feedstock supplied to the oxo diol manufacturer, or may be used as a basis for relating or calculating the amount of recycled content in the pr-olefin or pr-aldehyde, for example when a source of pr-olefin or pr-aldehyde is blended with a non-recycled component olefin or pr-aldehyde to produce an olefin or aldehyde composition having the aforementioned amounts of pr-olefin or pr-aldehyde.

[0478] In one embodiment or in combination with any of the recited embodiments, the oxodiol composition has associated therewith, or contains, or is labeled, advertised, or certified as containing, an amount of recycled content 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 %, or up to 15 wt %, or up to 14 wt %, or up to 13 wt %, or up to 11 wt %, or up to 10 wt %, or up to 8 wt %, or up to 6 wt %, or up to 4 wt %, or up to 5 wt %, or up to 5 wt %, or up to 6 wt %, or up to 7 wt %, or up to 8 wt %, or up to 9 wt %, or up to 10 wt %, or up to 11 wt %, or up to 10 wt %, or up to 8 wt %, or up to 6 wt %, or up to 5 wt %, or up to 4 wt %, or up to 3 wt %, or up to 2 wt %, or up to 1 wt %, or up to 0.9 wt %, or up to 0.8 wt %, or up to 0.7 wt %, based on the weight of the oxodiol composition.

[0479] The recovery component associated with oxodiol can be established by applying the recovery component value to oxodiol, such as by deducting the recovery component value from the recovery stock filled with quota (credit or allocation), or by making r-olefin or r-aldehyde feedstock react to prepare r-oxodiol.The quota can be included in the recovery stock created, maintained or operated by the oxodiol manufacturer or created, maintained or operated for the oxodiol manufacturer.The quota is obtained from any source along any manufacturing chain of the product.In one embodiment, the source of the quota is indirectly derived from pyrolysis recovery waste, or derived from cracking r-pyrolysis oil or r-pyrolysis gas.

[0480] The amount of recovered component in the r-olefin or r-aldehyde feedstock fed to the oxodiol reactor, or the amount of recovered component applied to the r-OG, or the amount of r-olefin or r-aldehyde that needs to be fed to the reactor to require the desired amount of recovered component in the oxodiol (in the case where all recovered component from the r-olefin or r-aldehyde is applied to the oxodiol), can be determined or calculated by any of the following methods:

[0481] (i) the amount of quota associated with the r-olefin or r-aldehyde for feeding to the reactor in question, as determined by the amount certified or declared by the supplier of the olefin or aldehyde composition transferred to the oxodiol manufacturer, or

[0482] (ii) the amount declared by the oxodiol manufacturer as fed to the oxodiol reactor, or

[0483] (iii) using a mass balance approach to back-calculate the minimum amount of recycled content in the feedstock from the amount of recycled content stated, advertised or accounted for by the manufacturer, whether or not accurate, as applied to the oxodiol product, or

[0484] (iv) Using a proportional mass method, blending the non-recycled content with the recycled content feedstock olefin or aldehyde, or combining the recycled content with a portion of the feedstock.

[0485] Satisfying any of methods (i)-(iv) is sufficient to establish the portion of the r-olefin or r-aldehyde that is derived directly or indirectly from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced from pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced from pyrolysis of recycled waste. In the case where the r-olefin or r-aldehyde feed is blended with recycled feed from other recycled sources, the percentage of the r-olefin or r-aldehyde attributable to the r-olefin or r-aldehyde (directly or indirectly obtained from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced from pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced from pyrolysis of recycled waste) in the statement is determined using a ratio method of the mass of r-olefin or r-aldehyde (directly or indirectly obtained from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced from pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced from pyrolysis of recycled waste) to the mass of recycled olefin or aldehyde from other sources.

[0486] Methods (i) and (ii) do not require calculations because they are determined based on what the olefin or aldehyde manufacturer or oxo diol manufacturer or supplier states, claims, or otherwise communicates to each other or to the public. Methods (iii) and (iv) are calculations.

[0487] In one embodiment or in combination with any of the described embodiments, the minimum amount of recycled component olefin or aldehyde fed to the reactor can be determined by knowing the amount of recycled component associated with the final product oxo diol and assuming that all of the recycled component in the oxo diol is attributable to the r-olefin or r-aldehyde fed to the reactor and not to any other component in the reaction zone.

[0488] The minimum portion of the r-olefin or r-aldehyde component that is derived directly or indirectly from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced from pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced from pyrolysis of recycled waste to produce the oxodiol product associated with a particular amount of recycled component can be calculated as:

[0489]

[0490] wherein P represents the minimum portion of r-olefins or r-aldehydes derived directly or indirectly from the cracking of recycled waste, pyrolysis of recycled waste, pyrolysis gas produced from pyrolysis of recycled waste and / or r-pyrolysis oil produced from pyrolysis of recycled waste, and

[0491] %D represents the percentage of the claimed recovered component in the product r-oxodiol, and

[0492] Pm represents the molecular weight of the product oxo diol, and

[0493] Rm represents the molecular weight of the reactant olefin or aldehyde as part of the oxo diol product, not exceeding the molecular weight of the reactant olefin or aldehyde, and

[0494] Y represents the percentage yield of product, e.g., oxo diol, determined as an annual average yield, independent of whether the feedstock is an r-olefin or r-aldehyde. If the average annual yield is unknown, it can be assumed to be the industry average yield using the same process technology.

[0495] If for the designation of a given recovery component in the oxodiol, the amount of the recovery component in the r-olefin or r-aldehyde feed can be greater than the minimum amount, resulting in a residual excess recovery component. In this case, the remainder of the available recovery component can be retained in the recovery stock. Excess recovery components can be stored in the recovery stock and applied to other oxodiol products, which are not made with r-olefins or r-aldehydes, or with respect to the amount of the recovery component that is desired to be applied to the oxodiol, the amount of its r-olefin or r-aldehyde recovery component is insufficient. However, no matter whether the manufacturer of the oxodiol actually specifies that the r-olefin or r-aldehyde feedstock contains the minimum amount of recovery components, it is considered that the r-oxodiol specified to contain a certain recovery component is made by the r-olefin or r-aldehyde feedstock containing the minimum recovery component by the above-mentioned calculation method.

[0496] In the case of the proportional mass approach in method (iv), the oxodiol portion (derived directly or indirectly from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced from pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced from pyrolysis of recycled waste) will be calculated based on the mass of recycled content available to the oxodiol manufacturer (either by purchase or transfer, or by creation in the case of olefins or aldehydes incorporated into r-olefin or r-aldehyde production) as the amount of feedstock attributable to the daily run divided by the mass of r-olefin or r-aldehyde feedstock or:

[0497]

[0498] where P represents the percentage of recovered components in the oxodiol feed stream, and

[0499] where Mr is the mass of recovered components attributed to the r-olefin or r-aldehyde stream per day, and

[0500] Ma is the mass of total olefin or aldehyde feed used to prepare oxo diols on the corresponding day.

[0501] For example, if the oxodiol manufacturer has access to 1000 kg of a recovery allotment or credit derived from pyrolysis recovery waste, and the oxodiol manufacturer elects to attribute 10 kg of the recovery allotment to the olefin or aldehyde feedstock used to make the oxodiol, and the olefin or aldehyde feedstock is employed at 100 kg / day to make the oxodiol, then the portion P of the r-olefin or r-aldehyde feedstock derived directly or indirectly from cracked pyrolysis oil would be 10 kg / 100 kg, or 10 wt%. The olefin or aldehyde feedstock composition would be considered to be the r-olefin or r-aldehyde composition because a portion of the recovery allotment is applied to the olefin or aldehyde feedstock used to make the oxodiol.

[0502] In another embodiment, methods are provided for distributing recycled content among various products manufactured by an oxodiol manufacturer, or among products manufactured by any one or combination of entities in a family of entities of which the oxodiol manufacturer is a part. For example, an oxodiol manufacturer, or any combination or all of its family of entities, or sites, may:

[0503] a. adopt a symmetrical distribution of recycled content values ​​in its products based on the same fractional percentage of recycled content in one or more feedstocks, or based on the amount of quota received. For example, if 5 wt% of the olefin or aldehyde feedstock is r-olefin or r-aldehyde, or if the quota value is 5 wt% of the total olefin or aldehyde feedstock, then all oxodiols prepared from the olefin or aldehyde feedstock may contain a 5 wt% recycled content value. In this case, the amount of recycled content in the product is proportional to the amount of recycled content in the feedstock from which the product is prepared; or

[0504] b. Adopting an asymmetric distribution of recycled content values ​​in its products based on the same fractional percentage of recycled content in one or more feedstocks, or based on the amount of quota received. For example, if 5 wt% of the olefin or aldehyde feedstock is r-olefins or r-aldehydes, or if the quota value is 5 wt% of the total olefin or aldehyde feedstock, one oxodiol volume or batch may receive a greater amount of recycled content value than other oxodiol batches or volumes, provided that the total amount of recycled content does not exceed the total amount of r-olefins or r-aldehydes received or allocated, or the total amount of recycled content in the recycled stock. One batch of oxodiol may contain 5 wt% recycled content, while another batch may contain zero 0 wt% recycled content, even though both volumes are made from the same volume of olefin or aldehyde feedstock. In an asymmetric distribution of recycled content, a manufacturer can tailor the recycled content to the volume of oxodiol sold as needed among customers, thereby providing flexibility among customers, some of whom may require more recycled content in the volume of oxodiol than others.

[0505] Symmetrical and asymmetric distribution of recovery 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 recovery component input (recovery component raw material or quota) can be to a site, and the recovery component value from the input is applied to one or more products manufactured at the same site, and at least one of the products manufactured at the site is oxodiol, and optionally, at least a portion of the recovery component value is applied to the oxodiol product. The recovery component value can be applied to the products of the site symmetrically or asymmetrically. The recovery component value can be applied to different oxodiol volumes symmetrically or asymmetrically, or to a combination of oxodiol and other products prepared at the site. For example, the recovery component value is transferred to the recovery inventory located at the site, generated at the site, or the raw material containing the recovery component value is reacted at the site (collectively referred to as "recovery input"), and the recovery component value obtained from the input is:

[0506] a. symmetrically distributed over at least a portion or all of the volume of oxodiol produced at said site over a period of time (e.g., within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously); or

[0507] b. symmetrically distributed over at least a portion or all of the volume of oxodiol produced at the site and over at least a portion or a second different product produced at the same site, each within the same time period (e.g., within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously); or

[0508] c. The recycled content is symmetrically distributed across all products that actually have recycled content applied to them that are manufactured at the site, in the same time period (e.g., within the same day, or within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously). Although a variety of products may be manufactured at a site, in this option, not all products necessarily receive a recycled content value, but rather the distribution is symmetrical for all products that do receive a recycled content value or have a recycled content value applied to them; or

[0509] d. which is asymmetrically distributed over at least two volumes of oxodiol produced at the same site, optionally within the same time period (e.g., within 1 day, or within 1 week, or within 1 month, or within 6 months, or within a calendar year, or continuously), or as sold to at least two different customers. For example, one volume of oxodiol produced may have a greater recovered content value than a second volume of oxodiol produced at the site, or one volume of oxodiol produced at the site and sold to one customer may have a greater recovered content value than a second volume of oxodiol produced at the site and sold to a second, different customer, or

[0510] e. which is asymmetrically distributed between at least one volume of oxo diol and at least one volume of a different product, each optionally produced at the same site within the same time period (e.g. within 1 day, or within 1 week, or within 1 month, or within 6 months, or within a calendar year, or continuously), or sold to at least two different consumers.

[0511] In one embodiment or in combination with any of the embodiments mentioned, a recovery component input or generation (a recovery component feedstock or quota) can be to or at a first site, and the recovery component value from the input is transferred to a second site and applied to one or more products prepared at the second site, and at least one of the products prepared at the second site is an oxodiol, and optionally, at least a portion of the recovery component value is applied to the oxodiol product prepared at the second site. The recovery component value can be applied symmetrically or asymmetrically to the products at the second site. The recovery component value can be applied symmetrically or asymmetrically to different oxodiol volumes, or to a combination of oxodiol and other products prepared at the second site. For example, the recovery component value is transferred to a recovery stock located at the first site, generated at the first site, or a feedstock containing the recovery component value is reacted at the first site (collectively referred to as "recovery input"), and the recovery component value obtained from the input is:

[0512] a. symmetrically distributed over at least a portion or all of the volume of oxodiol produced at the second site over a period of time (e.g., within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously); or

[0513] b. symmetrically distributed over at least a portion or all of the volume of oxodiol produced at the second site and over at least a portion or a second different product produced at the same second site, each within the same time period (e.g., within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously); or

[0514] c. The recycled content is symmetrically distributed over all products that actually have the recycled content applied that are manufactured at the second site in the same time period (e.g., within the same day, or within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously). Although a variety of products may be manufactured at the second site, in this option, not all products necessarily receive a recycled content value, but rather the distribution is symmetrical for all products that do receive a recycled content value or have a recycled content value applied; or

[0515] d. which is asymmetrically distributed over at least two oxodiol volumes produced at the same second site, optionally within the same time period (e.g., within 1 day, or within 1 week, or within 1 month, or within 6 months, or within a calendar year, or continuously), or sold to at least two different customers. For example, one volume of oxodiol produced may have a greater recovered content value than a second volume of oxodiol produced at a second site, or one volume of oxodiol produced at a second site and sold to one customer may have a greater recovered content value than a second volume of oxodiol produced at the second site and sold to a second, different customer, or

[0516] e. which is asymmetrically distributed between at least one volume of oxo diol and at least one volume of a different product, each optionally produced at the same second site within the same time period (e.g., within 1 day, or within 1 week, or within 1 month, or within 6 months, or within a calendar year, or continuously), or sold to at least two different consumers.

[0517] In one embodiment or in combination with any of the mentioned embodiments, an oxodiol manufacturer or one of its family of entities may prepare oxodiol by obtaining an olefin or aldehyde composition from any source from a supplier, or processing an olefin or aldehyde and preparing r-oxodiol, or preparing r-oxodiol, whether or not such olefin or aldehyde composition has any direct or indirect recycled content, and:

[0518] i. an olefin or aldehyde composition from the same supplier, also receiving a recycled content quota, or

[0519] ii. Obtaining a recovery component credit from any person or entity without providing the olefin or aldehyde composition from the person or entity to which the recovery component credit is transferred.

[0520] The quota in (i) is obtained from an olefin or aldehyde supplier, and the olefin or aldehyde supplier also supplies olefins or aldehydes to the oxodiol manufacturer or within its entity family. The situation described in (ii) allows the oxodiol manufacturer to obtain a supply of olefin or aldehyde compositions as non-recovery component olefins or aldehydes, and also obtain a recovery component quota from the olefin or aldehyde supplier. In one embodiment or in combination with any of the embodiments mentioned, the olefin or aldehyde supplier transfers the recovery component quota to the oxodiol manufacturer, and transfers the supply of olefins or aldehydes to the oxodiol manufacturer, wherein the recovery component quota is not associated with the olefins or aldehydes supplied, or even not associated with any olefins or aldehydes prepared by the olefin or aldehyde supplier. The recovered content quota need not be dependent on the amount of recovered content in the olefin or aldehyde composition, or on any compound used to prepare the oxodiol, but rather the recovered content quota transferred by the olefin or aldehyde supplier may be associated with other products (which other products are derived directly or indirectly from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced by pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced by pyrolysis of recycled waste), or with recovered content of any downstream compound obtained from pyrolysis of recycled waste, such as r-ethylene, r-propylene, r-butadiene, r-aldehyde, r-alcohol, r-benzene, etc. For example, an olefin or aldehyde supplier may transfer recovered content associated with r-ethylene to an oxodiol manufacturer and also supply a certain amount of olefin or aldehyde, even if the r-ethylene is not used in the synthesis of the olefin or aldehyde. This allows flexibility between the olefin or aldehyde supplier and the oxodiol manufacturer to allocate recovered content between the various products they each manufacture.

[0521] In one embodiment or in combination with any of the embodiments mentioned, the olefin or aldehyde supplier transfers the recovery component quota to the oxo diol manufacturer, and transfers the supply of olefin or aldehyde to the oxo diol manufacturer, wherein the recovery component quota is associated with the olefin or aldehyde. In this case, the olefin or aldehyde transferred need not be r-olefin or r-aldehyde (olefin or aldehyde derived directly or indirectly from the pyrolysis of recycled waste); on the contrary, the olefin or aldehyde provided by the supplier can be any olefin or aldehyde, such as non-recovery component olefin or aldehyde, as long as the provided allocation is associated with the manufacture of olefin or aldehyde. Alternatively, the olefin or aldehyde supplied can be r-olefin or aldehyde, and at least a portion of the recovery component quota transferred can be the recovery component in r-olefin or aldehyde. The recovery component quota transferred to the oxo diol manufacturer can be provided in advance with the olefin or aldehyde, optionally in batches, or with each batch of olefin or aldehyde, or distributed between the parties as needed.

[0522] The quota in (ii) is obtained by the oxodiol manufacturer (or its family of entities) from any person or entity without obtaining a supply of olefins or aldehydes from that person or entity. That person or entity may be an olefin or aldehyde manufacturer that does not supply olefins or aldehydes to the oxodiol manufacturer or its family of entities, or that person or entity may be a manufacturer that does not manufacture olefins or aldehydes.

[0523] In either case, the situation of (ii) allows the oxodiol manufacturer to obtain the recovery component quota without having to purchase any olefin or aldehyde from the entity supplying the recovery component quota. For example, an individual or entity can transfer the recovery component quota to the oxodiol manufacturer or its entity family by a buy / sell model or contract, without the need to purchase or sell quotas (e.g., as a product exchange for products that are not olefins or aldehydes), or an individual or entity can directly sell the quota to one of the oxodiol manufacturer or its entity family. Alternatively, an individual or entity can transfer the product except olefins or aldehydes together with the recovery component quota associated therewith to the oxodiol manufacturer. This is attractive for the oxodiol manufacturer with a diversified business, which manufactures various products except oxodiols, and the raw materials required for these products are not olefins or aldehydes that an individual or entity can provide to the oxodiol manufacturer.

[0524] The oxodiol manufacturer may deposit the allowance into the recycled stock. The oxodiol manufacturer also manufactures oxodiol, whether or not recycled content is applied to the oxodiol so manufactured, and whether or not the recycled content value—if applied to the oxodiol—is taken from the recycled stock. For example, the oxodiol manufacturer or any entity in its family of entities may:

[0525] a. deposit the allowances into the recycling stock and store them only; or

[0526] b. depositing the quota into a recycling stock and applying the recycled content value from the recycling stock to products other than oxodiol manufactured by the oxodiol manufacturer, or

[0527] c. Selling or transferring allowances from the recycling stock into which the allowances acquired as described above are deposited.

[0528] However, if necessary, any quota can be deducted from this recovery stock, and applied to oxodiol product in any quantity and at any time, until the point of selling or transferring oxodiol to a third party. Therefore, the recovery component quota applied to oxodiol can be directly or indirectly derived from pyrolysis recovery waste, or the recovery component quota applied to oxodiol is not directly or indirectly derived from pyrolysis recovery waste. For example, the recovery stock of quota can be generated, with various sources for creating quota. Some recovery component quotas (credits) can be derived from methanolysis of recovery waste, or from gasification of recovery waste, or from mechanical recovery of waste plastics or metal recovery, and / or from pyrolysis recovery waste, or from any other chemical or mechanical recovery technology. The recovery stock can track or not track the source or basis of obtaining the recovery component, or the recovery stock can not allow the source or basis of distribution to be associated with the allocated amount applied to oxodiol. Thus, in this embodiment, it is sufficient to deduct the recovered content value from the recovered stock and apply it to the oxodiol, regardless of the source or origin of the recovered content value, as long as the quota obtained from the pyrolysis recovered waste is also obtained by the oxodiol manufacturer as specified in step (i) or step (ii), regardless of whether the quota is actually deposited in the recovered stock. In one embodiment or in combination with any of the embodiments mentioned, the quota obtained in step (i) or (ii) is deposited in the recovered stock of the quota. In one embodiment or in combination with any of the embodiments mentioned, the recovered content value deducted from the recovered stock and applied to the oxodiol originates from the pyrolysis recovered waste.

[0529] As used throughout, the recovery stock of quota can be owned by oxodiol manufacturer, operated by oxodiol manufacturer, owned or operated by other manufacturers except oxodiol manufacturer, but at least partially used for oxodiol manufacturer, or licensed by oxodiol manufacturer.And, as used in full, oxodiol manufacturer also can include its entity family.For example, although oxodiol manufacturer may not own or operate recovery stock, one in its entity family can have such platform, or license it from independent supplier, or operate it for oxodiol manufacturer.Alternately, independent entity can own and / or operate recovery stock, and operate and / or manage at least a portion of recovery stock for oxodiol manufacturer for service fee.

[0530] In one embodiment or in combination with any of the embodiments mentioned, the oxodiol manufacturer obtains a supply of olefins or aldehydes from a supplier and also obtains a quota from (i) the supplier or (ii) any other person or entity, wherein such quota is derived from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced by pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced by pyrolysis of recycled waste, and optionally, the quota is obtained from the olefin or aldehyde supplier and may even be by means of obtaining a quota of r-olefins or r-aldehydes from the olefin or aldehyde supplier. The oxodiol manufacturer is considered to obtain a supply of olefins or aldehydes from a supplier if the supply of olefins or aldehydes is obtained by a person or entity in the entity family of the oxodiol manufacturer. The oxodiol manufacturer then performs one or more of the following steps:

[0531] a. applying the quota to oxo diols prepared from a supply of olefins or aldehydes;

[0532] b. applying the quota to oxodiol not produced from a supply of olefin or aldehyde, for example...

Claims

1. A method for preparing a recycled component oxodiol composition r-OG, the method comprising: hydroformylating a recycled component olefin composition, i.e., r-olefins, with synthesis gas to form a recycled component aldehyde, r-AD, wherein at least a portion of the recycled component olefin composition is derived directly or indirectly from pyrolysis recycled waste, then reacting at least a portion of the r-AD in the presence of a catalyst to produce an oxodiol effluent comprising r-oxodiol, r-OG; Wherein, the recycled olefin composition comprises ethylene or propylene, Wherein, the recycled waste is selected from: high-density polyethylene, low-density polyethylene, polypropylene, polystyrene, other polyolefins other than the above, and any combination thereof, wherein pyrolysis of the recycled waste produces recycled pyrolysis oil, i.e., r-pyrolysis oil, and the process derived from pyrolysis of the recycled waste includes cracking of the r-pyrolysis oil, wherein The r-pyrolysis oil comprises at least 95 wt% C5-C 25 hydrocarbons, the r-pyrolysis oil comprising at least 10 wt% and not more than 35 wt% of olefins, the r-pyrolysis oil comprising at least 5 wt% and not more than 35 wt% of aromatic hydrocarbons, The r-pyrolysis oil is not hydrotreated before the cracking, The cracker for carrying out said cracking comprises a convection section, a radiant section and a cross section between the convection section and the radiant section, wherein in said radiant section a feed stream comprising said r-pyrolysis oil is thermally cracked, The feed stream comprising r-pyrolysis oil contains at least 5 wt% and no more than 35 wt% of r-pyrolysis oil and at least 50 wt% of C2-C3 hydrocarbons, The cracker is a gas cracker that can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock. r- The pyrolysis oil is cracked in the presence of steam and the dilution steam ratio is at least 0.3, The temperature of the feed stream passing through the crossover section is in the range of 510 to 680°C, The residence time of the feed stream in the radiation section is at least 0.20 seconds and no more than 1.5 seconds, and the coil outlet temperature of the radiation section is at least 680 and no more than 830°C, The cracked olefin-containing effluent stream contains no more than 5 wt% aromatic hydrocarbons.

2. The process according to claim 1, wherein the oxodiol effluent is produced by hydrogenating at least a portion of the r-AD to produce an oxodiol effluent comprising r-oxodiol, r-OG.

3. A method for preparing oxo diols, the method comprising: a. The oxo diol manufacturer obtains the olefin or aldehyde composition from the supplier, and one of the following i, ii: i. also obtain a quota of pyrolysis recovery components from the supplier, or ii. receiving a pyrolysis recovery component quota from any person or entity without transferring said pyrolysis recovery component quota to said person or entity supplying an olefin or aldehyde composition; and b. the oxodiol manufacturer prepares the oxodiol composition OG from any olefin or aldehyde composition obtained from any source; and c. One of the following i, ii, iii: i. applying the pyrolysis recovery component quota to OG prepared by supplying the olefin or aldehyde obtained in step (a); or ii. applying the pyrolysis recovery component quota to OG not prepared by supplying the olefin or aldehyde obtained in step (a), or iii. depositing the pyrolysis recovery component credit into the recovery inventory deducted from the recovery component value, and applying at least a portion of the value to: 1.OG, thereby obtaining r-OG, or 2. Compounds or compositions other than OG, or 3. Both; Regardless of whether the recovered component value is obtained from the pyrolysis recovered component quota obtained in step a(i) or step a(ii); Wherein, the pyrolysis recovery component quota comprises a quota derived from the cracking of r-pyrolysis oil, wherein: The r-pyrolysis oil is obtained by pyrolyzing recycled waste, wherein the recycled waste is selected from: high-density polyethylene, low-density polyethylene, polypropylene, polystyrene, other polyolefins other than the above, and any combination thereof, The r-pyrolysis oil comprises at least 95 wt% C5-C 25 hydrocarbons, the r-pyrolysis oil comprising at least 10 wt% and not more than 35 wt% of olefins, the r-pyrolysis oil comprising at least 5 wt% and not more than 35 wt% of aromatic hydrocarbons, The r-pyrolysis oil is not hydrotreated before the cracking, The cracker for carrying out said cracking comprises a convection section, a radiant section and a cross section between the convection section and the radiant section, wherein in said radiant section a feed stream comprising said r-pyrolysis oil is thermally cracked, The feed stream comprising r-pyrolysis oil contains at least 5 wt% and no more than 35 wt% of r-pyrolysis oil and at least 50 wt% of C2-C3 hydrocarbons, The cracker is a gas cracker that can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock. r- The pyrolysis oil is cracked in the presence of steam and the dilution steam ratio is at least 0.3, The temperature of the feed stream passing through the crossover section is in the range of 510 to 680°C, The residence time of the feed stream in the radiation section is at least 0.20 seconds and no more than 1.5 seconds, and the coil outlet temperature of the radiation section is at least 680 and no more than 830°C, The cracked olefin-containing effluent stream comprises ethylene and / or propylene and contains no more than 5 wt% of aromatic hydrocarbons.

4. A method for preparing a recycled component oxodiol composition r-OG, the method comprising: a. reacting any olefin or aldehyde composition in a synthesis process to prepare an oxo diol composition OG; as well as b. applying the recovery component value to at least a portion of the OG to obtain a recovery component oxodiol composition r-OG; as well as c. Optionally, the recovered component value is obtained by deducting at least a portion of the recovered component value from the recovered inventory, and further optionally, the recovered inventory also contains a pyrolysis recovered component quota, or a pyrolysis recovered component quota has been deposited in the recovered inventory before the deduction; and d. Optionally, communicating to a third party that the r-OG has recycled content or is obtained or derived from recycled waste; Wherein, the recovered content value comprises a quota derived from the cracking of r-pyrolysis oil, wherein: The r-pyrolysis oil is obtained by pyrolyzing recycled waste, wherein the recycled waste is selected from: high-density polyethylene, low-density polyethylene, polypropylene, polystyrene, other polyolefins other than the above, and any combination thereof, The r-pyrolysis oil comprises at least 95 wt% C5-C 25 hydrocarbons, the r-pyrolysis oil comprising at least 10 wt% and not more than 35 wt% of olefins, the r-pyrolysis oil comprising at least 5 wt% and not more than 35 wt% of aromatic hydrocarbons, The r-pyrolysis oil is not hydrotreated before the cracking, The cracker for carrying out said cracking comprises a convection section, a radiant section and a cross section between the convection section and the radiant section, wherein in said radiant section a feed stream comprising said r-pyrolysis oil is thermally cracked, The feed stream comprising r-pyrolysis oil contains at least 5 wt% and no more than 35 wt% of r-pyrolysis oil and at least 50 wt% of C2-C3 hydrocarbons, The cracker is a gas cracker that can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock. r- The pyrolysis oil is cracked in the presence of steam and the dilution steam ratio is at least 0.3, The temperature of the feed stream passing through the crossover section is in the range of 510 to 680°C, where The residence time of the feed stream in the radiation section is at least 0.20 seconds and no more than 1.5 seconds, and the coil outlet temperature of the radiation section is at least 680 and no more than 830°C, The cracked olefin-containing effluent stream comprises ethylene and / or propylene and contains no more than 5 wt% of aromatic hydrocarbons.

5. The method according to claim 4, further comprising: a. pyrolyzing a pyrolysis feed comprising recycled waste material to form a pyrolysis effluent comprising recycled pyrolysis oil, i.e., r-pyrolysis oil and / or recycled pyrolysis gas, i.e., r-pyrolysis gas; b. optionally, cracking a cracker feed comprising at least a portion of r-pyrolysis oil, thereby producing a cracker effluent comprising r-olefins; or alternatively, cracking a cracker feed not containing r-pyrolysis oil to produce olefins, and applying the recovery component value to the olefins so produced by deducting the recovery component value from the recovery inventory and applying it to the olefins to produce r-olefins; as well as c. reacting any olefin volume in the synthesis process to produce an aldehyde composition; as well as d. reacting at least a portion of any aldehyde composition in a synthesis process to produce an oxo diol composition; as well as e. applying a recovery component value to at least a portion of the oxodiol composition based on: i. the pyrolysis recovery component olefin composition, pr-olefin or pyrolysis recovery component aldehyde composition pr-AD as a raw material feed, or ii. depositing at least a portion of the quota obtained from any one or more of steps a) or b) into a recycled stock, and deducting a recycled content value from said stock, and applying at least a portion of said recycled content value to OG, thereby obtaining said r-OG.

6. The method according to any one of claims 1 to 5, wherein: The r-olefins, r-AD or r-OG are derived directly or indirectly from cracked r-pyrolysis oil or obtained from r-pyrolysis gas.

7. The method according to any one of claims 1 to 5, wherein: The r-olefins, r-AD or r-OG are derived directly or indirectly from cracking r-pyrolysis oil in a gas fed cracker furnace.

8. The method according to claim 3 or 4, wherein: The olefin or aldehyde composition fed to the reaction vessel contains no recycled content.

9. The method according to any one of claims 1 to 5, wherein: The oxodiols are produced by an oxodiol manufacturer and the recovered component is allocated between products produced by the oxodiol manufacturer or products produced by any one entity or combination of entities in a family of entities of which the oxodiol manufacturer is a part, wherein the allocation is by asymmetrically distributing the recovered component value between their products and optionally at least one of the products is an oxodiol.

10. The method according to any one of claims 1 to 5, wherein: Oxodiols are produced by an oxodiol manufacturer and the recovered components are allocated between products produced by the OG manufacturer or products produced by any one entity or combination of entities in the family of entities of which the OG manufacturer is a part, wherein the allocation method is applied symmetrically or asymmetrically across the combination of OG and other products produced at the second site.

11. The method according to any one of claims 3 to 5, wherein: AD is supplied by an AD supplier, which transfers a recycling quota to the OG manufacturer and transfers the supply of AD to the OG manufacturer.

12. The method according to any one of claims 3 to 5, wherein: The reclaim component quota is not associated with the AD supplied.

13. The method according to any one of claims 3 to 5, wherein: AD is supplied by an AD supplier, which transfers a recycling component quota to the OG manufacturer and transfers the supply of AD to the OG manufacturer, and the recycling component quota is associated with the AD prepared by the supplier.

14. The method according to any one of claims 3 to 5, wherein: The supplied AD is r-AD, and at least a portion of the recycled component quota that is transferred is the recycled component in the supplied r-AD.

15. The method according to any one of claims 3 to 5, wherein: The recycled content value applied to OG is taken from the recycled stock, which is derived directly or indirectly from the pyrolysis of recycled waste.

16. The method according to any one of claims 3 to 5, wherein: The OG Manufacturer or a person or entity within its family of entities receives a supply and quota of ADs, and at least a portion of said quota: a. Applied to OG prepared from the supplied AD; b. applied to OG not prepared from the supply of AD; or c. depositing into a recovery stock, wherein a recovery component value is deducted from the recovery stock, and applying at least a portion of the recovery component value to: i.OG, thereby obtaining r-OG, or ii. a compound or composition other than OG, or iii. Both; or d. Deposited into the recovery stock and stored.

17. The method according to any one of claims 1 to 5, wherein: a. Olefin Suppliers: i. cracking a cracker feed comprising a recycled pyrolysis oil to produce a recycled component olefin composition, i.e., r-olefins, at least a portion of which is obtained by cracking the recycled pyrolysis oil, or ii. preparing a recycled component pyrolysis gas, i.e. r-pyrolysis gas, at least a portion of which is obtained by pyrolysis of a recycled waste stream, or iii. Both; and b. Oxodiol Manufacturers: i. obtaining quotas derived directly or indirectly from said r-olefins or said r-pyrolysis gas - from suppliers or third parties who transfer said quotas, ii. Preparation of oxodiols from olefins or aldehydes, and iii. associating at least a portion of said quota with at least a portion of said oxo diol, whether or not the olefin or aldehyde used to prepare said oxo diol contains r-olefin or r-aldehyde.

18. The method according to any one of claims 1 to 5, comprising: a. preparing r-olefins by cracking r-pyrolysis oil or separating olefins from r-pyrolysis gas; as well as b. converting at least a portion of the r-olefin in a synthesis process to produce an aldehyde, and c. converting any olefin or aldehyde or at least a portion of said olefin or aldehyde into an oxo diol; as well as d. applying the recovered component value to the oxo diol to prepare r-OG; as well as e. Optionally, r-pyrolysis oil or r-pyrolysis gas or both are prepared by pyrolysis recovery of raw materials.

19. The method according to claim 6, comprising: a. oxodiol OG, and b. an identifier associated with the oxodiol, the identifier being an indication that the oxodiol has recycled content or is made from a source having recycled content.

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