Recovered component (C4) alkanoic acid

Abstract

A process for preparing recycled component (C4) alkanoic acids (ie, butyric acid and / or isobutyric acid) derived from a recycled propylene composition and for recovering (C4) alkanals is provided.

Description

Background Art

[0001] Waste materials, especially non-biodegradable waste materials, 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 materials as possible. However, from an economic point of view, recycling waste materials can be challenging.

[0002] To maximize recycling efficiency, it is desirable for large-scale production facilities to process feedstocks with recycled content derived from a variety of waste materials.

[0003] Some recycling efforts involve complex and detailed separation of waste streams, which results in increased costs to obtain recycled waste component streams. It is desirable to establish recycled components without sorting them into a single type of plastic or scrap, or which can tolerate a variety of impurities in the waste stream.

[0004] 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 the product, particularly if the recycled content product is a gas or difficult to separate. Because gas infrastructure is continuous flow and often mixes gas streams from a variety of sources, separating and allocating a dedicated portion of the gas made specifically from recycled content feedstock can be difficult.

[0005] Additionally, there may be a desire to move away from reliance on natural gas, ethane or propane, as the sole source for manufacturing products such as ethylene and propylene and their downstream derivatives.

[0006] It would also be desirable to synthesize compounds, such as (C4)alkanoic acids, using existing equipment and processes without having to invest in additional expensive equipment to build a recycling component into the production of the compounds.

[0007] It is desirable to be able to determine the amount and time to establish a recycled component in a compound such as a (C4)alkanoic acid (e.g., butyric acid, isobutyric acid, and combinations thereof). In addition, it may be desirable to provide a (C4)alkanoic acid with more, less, or no recycled component at certain times or for different batches. The flexibility of this approach without the need to add significant assets is desirable. Summary of the invention

[0008] A method for preparing recovered (C4)alkanoic acid (r-(C4)alkanoic acid) is provided, the method comprising carboxylating a recovered propylene composition (r-propylene) to thereby produce a carboxylation effluent comprising (C4)alkanoic acid, wherein the r-propylene is directly or indirectly derived from a cracked recovered pyrolysis oil composition (r-pyrolysis oil).

[0009] Also provided is a method for preparing recovered (C4)alkanoic acid (r-(C4)alkanoic acid), the method comprising oxidizing recovered (C4)alkanal (r-(C4)alkanal) to thereby produce an oxidation effluent containing (C4)alkanoic acid, wherein the r-(C4)alkanal is produced from a recovered propylene composition (r-propylene), and the r-propylene is directly or indirectly derived from a cracked recovered pyrolysis oil composition (r-pyrolysis oil).

[0010] Also provided is a method for obtaining a recovered component from a (C4) alkanoic acid, comprising:

[0011] a. obtaining a propylene composition designated as having recycled content, and

[0012] b. feeding the propylene to a reactor under conditions effective to produce (C4) alkanoic acid, and

[0013] Therein, whether or not the designation so indicates, at least a portion of the propylene composition is derived directly or indirectly from a cracked recovered pyrolysis oil composition (r-pyrolysis oil).

[0014] Also provided is a method for obtaining a recovered component from a (C4) alkanoic acid, comprising:

[0015] a. obtaining a (C4) alkanal designated as having a recycled component, and

[0016] b. feeding the (C4) alkanal to a reactor under conditions effective to produce the (C4) alkanoic acid, and

[0017] Therein, whether or not the designation so indicates, at least a portion of said (C4) alkanals are produced from a recovered propylene composition derived directly or indirectly from a cracked recovered pyrolysis oil composition (r-pyrolysis oil).

[0018] Furthermore, there is now provided a method for treating a recovered propylene composition, at least a portion of which is derived directly or indirectly from cracked recovered pyrolysis oil (r-propylene), which method comprises feeding the r-propylene to a carboxylation reactor in which (C4) alkanoic acid is prepared.

[0019] Furthermore, a method is now provided for treating recovered (C4)alkanals (r-(C4)alkanals) produced from a recovered propylene composition, at least a portion of which is derived directly or indirectly from a cracked recovered pyrolysis oil composition (r-propylene), the method comprising feeding the r-(C4)alkanal to an oxidation reactor in which (C4)alkanoic acid is prepared.

[0020] The method may also be an integrated method for preparing (C4) alkanoic acid, comprising:

[0021] a. providing a propylene manufacturing facility and preparing a propylene composition, at least a portion of which is obtained from cracking recovered pyrolysis oil (r-propylene), and

[0022] b. providing a (C4) alkanoic acid manufacturing facility comprising a reactor for receiving propylene; and

[0023] c. Feeding r-propylene from a propylene production facility to a (C4)alkanoic acid production facility via a system in fluid communication between said facilities.

[0024] Also provided is an integrated recovered propylene composition generation and consumption system comprising:

[0025] a. a propylene production facility adapted to produce a propylene composition, at least a portion of which is obtained from cracking recovered pyrolysis oil (r-propylene), and

[0026] b. providing a (C4) alkanoic acid manufacturing facility comprising a reactor for receiving propylene; and

[0027] c. A pipeline system connecting the two facilities, optionally with intermediate equipment or storage facilities, capable of withdrawing propylene from the propylene manufacturing facility and receiving propylene at the (C4)alkanoic acid facility.

[0028] Methods for introducing or establishing a recovery component in a (C4)alkanoic acid include:

[0029] a. obtaining an allocation or credit of a recovered propylene composition (r-propylene),

[0030] b. converting propylene to produce (C4)alkanoic acid in a synthetic process,

[0031] c. designating at least a portion of the (C4) alkanoic acid to correspond to at least a portion of the r-propylene allocation or credit, and optionally

[0032] d. Offering to sell or selling (C4)alkanoic acid containing or obtained, the recovered components of which correspond to this designation.

[0033] Also provided is a method for introducing or establishing a recycling component in a compound, comprising:

[0034] a. a propylene supplier cracking a cracker feed comprising recycled pyrolysis oil to produce a propylene composition, at least a portion of which is obtained by cracking the recycled pyrolysis oil (r-propylene), and

[0035] b. Compound Manufacturer:

[0036] i. obtaining an allocation or credit related to said propylene from a supplier or a third party to whom said allocation or credit is transferred,

[0037] ii. Preparation of compounds from propylene or reaction schemes starting with propylene, and

[0038] iii. associating at least a portion of the allotment or credit with at least a portion of the compound,

[0039] It does not matter whether the propylene used to prepare the (C4)alkanal contains r-propylene molecules.

[0040] Also provided is a method for introducing or establishing a recovery component in a (C4) alkanoic acid, comprising:

[0041] a. obtaining a recovered propylene composition, at least a portion of which is directly derived from cracked recovered pyrolysis oil (dr-propylene),

[0042] b. preparing (C4) alkanoic acid from a feedstock comprising dr-propylene,

[0043] c. designating at least a portion of the (C4) alkanoic acid as containing a recovered component corresponding to at least a portion of the amount of dr-propylene contained in the feedstock, and optionally

[0044] d. offering to sell or selling (C4) alkanal containing or obtained, the recovered components of which correspond to the designation.

[0045] Also provided is the use of a recovered propylene composition derived directly or indirectly from cracked recovered pyrolysis oil (r-propylene), comprising converting r-propylene in a synthetic process to produce (C4) alkanoic acid.

[0046] Also provided is the use of recovered (C4)alkanals (r-(C4)alkanals), which are produced from a recovered propylene composition derived directly or indirectly from cracked recovered pyrolysis oil (r-propylene), and the use includes converting r-(C4)alkanals in a synthesis process to prepare (C4)alkanoic acids.

[0047] Also provided is a novel use of recycled propylene composition (r-propylene) quotas, comprising:

[0048] a. converting propylene or an intermediate derived from propylene to produce a (C4)alkanoic acid in a synthetic process, and

[0049] b. At least a portion of the designated (C4) alkanoic acid corresponds to the r-propylene quota.

[0050] In addition, a system is provided, comprising:

[0051] a. (C4) alkanoic acid, and

[0052] b. A recycled content identifier associated with the (C4) alkanoic acid, the identifier being an indication that the (C4) alkanoic acid contains or is derived from a recycled content.

[0053] The composition of the (C4)alkanoic acid may also be different. A (C4)alkanoic acid composition is provided, comprising:

[0054] a. (C4) alkanoic acid; and

[0055] b. at least one impurity comprising formaldehyde, methylene chloride or an aldol condensation product thereof.

[0056] Also provided is a (C4) alkanoic acid composition comprising:

[0057] a. (C4) alkanoic acid; and

[0058] b. at least one impurity comprising:

[0059] i. Formaldehyde: at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 25 ppm, or at least 30 ppm, or

[0060] ii. Methyl chloride: at least 1 ppm, or at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, or

[0061] iii. Total nitrogen compounds: at least 0.5 ppm, or at least 1 ppm, or at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, or

[0062] iv. Acetone: greater than 25 ppb, or at least 30 ppb, or at least 50 ppb, or at least 100 ppb, or at least 500 ppb, or at least 1000 ppb, or

[0063] v. Methanol: greater than 3, or at least 5, or at least 10, or at least 15, or at least 20, or

[0064] vi. Acetaldehyde: greater than 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, or

[0065] vii. oxygen-containing compounds other than acetone, methanol, CO and CO2: greater than 0.5 ppm, or at least 0.75 ppm, or at least 1 ppm, or at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, or

[0066] viii.COS: 0.5ppm, or at least 0.75ppm, or at least 1ppm, or at least 2ppm, or at least 5ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 30ppm, or MAPD: greater than 1ppm, or at least 2ppm, or at least 5ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 30ppm.

[0067] Also provided is a method for introducing an impurity into a (C4)alkanoic acid composition, comprising:

[0068] a. preparing (C4) alkanoic acid using a first propylene feedstock; and

[0069] b. providing a second propylene feedstock, at least a portion of which is obtained by cracking recycled pyrolysis oil and contains impurities that are not present in the first propylene feedstock or are present in more than the first propylene feedstock, the source of which is the cracking of recycled pyrolysis oil; and

[0070] c. preparing a (C4) alkanoic acid composition comprising a (C4) alkanoic acid and said impurities by step (b); and

[0071] d. optionally recovering the (C4)alkanoic acid composition containing the impurities.

[0072] Also provided is a method for introducing an impurity into a (C4)alkanoic acid composition, comprising:

[0073] a. preparing (C4) alkanal from a first propylene feedstock; and

[0074] b. providing a second propylene feedstock, at least a portion of which is obtained by cracking recycled pyrolysis oil and contains impurities that are not present in the first propylene feedstock or are present in more than the first propylene feedstock, the source of which is the cracking of recycled pyrolysis oil; and

[0075] c. preparing (C4) alkanal comprising (C4) alkanal and said impurities by step (b); and

[0076] d. preparing a (C4) alkanoic acid composition from the (C4) alkanal, wherein the (C4) alkanoic acid composition comprises (C4) alkanoic acid and the impurity; and

[0077] e. optionally recovering the (C4)alkanoic acid composition containing the impurities.

[0078] Also provided is a method for introducing an impurity into a (C4)alkanoic acid composition, comprising:

[0079] a. preparing (C4) alkanal from a first propylene feedstock; and

[0080] b. providing a second propylene feedstock, at least a portion of which is obtained by cracking recycled pyrolysis oil and contains impurities that are not present in the first propylene feedstock or are present in more than the first propylene feedstock, the source of which is the cracking of recycled pyrolysis oil; and

[0081] c. preparing (C4) alkanal comprising (C4) alkanal and said impurities by step (b); and

[0082] d. preparing a (C4) alkanoic acid composition from the (C4) alkanal, wherein the (C4) alkanoic acid composition comprises (C4) alkanoic acid and the impurity; and

[0083] e. optionally recovering the (C4)alkanoic acid composition containing the impurities.

[0084] Also provided is a method for preparing (C4) alkanoic acid from raw materials to final product (cradle to final product), comprising:

[0085] a. preparing a recovered pyrolysis oil composition by pyrolysis recovery of raw materials (r-pyrolysis oil); and

[0086] b. cracking r-pyrolysis oil to produce a first recovered propylene composition, at least a portion of which is obtained from cracking r-pyrolysis oil (r-propylene); and

[0087] c. converting at least a portion of the r-propylene during the synthesis process to produce a recovered (C4) alkanal (r-(C4) alkanal); and

[0088] d. converting at least a portion of the (C4)alkanal during the synthesis to produce (C4)alkanoic acid. In one embodiment, step e can be omitted and r-propylene can be directly converted to (C4)alkanoic acid.

[0089] Also provided is a (C4)alkanoic acid composition obtained by any of the methods described herein.

[0090] A method for processing a recovered propylene composition at least a portion of which is derived directly or indirectly from a cracked recovered pyrolysis oil composition (r-propylene) is provided, the method comprising feeding the r-propylene to a reactor to produce (C4) alkanoic acids, wherein the recovered pyrolysis oil is obtained by pyrolysis of a waste stream that does not contain non-kosher materials (or contains only post-industrial materials).

[0091] A method for treating recovered (C4)alkanals (r-(C4)alkanals) prepared from a recovered propylene composition, at least a portion of which is derived directly or indirectly from a cracked recovered pyrolysis oil composition (r-propylene), the method comprising feeding r-(C4)alkanals to a reactor to produce (C4)alkanoic acids, wherein the recovered pyrolysis oil is obtained by pyrolysis of a waste stream that does not contain non-clean materials (or contains only post-industrial materials). BRIEF DESCRIPTION OF THE DRAWINGS

[0092] 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).

[0093] 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.

[0094] Figure 3 is a schematic diagram of a pyrolysis process to produce an olefin-containing product.

[0095] 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.

[0096] Figure 5 is a schematic diagram of a cracking furnace suitable for receiving r-pyrolysis oil.

[0097] Figure 6 A furnace coil configuration with multiple tubes is shown.

[0098] Figure 7 Various feed positions of r-pyrolysis oil into the cracking furnace are shown.

[0099] Figure 8 A cracking furnace with a vapor liquid separator is shown.

[0100] Fig. 9 is a block diagram showing the process of recovering constituent furnace effluent.

[0101] Fig.10 A fractionation scheme is shown for separating and isolating the separation sections of the main r-compositions, including a demethanizer, a deethanizer, a depropanizer and a fractionation column, the main r-compositions including r-propylene, r-ethylene, r-butene, etc.

[0102] Fig.11 A laboratory scale cracking unit design is shown.

[0103] Fig.12Design features for a plant-based experimental feeding of r-pyrolysis oil to a gas-fed cracking furnace are described.

[0104] Fig.13 is a boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis with 74.86% C8+, 28.17% C15+, 5.91% aromatics, 59.72% alkanes and 13.73% unidentified components.

[0105] Fig.14 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0106] Fig.15 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0107] Fig.16 The boiling point curve of r-pyrolysis oil obtained by distillation in the laboratory and chromatography analysis.

[0108] Fig.17 is a boiling point graph of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350°C, 50% boils between 95°C and 200°C, and at least 10% boils at 60°C.

[0109] Fig.18 is a boiling point graph of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 150°C, 50% boils between 80°C and 145°C, and at least 10% boils at 60°C.

[0110] Fig.19 is a boiling point graph of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350°C, at least 10% boils at 150°C, and 50% boils between 220°C and 280°C.

[0111] Fig. 20 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with 90% boiling points between 250-300°C.

[0112] Fig.21 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with 50% boiling point between 60-80°C.

[0113] Fig. 22 is a boiling point graph of r-pyrolysis oil distilled in the laboratory with 34.7% aromatic content.

[0114] Fig.23 is a boiling point graph of r-pyrolysis oil having an initial boiling point of about 40°C.

[0115] Fig.24is a graph of the carbon distribution of the pyrolysis oil used in the plant trials.

[0116] Fig.25 is a graph of the carbon distribution of the pyrolysis oil used in the plant trials. DETAILED DESCRIPTION

[0117] In the embodiments, "r-(C4)alkanoic acid" refers to a (C4)alkanoic acid derived from r-propylene, where derived from means that at least some of the feedstock raw material has some r-propylene content.

[0118] The process for preparing a recovered component compound, such as a (C4)alkanal or (C4)alkanoic acid, begins by feeding a recovered propylene composition ("r-propylene") to a reactor in a reaction scheme for preparing intermediates and / or reactants, wherein the r-propylene is derived directly or indirectly from a cracked r-pyrolysis oil.

[0119] The terms "containing" and "including" are synonymous with comprising.

[0120] 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 an "or" relationship. For example, "at least 10, 20, 30, 40, 50, 75 wt.% ..." means the same as "at least 10 wt.%, or at least 20 wt.%, or at least 30 wt.%, or at least 40 wt.%, or at least 50 wt.%, or at least 75 wt.%", etc.; and "not more than 90 wt.%, 85, 70, 60 ..." means the same as "not more than 90 wt.%, or not more than 85 wt.%, or not more than 70 wt.% ....", etc.; and "at least 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by weight ..." means the same as “at least 1 wt.%, or at least 2 wt.%, or at least 3 wt.%...” etc.; and “at least 5, 10, 15, 20 and / or not more than 99, 95, 90 weight percent” means the same as “at least 5 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, and / or not more than 99 wt.%, or not more than 95 wt.%, or not more than 90 weight percent...” etc.; 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...” etc.

[0121] The process for producing recovered (C4)alkanoic acids begins by feeding a recovered propylene composition ("r-propylene"), derived directly or indirectly from cracked r-pyrolysis oil, to a reactor for producing (C4)alkanals. The (C4)alkanals are then oxidized to (C4)alkanoic acids.

[0122] Pyrolysis / cracking systems and processes

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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 ducts within the convection box 312, and may optionally extend outside the convection box 312 and return to or interconnect with ducts 314 within the convection box 312. The radiant zone 320 includes radiant coils / tubes 324 and burners 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 .

[0127] Unless otherwise indicated, all component amounts provided herein (eg, for feeds, materials, streams, compositions, and products) are expressed on a dry basis.

[0128] 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 of pressure, and at least a portion of which is obtained from the cracking of recycled waste (e.g., waste plastic or waste streams).

[0129] As used herein, "r-ethylene" refers to a composition comprising: (a) ethylene obtained from cracking a cracker feed containing r-pyrolysis oil, or (b) ethylene having a recovery content value attributable to at least a portion of the ethylene; and "r-propylene" refers to a composition comprising (a) propylene obtained from cracking a cracker feed containing r-pyrolysis oil, or (b) propylene having a recovery content value attributable to at least a portion of the propylene.

[0130] References to "r-ethylene molecules" refer to ethylene molecules derived directly from the cracking of a cracker feed containing r-pyrolysis oil. References to "r-propylene molecules" refer to propylene molecules derived directly from the cracking of a cracker feed containing r-pyrolysis oil.

[0131] As used herein, "(C4) alkanal" refers to a composition comprising butanal, isobutyraldehyde, or a combination thereof, whether or not the butanal or isobutyraldehyde has a recycled content.

[0132] As used herein, "r-(C4) alkanal" refers to a composition comprising butyraldehyde, isobutyraldehyde, or a combination thereof, having a recycled content.

[0133] As used herein, "(C4)alkanoic acid" refers to a composition comprising butyric acid, isobutyric acid, or a combination thereof, whether or not the butyric acid or isobutyric acid has a recycled component.

[0134] As used herein, "r-(C4)alkanoic acid" refers to a composition comprising butyric acid, isobutyric acid, or a combination thereof, having a recycled content.

[0135] As used herein, the term "predominantly" means greater than 50 weight percent, unless expressed in 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 weight percent propane, or if expressed in mol%, refers to a product that contains greater than 50 mol% propane.

[0136] As used herein, the term "recovered content" is used i) as a noun to refer to a physical component (e.g., a compound, molecule, or atom) derived from r-pyrolysis oil or ii) as an adjective modifying a specific composition (e.g., a feedstock or product) at least a portion of which is derived directly or indirectly from r-pyrolysis oil.

[0137] As used herein, a composition "directly derived from" cracked pyrolysis oil has at least one physical component traceable to an r-composition at least a portion of which was obtained by or in conjunction with cracking 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 cracking r-pyrolysis oil.

[0138] "Recovered Content Value" is a unit of measurement that represents the amount of material that originated as r-pyrolysis oil. The recovered content value may originate from any type of r-pyrolysis oil and any type of cracking furnace used to crack r-pyrolysis oil.

[0139] The specific recovery component value can be determined by mass balance method or mass ratio or percentage or any other measurement unit, and can be determined according to any system for tracing back, allocating and / or depositing and lending the recovery components in various compositions. The recovery component value can be deducted from the recovery component inventory and applied to the product or composition to attribute the recovery component 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 the quota is obtained is also cracked in a cracking furnace as described throughout one or more embodiments of this article.

[0140] In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the recovered component quota or recovered component value deposited into the recovered component inventory is obtained from the 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:

[0141] a. Quota, or

[0142] b. deposited into recycled content inventory, or

[0143] c. The recycled content value in the recycled content inventory, or

[0144] d. The recycled content value applied to the composition to prepare a recycled content product, intermediate or article (recycled PIA) is obtained from r-pyrolysis oil.

[0145] A PIA that is recovered is a product, intermediate or article that may include a compound or a composition containing a compound or polymer, and / or an article with a related recovery component value. A PIA does not have a recovery component value associated with it. As used herein, the term "recovery component quota" or "quota" means a recovery component value transferred from a starting composition to a receiving composition (a composition receiving a quota), at least a portion of which is obtained by cracking r-pyrolysis oil or obtained together with cracking r-pyrolysis oil, and the receiving composition may or may not have a physical component that can be traced back to the composition, at least a portion of which is obtained by cracking r-pyrolysis oil or obtained together with cracking r-pyrolysis oil, wherein the recovery component value (whether by mass or percentage or any other unit of measurement) is determined according to a standard system for tracking, allocating and / or recording the recovery components in various compositions. A "composition" that receives a quota or a recovery component value may include a composition of a substance, a compound, a product, a polymer or an article.

[0146] “Recycled Content Quota” or “Quota” means the recycled content value that:

[0147] a. from r-pyrolysis oil or recycled waste used to make r-pyrolysis oil (collectively referred to herein as "r-pyrolysis oil" for convenience) to a receiving composition or recycled PIA, which may or may not have physical components traceable to the r-pyrolysis oil; or

[0148] b. Deposited into a stock of recovered components, at least a portion of which is derived from r-pyrolysis oil.

[0149] The quota can be an allocation or a credit. In one embodiment or in combination with any embodiment mentioned herein, the composition receiving the recovery component quota can be a non-recovery composition, thereby converting the non-recovery composition into an r-composition. As used herein, "non-recovery" refers to a composition that is not directly or indirectly derived from the cracking of r-pyrolysis oil. As used herein, in the context of the feed of a cracker or furnace, "non-recovery feed" refers to a feed that is not obtained from a waste stream or r-pyrolysis oil. Once a non-recovery feed or PIA obtains a recovery component quota (e.g., by a credit or allocation), it becomes a recovery component feed, a composition, or recycles the PIA.

[0150] 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 associated with 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 person or entity or ultimately at least partially by various affiliates controlled or owned by a parent entity ("entity family"), or they can come from different entity families. Typically, the recovery component allocation travels with the composition and downstream derivatives of the composition. The allocation can be deposited into the recovery component stock and taken out from the recovery component stock as an allocation and applied to the composition to prepare an r-composition or recycle PIA.

[0151] The term "recovered component credit" refers to a recovered component quota, wherein the quota is not limited to being associated with a composition made from cracked r-pyrolysis oil or downstream derivatives thereof, but rather has the flexibility to be obtained from r-pyrolysis oil and is (i) applied to a composition or PIA made from a process other than cracking a feedstock in a furnace, or (ii) applied to downstream derivatives of a composition made from a process other than cracking a feedstock 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 to the receiving entity or person. For example, the quota can be a credit when the quota is taken from r-pyrolysis oil and applied by the quota owner to a BTX composition or fraction thereof, which is manufactured by the owner or within its family of entities and obtained through the refining and fractionation of petroleum other than from 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.

[0152] Credits may be available for sale, transfer or use, or may be sold, transferred or used, or:

[0153] a. not sell the composition, or

[0154] b. sell or transfer the Composition, but the Quota is not related to the sale or transfer of the Composition, or

[0155] c. Deposited into or withdrawn from a recycled content stock that does not trace back molecules of the recycled content raw materials to molecules of the resulting composition made with the recycled content raw materials, or that has such traceability but does not trace back to a specific quota applied to the composition.

[0156] In one embodiment or in combination with any of the embodiments mentioned, a quota may be deposited into a reclaimed component inventory, and a credit or allocation may be extracted from the inventory and applied to a composition. This would be the case where a quota is generated from an r-pyrolysis oil and deposited into a reclaimed component inventory, and a reclaimed component value is deducted from the reclaimed component inventory and applied to a composition to prepare an r-composition that does not have a portion of a product derived from a cracking furnace, or has a portion of a product derived from a cracking furnace, but such products constituting that portion of the composition are not obtained by cracking r-pyrolysis oil. In this system, there is no need to trace the source of reactants to cracking r-pyrolysis oil olefin-containing effluents or to any atom contained in r-pyrolysis oil olefin-containing effluents, but any reactant made by any process may be used and a reclaimed component quota associated with such reactant may be used.

[0157] 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 a cracker feedstock cracked in a cracker furnace. In one embodiment or in combination with any of the mentioned embodiments, a process is provided, wherein:

[0158] a. Obtaining r-pyrolysis oil,

[0159] b. Obtaining recovery component value (or quota) from r-pyrolysis oil and

[0160] i. Deposit to recycled content stock, withdraw allowance (or credit) from recycled content stock and apply it to any composition to obtain an r-composition, or

[0161] ii. directly applied to any composition without depositing into the recycled content stock to obtain an r-composition; and

[0162] 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

[0163] d. Optionally, at least a portion of the composition in step b originates from a cracker feed in a cracker furnace, optionally, the composition has been obtained by any of the feedstocks comprising r-pyrolysis oil and the methods described herein.

[0164] Steps b. and c. do not have to occur simultaneously. In one embodiment or in combination with any of the embodiments mentioned, they occur within one year of each other, or within six (6) months of each other, or within three (3) months of each other, or within one (1) month of each other, or within two (2) weeks of each other, or within one (1) week of each other, or within three (3) days of each other. The process allows for the passage of time between the time 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.

[0165] 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 traced. The inventory can be in any form (electronic or paper), using any one or more software programs, or using various modules or applications (which trace 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 or deposits 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, six (6) months, 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 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 recycling waste streams. 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 (from which the recycling component value is deposited into the recycling component inventory) is also processed by any one or more of the cracking processes described herein.

[0166] The determination of whether an r-composition is derived directly or indirectly from cracked r-pyrolysis oil 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 the reactor used to prepare the final product (such as (C4)alkanal or (C4)alkanoic acid) can be traced back to an r-composition prepared by cracking of the r-pyrolysis oil.

[0167] As described above, if at least a portion of the atoms or molecules in the reactant feedstock for preparing the product can be traced back to at least a portion of the atoms or molecules constituting the r-composition produced during the cracking r-pyrolysis oil fed to the cracking furnace via one or more intermediate steps or entities, the final product is considered to be directly derived from the cracking r-pyrolysis oil. Before preparing the r-composition, any number of intermediates and intermediate derivatives can be prepared. The r-composition manufacturer usually sells this r-composition to an intermediate entity after refining and / or purifying and compressing to produce a specific r-composition of the desired grade, and then the intermediate entity sells the r-composition or one or more derivatives thereof to another intermediate entity for preparing an intermediate product, or directly to a product manufacturer. Before preparing the final product, any number of intermediates and intermediate derivatives can be prepared. The actual r-composition volume, whether condensed into a liquid, supercritical or stored as a gas, can be left in the equipment that prepares it, or can be transported to a different location, or kept in an off-site storage device before being used by an intermediate or product manufacturer. For tracking purposes, once the r-composition produced by cracking r-pyrolysis oil is mixed with another volume of composition (e.g. r-ethylene mixed with non-recycled ethylene) in, for example, a storage tank, salt dome or cave, then the entire tank, dome or cave becomes the source of r-composition, and for tracking purposes, withdrawals from such storage facilities are withdrawals from the source of r-composition until 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.

[0168] An r-composition is considered to be indirectly derived from an r-pyrolysis oil if it is associated with a recycled content quota and may or may not contain physical components that are traceable to the r-composition, at least a portion of which is obtained by or in conjunction with cracking of the 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 claim recycled content through a system 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 for the association of a recycled content value with a portion or all of the compounds in the olefin-containing effluent or derivatives thereof and the transfer of such quota to the manufacturer of the product or any intermediary that obtains a supply of one or more compounds in the olefin-containing effluent or derivatives thereof from the supplier. The transfer may be made by the supplier transferring the r-compound to the manufacturer of the product or intermediary, or by transferring a quota (e.g., a credit) without associating such quota with the transferred compound. In this system, there is no need to track the source of the olefin volume from cracked r-pyrolysis oil, but rather any olefin volume produced by any process can be used and a recovery component quota associated to that olefin volume.

[0169] Examples of (C4) alkanoic acids wherein the r-composition is r-propylene and the product is an amount of r-composition directly or indirectly derived from r-pyrolysis oil prepared using r-pyrolysis oil include:

[0170] (i) a cracker facility, wherein the r-propylene produced in the facility may be in continuous or intermittent fluid communication with a (C4)alkanoic acid formation facility (which may be a storage vessel to the (C4)alkanoic acid facility or directly to a (C4)alkanoic acid formation reactor) via interconnected pipelines, optionally via one or more storage vessels and valves or interlocks, and the r-propylene feedstock may be supplied via interconnected pipelines:

[0171] a. withdrawn from a cracker facility during r-propylene production or thereafter during the time r-propylene is piped to a (C4) alkanoic acid formation facility; or

[0172] b. withdrawn from one or more storage tanks at any time, provided that at least one storage tank is fed with r-propylene, as long as the entire volume of the one or more storage tanks is replaced by feed containing no r-propylene; or

[0173] (ii) transporting propylene containing or having been fed with r-propylene from a storage vessel, vault or facility, or 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 propylene feedstock containing no r-propylene; or

[0174] (iii) a manufacturer of a (C4)alkanoic acid certifies, represents, or advertises to its customers or the public that its (C4)alkanoic acid contains recycled content or is derived from a feedstock derived from recycled content, wherein such recycled content is claimed to be based in whole or in part on a propylene feedstock associated with a quota of propylene produced from cracked r-pyrolysis oil; or

[0175] (iv) Manufacturers of (C4)alkanoic acids have obtained:

[0176] a. the amount of propylene produced from r-pyrolysis oil as certified, represented or advertised, or

[0177] b. has transferred to the (C4)alkanoic acid manufacturer a credit for the supply of propylene sufficient to allow the (C4)alkanoic acid manufacturer to meet the certification requirements or make its representations or claims, or

[0178] c. The propylene has been allocated to its recovery component, whereby the quota is obtained through one or more intermediate entities from cracked propylene quantities, at least part of which is obtained by cracking r-pyrolysis oil.

[0179] In one embodiment or in combination with any embodiment mentioned herein, the recycled content may be derived directly or indirectly from cracked r-pyrolysis oil, wherein at least a portion of the r-pyrolysis oil is obtained from pyrolysis of recycled waste (e.g., waste plastic or waste stream).

[0180] In one embodiment or in combination with any of the mentioned embodiments, various methods are provided for allocating recovered components among various olefin-containing effluent volumes or compounds thereof produced by any one or combination of entities in a family of entities. For example, a cracking furnace owner or operator, or any one of a family of entities, or a site, may:

[0181] a. A symmetrical distribution of recovery component values ​​between at least two compounds in the olefin-containing effluent or between RIAs based on the same fractional percentage of the recovery component in one or more feedstocks or based on the quota amount received. For example, if 5 wt% of the total cracker feed added to the furnace is r-pyrolysis oil, then one or more compounds in the olefin-containing effluent may contain a 5 wt% recovery component value, or one or more compounds may contain a 5 wt% recovery component value minus any yield losses, or one or more PIAs may contain a 5% recovery component value. In this case, the amount of recovery component in the compound is proportional to all other products that receive a recovery component value; or

[0182] b. adopting an asymmetric distribution of recovery component values ​​between compounds in the olefin-containing effluent or between its PIAs. In this case, the recovery component value associated with a compound or RIA can exceed the recovery component value associated with other compounds or RIAs. For example, a volume or batch of olefin-containing effluent can receive a larger amount of recovery component value than other batches or volumes of olefin-containing effluent, or one or a combination of compounds in the olefin-containing effluent can receive a disproportionately higher amount of recovery component value relative to other compounds in the olefin-containing effluent or other PIAs, some of which may not receive a recovery component value. One volume of the olefin-containing effluent or PIA may contain 20% by mass of recycled content and another volume or RIA may contain 0% recycled content, even though the two volumes may be identical in composition and produced continuously, provided that the value of recycled content withdrawn from the recycled content stock and applied to the olefin-containing effluent does not exceed the value of recycled content deposited into the recycled content value stock, or if a shortfall occurs, the overdraft is rebalanced to zero or a positive credit available as described above, or if there is no recycled content value stock, provided that the total amount of recycled content value associated with any one or more compounds in the olefin-containing effluent does not exceed the quota obtained from r-pyrolysis oil or exceeds the quota, then rebalance. In an asymmetric distribution of recycled content, the manufacturer can adapt the recycled content to the volume of the olefin-containing effluent or to the compounds of interest in the olefin-containing effluent or PIA, which is sold according to customer needs, thereby providing flexibility among customers, some of whom may require more recycled content than other customers in the r-compound or recycled PIA.

[0183] In one embodiment or in combination with any embodiment mentioned herein, the symmetrical and asymmetrical distribution of recovered 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 recovered components obtained from the r-pyrolysis oil can be within a site, and the recovered component values ​​from the r-pyrolysis oil can be applied to one or more olefin-containing effluent volumes or one or more compounds in the olefin-containing effluent volumes or to one or more PIAs prepared from compounds in the olefin-containing effluent at the same site. The recovered component values ​​can be symmetrically or asymmetrically applied to one or more different olefin-containing effluent volumes or one or more compounds in the olefin-containing effluent or the PIA prepared at the site.

[0184] In one embodiment or in combination with any of the embodiments mentioned, the input or generation of the recovery component (recovery component raw material or quota) can be to or at the first site, and the recovery component value from the input is transferred to the second site and applied to one or more compositions prepared at the second site. The recovery component value can be applied to the composition symmetrically or asymmetrically at the second site. The recovery component value of "derived from cracked r-pyrolysis oil" or "obtained from cracked r-pyrolysis oil" or the recovery component value derived from cracked r-pyrolysis oil directly or indirectly does not imply when the recovery component value or quota is taken, captured, deposited in the recovery component inventory or the time of transfer. The timing of depositing the quota or recovery component value in the recovery component inventory or realizing, identifying, capturing or transferring it is flexible, and can be carried out as early as receiving the r-pyrolysis oil at a site within the entity family that owns it or by an entity or r-pyrolysis oil that owns or operates a cracking facility into the inventory or within the entity family. Thus, a quota or recovered component value for a volume of r-pyrolysis oil may be obtained, captured, deposited into a recovered component inventory, or transferred to a product, without that volume having been 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. The quota taken when r-pyrolysis oil is owned, possessed, or received and deposited into a recovered component inventory is a quota associated with, obtained from, or derived from cracked r-pyrolysis oil, even if the r-pyrolysis oil has not yet been cracked when the quota is taken or deposited, provided that the r-pyrolysis oil is cracked at some point in the future.

[0185] In one embodiment, the r-composition, or a downstream reaction product thereof, or a recycled PIA has associated therewith, or contains, or is labeled, advertised or certified as containing, a recycled component in an amount of at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, or at least 0.5 wt.%, or at least 0.75 wt.%, or at least 1 wt.%, or at least 1.25 wt.%, or at least 1.5 wt.%, or at least 1.75 wt.%, or at least 2 wt.%, or at least 2.25 wt.%, or at least 2.5 wt.%, or at least 2.75 wt.%, or at least 3 wt.%, or at least 3.5 wt.%, or at least 4 wt.%, or at least 4.5 wt.%, or at least 5 wt.%, or at least 6 wt.%, or at least 7 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%. %, or at least 45 wt.%, or at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.%, or at least 65 wt.% and / or the amount may be at most 100 wt.%, or at most 95 wt.%, or at most 90 wt.%, or at most 80 wt.%, or at most 70 wt.%, or at most 60 wt.%, or at most 50 wt.%, or at most 40 wt.%, or at most 30 wt.%, or at most 25 wt.%, or at most 22 wt.%, or at most 2 %, or up to 18wt.%, or up to 16wt.%, or up to 15wt.%, or up to 14wt.%, or up to 13wt.%, or up to 11wt.%, or up to 10wt.%, or up to 8wt.%, or up to 6wt.%, or up to 5wt.%, or up to 4wt.%, or up to 3wt.%, or up to 2wt.%, or up to 1wt.%, or up to 0.9wt.%, or up to 0.8wt.%, or up to 0.7wt.%. The recycled component value associated with an r-composition, r-compound, or its downstream reaction product can be associated by applying a quota (credit or allocation) to any manufactured or sold composition, compound, PIA. The quota can be included in a quota inventory created, maintained, or operated by or for a manufacturer of recycled PIA or r-composition. The quota can be obtained from any source along any manufacturing chain of the product as long as it is derived from cracking a feedstock containing r-pyrolysis oil.

[0186] In one embodiment or in combination with any of the mentioned embodiments, a recycled PIA manufacturer can manufacture a recycled PIA, or process reactants to manufacture a recycled PIA by obtaining reactants (e.g., any compound of an olefin-containing cracker effluent) from a supplier (e.g., a cracker manufacturer or one of its family of entities) from any source, whether or not such reactants have any recycled content, and:

[0187] i. also receive a recycling quota for that reactant from the same reactant supplier, or

[0188] ii. Obtaining a Recovery Content Credit from any person or entity without providing reactants from said person or entity to which said Recovery Content Credit is transferred.

[0189] The quota in (i) is obtained from the reactant supplier, and the reactant supplier also supplies reactants to the recovery PIA manufacturer or in its entity family. The situation described in (i) allows the recovery PIA manufacturer to obtain the supply of non-recovery component reactants, and also obtains the recovery component quota from the supplier. In one embodiment or in combination with any embodiment mentioned, the reactant (for example, propylene, ethylene, butene, etc.) supplier transfers the recovery component quota to the recovery PIA manufacturer, and the supply of reactants is transferred to the recovery PIA manufacturer, wherein the recovery component quota is not associated with the supplied reactant, or even not associated with any reactant prepared by the reactant supplier. The recovery component quota need not be associated with the amount of the recovery component in the reactant supplied or for preparing the recovery PIA, containing olefin effluent, which makes the reactant supplier and the recovery PIA manufacturer flexibly distribute the recovery component between the various products prepared by them separately. However, in each of these situations, the recovery component quota is associated with cracking r-pyrolysis oil.

[0190] In one embodiment or in combination with any of the embodiments mentioned, the reactant supplier transfers the recovery component quota to the recovery PIA manufacturer, and the supply of reactant is transferred to the recovery PIA manufacturer, wherein the recovery component quota is associated with the reactant. The transfer of this quota can be carried out only by supplying the reactant with associated recovery components. Optionally, the reactant supplied is the r-compound separated from the olefin-containing effluent obtained by cracking r-pyrolysis oil, and at least a portion of the recovery component quota is associated with the r-compound (or r-reactant). The recovery component quota transferred to the recovery PIA manufacturer can be provided in advance with the reactant, optionally provided in batches, or with each batch of reactants, or distributed between the parties as needed.

[0191] The quota in (ii) is obtained from any individual or entity by the recovery PIA manufacturer (or its entity family), and the supply of reactants is not obtained from the individual or entity. The individual or entity can be a reactant manufacturer that does not provide reactants to the recovery PIA manufacturer or its entity family, or the individual or entity can be a manufacturer that does not manufacture reactants. In either case, the situation of (ii) allows the recovery PIA manufacturer to obtain the recovery component quota without having to purchase any reactants from the entity or individual that supplies the recovery component quota. For example, an individual or entity can transfer the recovery component quota to the recovery PIA manufacturer or its entity family through a buy / sell model or contract, without the need to purchase or sell quotas (for example, as a product exchange of products that are not reactants), or an individual or entity can directly sell quotas to one of the recovery PIA manufacturer or its entity family. Alternatively, an individual or entity can transfer products other than reactants together with their associated recovery component quotas to the recovery PIA manufacturer. This is attractive for the recovery PIA manufacturer with the diversified business of preparing various PIAs instead of requiring the PIA manufactured by the reactants provided.

[0192] The quota can be deposited into a reclaimed component inventory (e.g., a quota inventory). In one embodiment or in combination with any of the embodiments mentioned, the quota is generated by a manufacturer of an olefin-containing effluent containing olefin-containing effluent containing olefin-containing effluent. The manufacturer can also manufacture a PIA, whether or not the reclaimed component is applied to the PIA, and whether or not the reclaimed component (if applied to the PIA) is taken out of the reclaimed component inventory. For example, a manufacturer of an olefin-containing effluent containing olefin-containing effluent containing olefin-containing effluent can:

[0193] a. deposit the allowance into stock and store it only; or

[0194] b. Olefin-containing effluents Olefin-containing effluents deposit the quota into inventory and apply the quota from the inventory to one or more compounds in the olefin-containing effluent or to any PIA produced by the manufacturer, or

[0195] c. Selling or transferring the allowances from the recycled content stock to a third party, wherein at least one allowance acquired as described above is deposited into the recycled content stock.

[0196] If desired, any recovery component quota of any amount can be deducted and applied to PIA to prepare recovery PIA, or applied to non-recovered olefin effluent to prepare olefin effluent. For example, quotas with various sources for creating quotas can be generated. Some recovery component quotas (credits) can be derived from methanol decomposition of recycled waste, or from gasification of other types of recycled waste, or from mechanical recycling of waste plastics or metal recycling, or from any other chemical or mechanical recycling technology. The recovery component inventory can track or not track the source or basis of the recovery component value, or the inventory can not allow the source or basis of the quota to be associated with the quota applied to the r-composition. It is sufficient that the allowance is deducted from the recovered component inventory and applied to the PIA or non-recovered olefin-containing effluent, regardless of the source of the allowance, so long as the recovered component allowance obtained from the r-pyrolysis oil is present in the recovered component inventory at the time of withdrawal, or the recovered component allowance is obtained from the recycled PIA manufacturer as specified in step (i) or step (ii), regardless of whether the recovered component allowance is actually deposited in the recovered component inventory.

[0197] In one embodiment or in combination with any of the embodiments mentioned, the recovered component quota obtained in step (i) or (ii) is deposited into the quota inventory. In one embodiment or in combination with any of the embodiments mentioned, the recovered component quota deducted from the recovered component inventory and applied to the PIA or non-recovered olefin-containing effluent (or any compound therein) is derived from r-pyrolysis oil.

[0198] As used throughout, the recovery component inventory can be owned by the owner of the cracking furnace that processes r-pyrolysis oil or one of its entity families, olefin-containing effluents or owned by the recovery PIA manufacturer, or operated by any of them, or owned or operated by any of them but at least partially benefited by any of them, or licensed by any of them or licensed to any of them. Similarly, the cracker olefin-containing effluent manufacturer or the recovery PIA manufacturer can also include any of their entity families. For example, although any of them may not own or operate inventory, one of its entity families can own such a platform, or license it from an independent supplier, or operate it for any of them. Alternatively, an independent entity can own and / or operate inventory, and operate and / or manage at least a portion of the inventory for any of them for a service fee.

[0199] In one embodiment or in combination with any of the mentioned embodiments, the recycled PIA manufacturer obtains a supply of reactants from a supplier and also obtains a quota from the supplier, wherein such quota is derived from r-pyrolysis oil and optionally the quota is associated with the reactants supplied by the supplier. In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the quota obtained by the recycled PIA manufacturer is:

[0200] a. Applied to PIA prepared by supplying reactants;

[0201] b. Applied to PIAs made from the same type of reactants, but not from the volume of reactants supplied, such as PIAs made from the same type of reactants already made and stored in inventory or to future manufactured PIAs; or

[0202] c. deposited into the stock, deducted from the stock the allowance applicable to PIA made from a different type of reactant than that supplied, or

[0203] d. Deposit into inventory and store.

[0204] It is not necessary to use r-reactants to prepare recovery PIA in all embodiments, or to obtain recovery PIA from recovery component quotas associated with reactants. In addition, it is not necessary to apply quotas to raw materials to prepare recovery PIA to which recovery components are applied. On the contrary, as described above, even if associated with reactants when reactants are obtained, the quota can be deposited into the electronic inventory. However, in one embodiment or in combination with any of the embodiments mentioned, the reactants associated with the quota are used to prepare recovery PIA. In one embodiment or in combination with any of the embodiments mentioned, recovery PIA is obtained from recovery component quotas associated with r-reactants or r-pyrolysis oil or with cracked r-pyrolysis oil.

[0205] 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:

[0206] a. applying the quota to any PIA produced directly or indirectly (e.g. via a reaction scheme with several intermediates) from cracking r-pyrolysis oil containing olefins; or

[0207] b. applying the quota to any PIA not produced directly or indirectly from cracked r-pyrolysis oil olefin-containing effluent, such as where PIA has already been produced and stored in inventory or where PIA is produced in the future; or

[0208] 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

[0209] d. is deposited into inventory and stored for later use.

[0210] In an embodiment, a package or combination of a recycled PIA and a recycled component identifier associated with the recycled PIA is also provided, wherein the identifier is or includes an indication that the recycled PIA includes or is derived from or is associated with a recycled component. The package can be any suitable package for containing polymers and / or articles, such as a plastic or metal drum, railroad car, isotainer, tote, polytote, bale, IBC tote, bottle, compressed bale, oil drum, plastic bag, spool, roving, winding or cardboard packaging. The identifier can be a certification document, a product manual stating the recycled content, a label, a logo or certification mark from a certification body, which indicates that the product or packaging contains the content or the recycled PIA contains the content, or is made from a source or is associated with recycled content, or it can be an electronic statement accompanying a purchase order or product by the manufacturer of the recycled PIA, or posted on a website as a statement, display, or a logo indicating that the recycled PIA contains or is associated with recycled content or is made from a source that contains recycled content, or it can be an advertisement electronically transmitted, by a website or in a website, by email, or by television or through a trade show in each case associated with the recycled PIA. The identifier does not need to declare or indicate that the recycled content is derived from r-pyrolysis oil. Instead, the identifier can simply convey or communicate that the recycled PIA has or is derived from recycled content, regardless of the source. However, the recycled PIA has a recycled content quota that is at least partially associated with r-pyrolysis oil.

[0211] 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.

[0212] In one embodiment or in combination with any of the mentioned embodiments, there is provided a system or package comprising:

[0213] a. Reclaim PIA, and

[0214] b. An identifier, such as a credit, label or certificate associated with the PIA, wherein the identifier is an indication that the PIA has or is derived from recycled content (which does not necessarily identify the source of the recycled content or quota), provided that the recycled PIA prepared therefrom has a quota, or is prepared from reactants, at least in part, associated with r-pyrolysis oil.

[0215] The system can be a physical combination, such as a package having at least some recycled PIA as its contents, and a label, such as a logo, which identifies that the contents of the recycled PIA, for example, have or are derived from recycled components. Alternatively, whenever it transfers or sells a recycled PIA with or derived from recycled components, the label or certificate can be issued to a third party or customer as part of the entity's standard operating procedures. The identifier does not have to be physically on the recycled PIA or on the packaging, and does not have to be on any physical document accompanying the recycled PIA or associated with the recycled PIA or packaging. For example, the identifier can be an electronic document, certificate, or identification mark associated with selling the recycled PIA to a household. The identifier itself only needs to convey or communicate that the recycled PIA has or is derived from recycled components, regardless of the source. In one embodiment or in combination with any of the embodiments mentioned, an article manufactured by recycling PIA can have an identifier, such as a stamp or logo embedded or adhered to the article or packaging. In one embodiment or in combination with any of the embodiments mentioned, the identifier is an electronic recycled component credit from any source. In one embodiment or in combination with any of the embodiments mentioned, the identifier is an electronic recycled component credit from r-pyrolysis oil.

[0216] The recycled PIA is supported by the reactants, whether or not the reactants are recycled component reactants. Once the PIA is prepared, it can be designated as having recycled components based on and derived from at least a portion of the quota. The quota can be taken or deducted from the recycled component stock. The amount deducted and / or applied to the PIA can correspond to any method, such as a mass balance method.

[0217] In one embodiment, the recycled PIA can be prepared by having a stock of recycled components, reacting reactants in a synthesis process to prepare PIA, extracting a quota from the stock of recycled components having a recycled component value, and applying the recycled component value to PIA to obtain the recycled PIA. The amount of quota deducted from the stock is flexible and will depend on the amount of recycled components applied to PIA. If it is not a complete amount, it is sufficient to correspond to at least a portion of the recycled components applied to PIA. The recycled component quota applied to PIA does not necessarily have to be derived from r-pyrolysis oil, but can be derived from any other method of generating a quota from recycled waste, such as by methanolysis or gasification of recycled waste, as long as the recycled component stock also contains a quota or has a quota deposit, which is derived from r-pyrolysis oil. However, in one embodiment or in combination with any of the embodiments mentioned, the recycled component quota applied to PIA is a quota obtained from r-pyrolysis oil.

[0218] The following are examples of the application of recycled content to PIA or to effluents or compounds containing non-recycled olefins therein:

[0219] 1. The PIA manufacturer applies at least a portion of the quota to the PIA to obtain recycled PIA, where the quota is associated with r-pyrolysis oil and the reactants used to prepare the PIA do not contain any recycled content; or

[0220] 2. The PIA manufacturer applies at least a portion of the quota to PIA to obtain recycled PIA, where the quota is obtained from recycled component reactant, regardless of whether the reactant volume is used to prepare the recycled PIA; or

[0221] 3. The PIA manufacturer applies at least a portion of the quota to the PIA to produce recycled PIA, wherein the quota is obtained from the r-pyrolysis oil, and:

[0222] a. Apply all the recovered components in the r-pyrolysis oil to determine the amount of recovered components in the recovered PIA, or

[0223] b. applying only a portion of the recovered content in the r-pyrolysis oil feedstock to determine the amount of recovered content in the recovered PIA, with the remainder stored in a recovered content inventory for future use or for application to other PIAs, or for increasing the recovered content on an existing recovered PIA, or a combination thereof, or

[0224] The recovered content in the cr-pyrolysis oil feedstock is not applied to the PIA but is stored in an inventory and the recovered content from any source is deducted from the inventory and applied to the PIA to prepare the recovered PIA; or

[0225] 4. A recycled PIA manufacturer applies at least a portion of a quota to reactants used to make the recycled PIA, thereby obtaining the PIA, wherein the quota is obtained by transferring or purchasing the same reactants used to make the PIA and the quota is associated with the recycled content in the reactants; or

[0226] 5. A recycled PIA manufacturer applies at least a portion of a quota to reactants used to make the recycled PIA, thereby obtaining the PIA, wherein the quota is obtained by transferring or purchasing the same reactants used to make the PIA, and the quota is not associated with the recycled content of the reactants but is associated with the recycled content of the monomers used to make the reactants; or

[0227] 6. A recycled PIA manufacturer applies at least a portion of a quota to reactants used to make the recycled PIA, thereby obtaining the PIA, wherein the quota is not obtained through the transfer or purchase of the reactants and the quota is associated with the recycled content of the reactants; or

[0228] 7. A recycled PIA manufacturer applies at least a portion of a quota to reactants used to make PIA, thereby obtaining recycled PIA, wherein the allocation is not obtained through the transfer or purchase of reactants and the quota is not associated with the recycled content of the reactants but rather with the recycled content of any monomer used to make the reactants; or

[0229] 8. Recycling PIA manufacturers obtain quotas derived from r-pyrolysis oil, and:

[0230] a. not applying a portion of the quota to the reactants to prepare PIA, but applying at least a portion of the quota to PIA to prepare recovered PIA; or

[0231] b. Less than all of the portion is applied to reactants used to prepare the recovered PIA, while the remainder is stored in inventory or applied to future prepared PIA or to existing recovered PIA in inventory to increase its recovered component value.

[0232] In one embodiment or in combination with any of the embodiments mentioned, recycled PIA or articles made therefrom can be offered for sale or sold as recycled PIA containing recycled content or obtained with recycled content. The sale or offer for sale can be accompanied by a certification or representation of a recycled content claim associated with the recycled PIA.

[0233] Designation of at least a portion of the recycled PIA or olefin-containing effluent as corresponding to at least a portion of a quota (e.g., an allotment or credit) can be performed in a variety of ways and according to the system employed by the recycled PIA manufacturer or olefin-containing effluent manufacturer, which can vary from manufacturer to manufacturer. For example, the designation can occur solely internally, through a log entry in a book or file of the manufacturer or other inventory software program, or through an instruction manual, packaging, advertisement or statement on the product, through a label associated with the product, through a certification declaration associated with the product sold, or through a formula that calculates the amount to be deducted from the inventory relative to the amount of recycled content applied to the product.

[0234] Alternatively, the recycled PIA may be sold. In one embodiment or in combination with any of the mentioned embodiments, there is provided a method of offering for sale or selling a polymer and / or article by:

[0235] a. A recycled PIA manufacturer or an olefin-containing effluent manufacturer or any of their family of entities (collectively, the Manufacturers) obtains or generates a recycled component quota, and the quota can be obtained by any method described herein and can be deposited into the recycled component inventory, and the source of the recycled component quota is r-pyrolysis oil,

[0236] b. converting a reactant in a synthetic process to prepare PIA, and the reactant may be any reactant or r-reactant,

[0237] c. designating (e.g., assigning or associating) recycled content to at least a portion of a PIA from a stock of recycled content to prepare a recycled PIA, wherein the stock contains at least one entry as a quota associated with r-pyrolysis oil. The designation can be a quota amount deducted from the stock, or an amount of recycled content declared or determined by the recycled PIA manufacturer in its accounts. Thus, the amount of recycled content does not necessarily have to be physically applied to the recycled PIA product. The designation can be an internal designation made to or by the manufacturer, or a service provider with whom the manufacturer has a contractual relationship, and

[0238] d. Offering to sell or selling a recycled PIA containing or obtained with the following recycled content, which recycled content at least partially corresponds to the designation. The amount of recycled content expressed as contained in the recycled PIA sold or offered for sale has a relationship or association with the designation. The amount of recycled content can be a 1:1 relationship between the amount of recycled content declared on the recycled PIA offered for sale or sold and the amount of recycled content allocated or designated to the recycled PIA by the recycled PIA manufacturer.

[0239] The steps do not have to be sequential and can be independent of each other. For example, step a) of obtaining a quota and the step of preparing recycled PIA can be performed simultaneously.

[0240] As used throughout, the step of deducting quotas from the inventory of recycled components does not need to be applied to the recycled PIA products. Deduction does not mean that the quantity disappears or is removed from the inventory log. Deduction can be an adjustment entry, a withdrawal, an addition as a debit entry, or any other algorithm that adjusts input and output based on the amount of recycled components associated with the product and one or the accumulated deposited quota amount in the inventory. 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 quotas to PIA (where such quotas are deducted from the inventory) does not need to physically apply quotas to recycled PIA products or to any documents issued in association with the recycled PIA products sold. For example, a recycled PIA manufacturer can ship recycled PIA products to customers, and the "application" of quotas to recycled PIA products is met by electronically transmitting recycled component credits to customers.

[0241] 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 of the deposits into the stock is associated with the r-pyrolysis oil.

[0242] In one embodiment or in combination with any of the mentioned embodiments, there is provided a recovered PIA obtained by any of the methods described above.

[0243] The reactants can be stored in storage containers and transported by truck, pipeline or ship to a recycled PIA manufacturing facility, or as further described below, an olefin-containing effluent manufacturing facility can be integrated with a PIA facility. The reactants can be transported or transferred to an operator or facility that prepares polymers and / or articles.

[0244] In one embodiment, the method for preparing the recovered PIA can be an integrated method. One such example is a method for preparing the recovered PIA by the following steps:

[0245] a. cracking r-pyrolysis oil to produce an olefin-containing effluent; and

[0246] b. separating the compounds in the olefin-containing effluent to obtain separated compounds; and

[0247] c. reacting any reactants in the synthesis process to prepare PIA;

[0248] d. depositing the quota into the quota stock, the quota being derived from r-pyrolysis oil; and

[0249] e. Apply any allowance from the stock to the PIA, thereby obtaining a recycled PIA.

[0250] 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:

[0251] a. providing an olefin-containing effluent manufacturing facility configured to produce reactants;

[0252] b. providing a PIA manufacturing facility having a reactor configured to receive reactants from the olefin-containing effluent manufacturing facility: and

[0253] 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,

[0254] wherein the olefin-containing effluent production facility generates or participates in the generation of quota and cracked r-pyrolysis oil. And:

[0255] (i) applying the quota to the reactants or to the PIA, or

[0256] (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.

[0257] 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 with the reactants by deducting allowances from their inventory and applying them to the PIA.

[0258] In one embodiment or in combination with any of the mentioned embodiments, there is also provided a system for producing recycled PIA as follows:

[0259] a. Providing an olefin-containing effluent manufacturing facility configured to produce an output composition comprising an olefin-containing effluent:

[0260] 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;

[0261] c. providing a PIA manufacturing facility having a reactor configured to receive reactants and produce an output composition comprising PIA;

[0262] 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.

[0263] A PIA production 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,

[0264] Fluid communication can be gaseous or liquid or both. Fluid communication does not need to be continuous and can be interrupted by storage tanks, valves or other purification or treatment facilities, as long as the fluid can be transported from the manufacturing facility to subsequent facilities through an interconnected pipeline network and without the use of trucks, trains, ships or aircraft. In addition, facilities can share the same site, or in other words, a site can contain 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 boundaries.

[0265] 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.

[0266] In one embodiment, an integrated recycling PIA production and consumption system is also provided. The system includes:

[0267] a. Providing an olefin-containing effluent manufacturing facility configured to produce an output composition comprising an olefin-containing effluent:

[0268] 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;

[0269] c. providing a PIA manufacturing facility having a reactor configured to receive reactants and produce an output composition comprising PIA;

[0270] d. A piping system interconnecting at least two of the facilities, optionally with intermediate processing equipment or storage facilities, the piping system being capable of taking an output composition from one facility and receiving the output at any one or more of the other facilities.

[0271] The system does not necessarily need the fluid communication between the two facilities, although fluid communication is desirable.For example, the compound separated from the olefin-containing effluent can be transported to the reactant facility by the interconnected pipeline network, and the interconnected pipeline network can be interrupted by other processing equipment, and the other processing equipment is such as processing, purifying, pumping, compressing or being suitable for merging the equipment or storage facilities of stream, and all these facilities comprise optional metering, valve or interlocking device.The equipment can be fixed to the ground or fixed to the structure fixed to the ground.The interconnected pipeline does not need to be connected to the reactant reactor or cracker, but is connected to the delivery and receiving point at the respective facilities.The interconnected pipeline system does not need to connect all three facilities to each other, but the interconnected pipeline system can be between the facility a)-b), or between b)-c), or between a)-b)-c).

[0272] A ring manufacturing method is also provided, the method comprising:

[0273] a. Providing r-pyrolysis oil, and

[0274] b. cracking r-pyrolysis oil to produce an olefin-containing effluent, and

[0275] (i) reacting compounds separated from the olefin-containing effluent to produce recovered PIA, or

[0276] (ii) combining the recovered component quota of the obtained r-pyrolysis oil with PIA prepared from compounds separated from the non-recovered olefin-containing effluent to produce recovered PIA; and

[0277] c. 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.

[0278] In the above process, a fully circular or closed loop process is provided, wherein the recovered PIA can be recycled multiple times.

[0279] Examples of articles included in the PIA are fibers, yarns, tows, continuous filaments, staple fibers, rovings, fabrics, textiles, flakes, films (e.g., polyolefin films), sheets, composite sheets, plastic containers, and consumer articles. In one embodiment or in combination with any of the mentioned embodiments, the recycled PIA is a polymer or article of the same family or class as the polymer or article used to prepare the r-pyrolysis oil.

[0280] As used herein, 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 being permanently disposed of (e.g., in a landfill or incinerator). A recycled waste stream is a flow or accumulation of waste from industrial and consumer sources that is at least partially recycled. Recycled waste streams include materials, products, and articles (collectively referred to as "materials" when used alone). Waste materials can be solid or liquid. Examples of solid waste streams include plastics, rubber (including tires), textiles, wood, biowaste, modified cellulose, wetlaid products, and any other material capable of pyrolysis. Examples of liquid waste streams include industrial sludge, oils (including those derived from plants and petroleum), recycled lubricating oils, or vegetable or animal oils, and any other chemical streams from industrial plants.

[0281] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolyzed recycled waste stream includes a stream containing at least in part post-industrial materials, or post-consumer materials, or both post-industrial and post-consumer materials. In one embodiment or in combination with any of the embodiments mentioned herein, post-consumer materials are materials that have been used at least once for their intended application for any duration regardless of wear and tear, or materials that have been sold to an end-use consumer, or materials that have been discarded into a recycling bin by any person or entity other than the manufacturer or business engaged in the manufacture or sale of materials. In one embodiment or in combination with any of the embodiments mentioned herein, post-industrial materials are materials that have been generated and have not yet been used for their intended application, or have not yet been sold to an end-use customer, or have not been discarded by the manufacturer or any other entity involved in the sale of materials. Examples of post-industrial materials include reprocessing, regrind, scrap, offcuts, substandard 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.

[0282] The form of the recycled waste stream fed to the pyrolysis unit is not limited and can include any form of articles, products, materials or parts thereof. A portion of the article can take the form of sheets, extruded profiles, molded products, films, laminates, foam sheets, fragments, flakes, particles, agglomerates, briquettes, powders, fragments, strips, or sheets of any shape in various shapes, or any other form except the original form of the article, and is suitable for feeding to the pyrolysis unit. In one embodiment or in combination with any of the embodiments mentioned herein, the waste material is reduced in diameter. Reduction in diameter can be performed in any manner, including chopping, shredding, harrowing, grinding, pulverizing, cutting raw materials, molding, compressing or dissolving in a solvent.

[0283] The recycled waste plastics can be separated as a type of polymer stream, or can be a stream of mixed waste plastics. Plastics can be any organic synthetic polymer that is solid at 25°C and 1atm. 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, polyamide, poly (methyl methacrylate), polytetrafluoroethylene, acrylonitrile-butadiene-styrene (ABS), polyvinyl chloride esters, cellulose and its derivatives, 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 polymers containing melamine.

[0284] 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 embodiment mentioned herein, 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 embodiment mentioned herein, the pyrolyzed waste stream contains less than 10 weight percent, or no more than 5 weight percent, or no more than 3 weight percent, or no more than 2 weight percent, or no more than 1 weight percent, or no more than 0.5 weight percent, or no more than 0.2 weight percent, or no more than 0.1 weight percent, or no more than 0.05 weight percent of No. 3 plastic (polyvinyl chloride), or alternatively No. 3 and No. 6 plastics, or alternatively No. 3, 6 and No. 7 plastics.

[0285] The example of the rubber of recovery comprises natural and synthetic rubber.The form of rubber is not limited, comprises tire.The example of the waste wood of recovery comprises softwood and hardwood, wood chips, paper pulp or finished product.The source of a large amount of waste wood is industry, construction or demolition.The example of the biowaste of recovery comprises household biowaste (for example food), green or garden biowaste and biowaste from industrial food processing industry.

[0286] The example of the textiles of recovery comprises natural and / or synthetic fiber, roving, yarn, nonwoven web, cloth, fabric and the product made by any of the above-mentioned articles or comprising any of the above-mentioned articles.Textiles can be woven, knitted, knotted, stitched, tufted, the fiber is pressed together, such as carried out in a felting operation, embroidered, lace, crocheted, braided or nonwoven web and material.Textiles include fabrics and fibers separated from textiles or other products comprising fibers, waste or substandard fibers or yarns or textiles, or any other loose fibers and yarn sources.Textiles also include staple fibers, continuous fibers, lines, tow bands, twisting and / or staple yarns, grey cloths made of yarn, finished textiles made by wet processing grey cloths, and clothing made by finished textiles or any other textiles.Textiles include clothing, interior furnishings and industrial textiles.

[0287] 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.

[0288] 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 those 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.

[0289] 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.

[0290] 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.

[0291] 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. Examples of recycled vegetable or animal oils include oils recycled from animal processing facilities and waste from restaurants.

[0292] The sources of post-consumer or post-industrial wastes obtained for recycling are not limited and may include wastes 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 or for or on behalf of textile brand owners or alliances or organizations, or by brokers, or from post-industrial sources, such as scraps 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 at docks or on ships.

[0293] In one embodiment or in combination with any embodiment mentioned herein, 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 at least, 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 embodiment mentioned herein, 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 embodiment mentioned herein, the recycled waste stream contains at least one, two or three plasticized plastics.

[0294] 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 2The 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.

[0295] 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 feedstock 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 FIG. 1 , pyrolysis system 110 may also include additional sources of other types of recycled waste, which may be used to provide other feed types to system 110 .

[0296] 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.

[0297] 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 combinations thereof.

[0298] 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.

[0299] like Figure 2 As 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%.

[0300] 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.

[0301] While 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 a pyrolysis oil (e.g., r-pyrolysis oil) and a 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 combination of these reactors.

[0302] Generally, pyrolysis is a process involving the chemical and thermal decomposition of an introduced 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.

[0303] 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.

[0304] 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.

[0305] In one embodiment or in combination with any of the embodiments 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 of the embodiments 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.

[0306] 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, 3 seconds or at least, 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, 2 hours, or no more than 1 hour, or no more than 0.5 hours, 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.

[0307] 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.

[0308] 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 introduced directly 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, 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.

[0309] 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.

[0310] 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.

[0311] 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 oil," 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).

[0312] 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 comprise 20 to 99 weight percent, 40 to 90 weight percent, or 55 to 90 weight percent pyrolysis vapor.

[0313] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may 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 may 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 to 90 weight percent, or 5 to 60 weight percent, or 10 to 60 weight percent, or 10 to 30 weight percent, or 5 to 30 weight percent pyrolysis gases.

[0314] 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.

[0315] 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 comprises a recycled component catalytic pyrolysis oil (r-catalytic pyrolysis oil) and a recycled component pyrolysis oil (r-pyrolysis oil). The r-pyrolysis oil is a pyrolysis oil prepared without adding a pyrolysis catalyst. The cracker feedstock may include at least 5, 10, 15 or 20 weight percent of r-catalytic pyrolysis oil, which may be optionally hydrotreated. The t-pyrolysis oil and r-catalytic pyrolysis oil containing r-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-pyrolysis oil to form a blended stream cracked in a cracker unit. Alternatively, the mixed stream may contain no more than 10, 5, 3, 2, 1 weight percent of r-catalytic pyrolysis oil that has not been hydrotreated. In one embodiment or in combination with any of the embodiments mentioned, the r-pyrolysis oil does not contain r-catalytic pyrolysis oil.

[0316] like Figure 2As 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 a pipeline 145 and discharged from the system.

[0317] 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.

[0318] 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.

[0319] 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 can 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 carried out in the liquid phase pyrolysis oil. In this embodiment, post-hydrogenation or post-hydroprocessing does not require a quenching step.

[0320] 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 in any combination and exist.

[0321] The pyrolysis oil may mainly contain hydrocarbons having 4 to 30 carbon atoms per molecule (e.g., C4 to C 30 As used herein, the term "Cx" or "Cx hydrocarbon" refers to a hydrocarbon compound that includes x total carbons per molecule, and includes all olefins, alkanes, aromatic hydrocarbons, and isomers having that number of carbon atoms. For example, each of normal, iso-, and tert-butane and butene and butadiene molecules would fall within the general description "C4".

[0322] 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.

[0323] 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-C22 or C5-C20 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.

[0324] The gas furnace can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock, thereby avoiding the necessity to subject 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 fraction from the lighter hydrocarbon fraction relative to each other before feeding the pyrolysis oil to the cracker 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-C 25 A hydrocarbon stream containing 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 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).

[0325] 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 C6-C 12 The hydrocarbon content is based on the weight of the pyrolysis oil. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a C6-C ... 12 In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have 10 to 95 weight percent, 20 to 80 weight percent, or 35 to 80 weight percent C6-C 12 Hydrocarbon content.

[0326] 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 -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 to 80 weight percent, 5 to 65 weight percent, or 10 to 60 weight percent of C 13 To C 23 Hydrocarbon content.

[0327] 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+ In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have 1 to 15 weight percent, 3 to 15 weight percent, 2 to 5 weight percent, or 5 to 10 weight percent of C 24+ Hydrocarbon content.

[0328] 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.

[0329] 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.

[0330] 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 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a 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. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a cycloalkane content of no more than 5, or no more than 2, or no more than 1 wt.%, or undetectable amounts. Alternatively, the pyrolysis oil may contain 1 to 50 weight percent, 5 to 50 weight percent, or 10 to 45 weight percent cycloalkanes, especially if the r-pyrolysis oil is subjected to a hydrotreating process.

[0331] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an alkane content of at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an alkane 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 an alkane content of 25 to 90 weight percent, 35 to 90 weight percent, or 40 to 80 weight percent, or 40 to 70 weight percent, or 40 to 65 weight percent.

[0332] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an n-alkane content of at least 5, or at least 10, or at least 15, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an n-alkane 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 an n-alkane content of 25 to 90 weight percent, 35 to 90 weight percent, or 40 to 70 weight percent, or 40 to 65 weight percent, or 50 to 80 weight percent.

[0333] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have an alkane to olefin weight ratio of at least 0.2: 1, or at least 0.3: 1, or at least 0.4: 1, or at least 0.5: 1, or at least 0.6: 1, or at least 0.7: 1, or at least 0.8: 1, or at least 0.9: 1, or at least 1: 1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have an alkane 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 weight ratio of alkanes to olefins 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.

[0334] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a normal alkane to isoalkane 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 alkane to isoalkane 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-iso-alkanes weight ratio in the range of 1 :1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0335] It should be noted that all of the above hydrocarbon weight percentages can be determined using gas chromatography-mass spectrometry (GC-MS).

[0336] 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 .

[0337] 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.

[0338] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a medium boiling point of at least 75°C, or at least 80°C, or at least 85°C, or at least 90°C, or at least 95°C, or at least 100°C, or at least 105°C, or at least 110°C, or at least 115°C. The value may be measured according to ASTM D-2887 or the procedure described in the working examples. If the value is obtained in any method, the medium boiling point having the value is satisfied. 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 met. 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 weight percent of the pyrolysis oil boils above the medium boiling point and 50 weight percent of the pyrolysis oil boils below the medium boiling point.

[0339] 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.

[0340] Turning to the pyrolysis gases, the pyrolysis gases may have a methane content of at least 1, or at least 2, or at least 5, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20 weight percent. Additionally or alternatively, in one embodiment or in combination with any 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 to 50 weight percent, 5 to 50 weight percent, or 15 to 45 weight percent.

[0341] In one embodiment or in combination with any of the embodiments 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 of the embodiments 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 of the embodiments mentioned herein, the pyrolysis gas may have a C3 hydrocarbon content of 1 to 50 weight percent, 5 to 50 weight percent, or 20 to 50 weight percent.

[0342] In one embodiment or in combination with any of the embodiments 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 of the embodiments 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 of the embodiments mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of 1 to 50 weight percent, 5 to 50 weight percent, or 20 to 50 weight percent.

[0343] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil of the present invention may be a recycled content pyrolysis oil composition (r-pyrolysis oil).

[0344] 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.

[0345] 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.

[0346] 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.

[0347] In one embodiment or in combination with any embodiment mentioned herein, the C4-C7 content or C8+ content of the heavy fraction can be at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 weight percent. The light fraction can include at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% 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-C7 content or C7 content higher than the pyrolysis oil taken from the pyrolysis zone. 8+ The C4-C7 content or C4-C7 content is 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.

[0348] 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.

[0349] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can be combined with a non-recovery 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, aromatic hydrocarbons, or other compounds described herein), the r-pyrolysis oil can be combined with the cracker feed so that the total concentration of the less desirable compounds in the combined stream is less than the original content of the compounds in the r-pyrolysis oil stream (calculated as the difference between the r-pyrolysis oil and the combined stream divided by the r-pyrolysis oil content, expressed as a percentage) by at least 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% combined. In some cases, the amount of non-recovery cracker feed to be combined with the r-pyrolysis oil stream can be determined by comparing the measured amount of one or more less desirable compounds present in the r-pyrolysis oil with the target value of these compounds to determine the difference, and then based on the difference, the amount of non-recovery hydrocarbons to be added to the r-pyrolysis oil stream is determined. The amounts of r-pyrolysis oil and non-recovered hydrocarbons are within one or more ranges described herein.

[0350] At least a portion of the r-propylene is derived directly or indirectly from the cracking of r-pyrolysis oil. The process for obtaining r-olefins by cracking (r-pyrolysis oil) can be as follows and as Figure 4 As described in.

[0351] Steering Figure 4 , which is a flow chart of the steps associated with the cracking furnace 20 and 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.

[0352] In one embodiment or in combination with any embodiment mentioned herein, the feed stream containing r-pyrolysis oil can contain 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, in an amount, in each case, 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, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, Or at least 97, or at least 98, or at least 99, or at least or 100 weight percent and / or 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 of r-pyrolysis oil, based on the total weight of the feed stream containing r-pyrolysis oil.

[0353] In one embodiment or combination with any embodiment mentioned herein, at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 97, or at least 98, or at least 99, or 100 weight percent of the r-pyrolysis oil 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, or no more than 15, or no more than 10 weight percent of the r-pyrolysis oil is obtained from pyrolysis of a waste stream. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock containing plastic waste. Desirably, in each case, at least 90, or at least 95, or at least 97, or at least 98, or at least 99, or at least or 100 wt.% of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock containing plastic waste, or a feedstock containing at least 50 wt.% plastic waste, or a feedstock containing at least 80 wt.% plastic waste, or a feedstock containing at least 90 wt.% plastic waste, or a feedstock containing at least 95 wt.% plastic waste.

[0354] 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.

[0355] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can contain at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent 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, 60, 65, 70, 75, 80, 85, 90 or 95 weight percent C5-C 25 、C5-C 22 or C5-C 20 hydrocarbon.

[0356] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil composition may include 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.

[0357] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil composition may include C 13 -C 22 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) 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.

[0358] 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).

[0359] The r-pyrolysis oil includes one or more of alkanes, cycloalkanes or cycloaliphatic hydrocarbons, aromatic hydrocarbons, aromatic-containing hydrocarbons, olefins, oxygen-containing compounds and polymers, heteroatom compounds or polymers, and other compounds or polymers.

[0360] 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. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane content of 25 to 90, 35 to 90, or 40 to 80, or 40 to 70, or 40 to 65 weight 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.

[0361] 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 in an undetectable amount, 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, or no more than 2, or no more than 1 wt.%, or in an undetectable amount. 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.

[0362] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have an alkane to olefin weight ratio of at least 0.2: 1, or at least 0.3: 1, or at least 0.4: 1, or at least 0.5: 1, or at least 0.6: 1, or at least 0.7: 1, or at least 0.8: 1, or at least 0.9: 1, or at least 1: 1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have an alkane 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 of the embodiments mentioned herein, the r-pyrolysis oil can have a weight ratio of alkanes to olefins in the range of 0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1 to 4.5:1, or 0.2:1 to 4:1, or 0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

[0363] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a normal alkane to isoalkane 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 alkane to isoalkane 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-iso-alkanes weight ratio in the range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0364] 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, or at least 2, or at least 5, or at least 8, or at least 10 weight percent of aromatic hydrocarbons, based on the total weight of the r-pyrolysis oil in each case.

[0365] 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 aromatic hydrocarbons, or undetectable, in each case by weight, based on the total weight of the r-pyrolysis oil. Aromatic compounds include the above aromatic hydrocarbons and any compounds containing aromatic moieties, such as terephthalate residues and fused ring aromatic hydrocarbons, such as naphthalene and tetralin.

[0366] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can include olefins in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20, or at least 30, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65 olefins in each case by weight percent olefins, and / 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, or no more than 10 weight percent in each case, based on the weight of the r-pyrolysis oil. Olefins include mono-olefins and di-olefins. Examples of suitable ranges include wt. % ratios 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.

[0367] 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 in each case, 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. Oxygenates 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 0.01-5wt.%, based on the weight of the r-pyrolysis oil.

[0368] 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 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.

[0369] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include heteroatom compounds or polymers in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20 weight percent, and / or 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 6, or no more than 5, or no more than 3, or no more than 2 weight percentages, based on the weight of the r-pyrolysis oil. Heteroatom compounds or polymers are 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.

[0370] 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 the r-pyrolysis oil. Desirably, the solubility of water in r-pyrolysis oil is no more than 0.1 wt.%, based on the weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, the 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 as wt.% water based on the weight of the r-pyrolysis oil.

[0371] 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.

[0372] 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 wt.% based on the weight of the r-pyrolysis oil.

[0373] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have the following component contents:

[0374] The carbon atom content is at least 75 wt.%, or at least 77, or at least 80, or at least 82, or at least 85, in each case wt.%, and / or at most 90, or at most 88, or at most 86, or at most 85, or at most 83, or at most 82, or at most 80, or at most 77, or at most 75, or at most 73, or at most 70, or at most 68, or at most 65, or at most 63, or at most 60, in each case wt.%, desirably at least 82% and at most 93%, and / or

[0375] 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.%,

[0376] 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.

[0377] In each case based on the weight of the r-pyrolysis oil.

[0378] 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.

[0379] In one embodiment or in combination with any embodiment mentioned herein, the metal content of the r-pyrolysis oil is desirably low, e.g., 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 wt.% based on the weight of the r-pyrolysis oil.

[0380] 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, e.g., 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 wt.% based on the weight of the r-pyrolysis oil.

[0381] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of alkanes 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.

[0382] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of the combination of alkanes 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 alkanes 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.

[0383] 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 weight percentages of the composition boil at the boiling point.

[0384] 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 22 5, or no more than 220, or no more than 215, or no more than 200, or no more than 190, or no more than 180, or no more than 170, or no more than 160, or no more than 150, or no more than 140, 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, in each case °C, and / or no more than 25, 20, 15, 10, 5, or 2 weight percent of the r-pyrolysis oil may have a boiling point of 300°C or higher.

[0385] 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.% pyrolysis oil based on the weight of the cracker feed stream) or in combination with one or more non-recovery cracker feed streams. When introduced into a cracker 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.

[0386] 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 at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.%, based on the total weight of the feed, and / or 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 C2-C4 hydrocarbons or linear alkanes 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.

[0387] 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 %, or at least 90, or at least 95, or at least 92, or at least 90, or at least 85, 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 C5-C 22 , or C5-C20 The hydrocarbon weight percentage is 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 at least 0.5, or at least 1, or at least 2, or at least 5 C 15 and heavier (C 15+ ) content, in each case as weight percent, and / or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 18, or not more than 15, or not more than 12, or not more than 10, or not more than 5, or not more than 3, in each case as weight percent, based on the total weight of the feed.

[0388] 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.

[0389] 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.

[0390] 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.

[0391] 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.

[0392] 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.

[0393] 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 16or alternatively, having at least one coil receiving 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% heavy fuel oil, and / or more than 50% marine grade C, and / or more than 50% 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 embodiment mentioned herein, at least one coil in the convection zone or in the convection box of the furnace and not more than 75% of the coils, or not more than 50% of the coils, or not more than at least 40% of the coils are liquid coils. In one embodiment or in combination with any embodiment mentioned herein, the liquid coil receives a vapor-phase feed at the coil inlet at the inlet of the convection zone, wherein 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.

[0394] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil is cracked in a thermal gas cracker. 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. In one embodiment or in combination with any of the embodiments mentioned herein, the r-composition is derived directly or indirectly from cracking the r-pyrolysis oil in a gas furnace. The coils in the gas furnace can consist entirely of gas coils, or the gas furnace can be a cracking furnace.

[0395] 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.

[0396] 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.

[0397] In one embodiment or combination of any of the mentioned embodiments, there is provided a method for preparing one or more olefins (e.g., propylene), comprising:

[0398] (a) feeding a first cracker feed comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to a cracker furnace;

[0399] (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

[0400] (c) cracking said first and said second cracker feeds in respective first and second tubes to form olefin-containing effluent streams.

[0401] 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.

[0402] 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 a 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 a 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, 5-40, 5-35, 5-30, 5-25, 5-20 or 5-15 wt.%.

[0403] 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 within the same cracker furnace.

[0404] The second cracker stream may be free of r-pyrolysis oil or contain less (by weight) of the 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 mainly 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, 60, 65, 70, 75, 80, 85 or at least 90 weight percent, 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 less than the amount of r-pyrolysis oil in the first cracker feed by weight by at least 10%, 20, 30, 40, 50, 60, 70, 80, 90, 95, 97 or 99%.

[0405] 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.

[0406] 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.

[0407] 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) fan 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.

[0408] 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.

[0409] 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.

[0410] 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.

[0411] 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 180° ("U" shaped) bends. Figure 6 One example of a furnace coil 410 having a plurality of tubes 420 is shown in FIG.

[0412] 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 embodiment mentioned herein, the furnace is a liquid or naphtha cracker that receives a cracker feed stream passing through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, wherein the cracker feed stream contains at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.% liquid hydrocarbons having carbon numbers of C5-C22 (when measured at 25°C and 1 atm), based on the weight of all cracker feeds to the furnace. In one embodiment or in combination with any embodiment mentioned herein, the cracker is a cracking furnace which 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, wherein the cracker feed stream contains 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.

[0413] Now turn to Figure 7 , showing several possible locations for introducing a feed stream containing r-pyrolysis oil and a non-recovery cracker feed stream into a cracking furnace. In one embodiment or in combination with any of the embodiments mentioned herein, a feed stream 550 containing r-pyrolysis oil can be combined with a 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 a first furnace coil, while the non-recovery cracker feed 552 can be introduced into a separate or second furnace coil, within the same furnace or within the same convection zone. The two streams can then travel parallel to each other through the convection section 510 within the convection box 512, the crossover 530, and the radiant section 520 within 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 within the convection section 510 may flow through the convection section 510 and flow into the radiation 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 .

[0414] 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.

[0415] 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.

[0416] 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 a portion of the stream comprising r-pyrolysis oil, and can, for example, vaporize at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 weight percent of the stream comprising r-pyrolysis oil.

[0417] 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.

[0418] In one embodiment or in combination with any of the embodiments 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 of the embodiments mentioned herein, the r-pyrolysis oil stream may comprise at least 1, 2, 5, 8, 10, or 12 weight percent C 15 The separation can remove at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 weight percent of the heavier components from the r-pyrolysis oil stream.

[0419] 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.

[0420] 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. When combined with steam and fed into or near the inlet of convection section 510, the r-pyrolysis oil and / or cracker streams 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.

[0421] 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.

[0422] 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:

[0423] (a) feeding a first cracker stream having r-pyrolysis oil to a first tube inlet in a cracker furnace;

[0424] (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.

[0425] 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 (wherein the percentage is calculated as the difference between the two molar flow rates divided by the flow rate of the non-recovery stream).

[0426] 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

[0427] 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.

[0428] In one embodiment or in combination with any of the embodiments 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.

[0429] 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 may be different from the temperature of the non-recovery cracker feed as it passes through the crossover section when the stream is introduced and passed through the furnace separately. For example, the temperature of the r-pyrolysis oil stream as it passes through the crossover section may differ from the temperature of the non-recovery hydrocarbon stream (e.g., C2-C4 or C5-C22) passing through the crossover section in another coil by at least 0.01, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75%. This percentage can be calculated based on the temperature of the non-recovery stream according to the following formula:

[0430] (r - temperature of pyrolysis oil stream - temperature of non-recovery cracker stream) / (temperature of non-recovery cracker steam), expressed as a percentage.

[0431] 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.

[0432] 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.

[0433] 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.

[0434] 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 1, 2, 4, 5, 8, 10, 12, 15, 10, 25 or 30 weight percent, and / or the amount of no more than 50, 45, 40, 35, 30, 25, 20, 15 or 10 weight percent is present in the stream to be atomized (for example, the composition containing r-pyrolysis oil).

[0435] 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.

[0436] 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.

[0437] 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 cracker 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 cracker 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.

[0438] 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.

[0439] 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 .

[0440] 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.

[0441] 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.

[0442] 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 5 Steam 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.

[0443] a heated cracker stream, which 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 to 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,

[0444] 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.

[0445] 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.

[0446] 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 a first set of processing conditions can differ from a target value for the same parameter in a 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 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 to 30, 0.01 to 20, 0.01 to 15, 0.03 to 15%. The percentages are calculated according to the formula:

[0447] [(measured value of operating parameter) - (target value of operating parameter)] / [(target value of operating parameter)], expressed as a percentage. As used herein, the term "different" means higher or lower.

[0448] 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.

[0449] 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 percentage is calculated according to the following formula:

[0450] [(measured value of the operating parameter) - (target value of the operating parameter)] / [(target value of the operating parameter)], expressed as a percentage.

[0451] 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.

[0452] 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 at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% higher than the 50% boiling point of the cracker stream, and / or no more than 80, 75, 70, 65, 60, 55, or 50%. The percentages are calculated according to the following formula:

[0453] [(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.

[0454] 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.

[0455] 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:

[0456] [(r - 50% boiling point of pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0457] 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.

[0458] 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.

[0459] 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.

[0460] In one embodiment or in combination with any of the mentioned embodiments, there is provided a process for preparing one or more olefins by:

[0461] (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit;

[0462] (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

[0463] (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.

[0464] 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, 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).

[0465] 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.

[0466] 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 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.

[0467] In the set mode, the temperature can be fixed or set by adjusting the fuel ratio of the furnace to the burner. In one embodiment or in combination with any other mentioned embodiment, COT2 is in free floating mode and is the temperature of the coil of the pyrolysis oil feed without fixing it due to supplying pyrolysis oil and allowing COT2 to rise or fall. In this embodiment, not all coils contain r-pyrolysis oil. The thermal energy provided to the coil containing r-pyrolysis oil can be provided by maintaining a constant temperature or fuel feed rate of the burner on the coil containing non-recovery cracker feed. In the case of not fixing or setting COT2, when pyrolysis oil is fed to the cracker stream to form a combined cracker stream with 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.

[0468] 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.

[0469] 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, as measured on a calendar year, such as at least 2x / yr, or at least 3x / yr, or at least 4x / yr, or at least 5x / yr, or at least 6x / yr, or at least 8x / yr, or at least 12x / yr. 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 down, COT1 is allowed to reach a steady-state temperature before engaging step (b). Alternatively, the feeding of pyrolysis oil to the cracker feed may be continuous throughout at least 1 calendar year or at least 2 calendar years.

[0470] 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.

[0471] In one embodiment or in combination with any of the mentioned embodiments, COT2 is below or at least 1, 2, 3, 4 or at least 5°C lower for at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 85%, or at least 90%, or at least 95% of the time that pyrolysis oil is fed to the cracker stream to form the combined cracker 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.

[0472] 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:

[0473] (a) cracking a cracker stream at a first hydrocarbon mass flow rate (MF1) in a cracking unit;

[0474] (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

[0475] (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.

[0476] 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 processes r-pyrolysis oil. Alternatively, the increase in combined production of ethylene and propylene 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.

[0477] 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:

[0478]

[0479] wherein Omf1 is the combined production of propylene and ethylene content in the cracker effluent under MF1 produced without using r-pyrolysis oil; Omf2 is the combined production of propylene and ethylene content in the cracker effluent under MF2 produced with using r-pyrolysis oil.

[0480] 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 at most 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:

[0481]

[0482] where 1% is the percentage increase between the combined production of propylene and ethylene content in the cracker effluent for MF1 made without r-pyrolysis oil and MF2 made with r-pyrolysis oil (using the above formula); and

[0483] ΔMF% is the percentage of increase of MF2 compared to MF1.

[0484] Alternatively, the olefin-containing effluent stream may have a total wt.% of propylene and ethylene from the combined cracker stream at MF2 that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% higher than the wt.% of propylene and ethylene of an effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, determined as follows:

[0485]

[0486] wherein Emf1 is the combined wt.% of propylene and ethylene contents in the cracker effluent under MF1 produced without using r-pyrolysis oil; Emf2 is the combined wt.% of propylene and ethylene contents in the cracker effluent under MF2 produced with using r-pyrolysis oil.

[0487] Also provided is a method for preparing one or more olefins, the method comprising:

[0488] (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);

[0489] (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

[0490] (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),

[0491] wherein when the r-pyrolysis oil is heavier than the cracker stream, COT2 is equal to or less than COT1, and

[0492] Wherein, when the r-pyrolysis oil is lighter than the cracker stream, COT2 is greater than or equal to COT1.

[0493] In the process, the above embodiments are applicable here for COT2 being at least 5°C 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.

[0494] In one embodiment or in combination with any of the mentioned embodiments, there is provided a process for preparing one or more olefins by:

[0495] (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit;

[0496] (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

[0497] (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. 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.

[0498] 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.

[0499] 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:

[0500] a. requiring lower thermal energy to crack the pyrolysis oil in the combined stream; or

[0501] b. Exothermic reactions occur in the cracking products of the pyrolysis oil, such as the Diels-Alder reaction.

[0502] 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.

[0503] 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.

[0504] 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.

[0505] 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).

[0506] 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.

[0507] 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.

[0508] 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 at least about 30, or at least 40, or at least 50, or at least 60, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case as a weight percentage of ethylene, propylene, or ethylene and propylene, based on the total weight of the effluent stream.

[0509] In one embodiment or in combination with one or more embodiments mentioned herein, the olefin-containing effluent stream 670 can contain C2-C4 olefins, or propylene, or ethylene, or C4 olefins in an amount of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 weight percent, based on the weight of the olefin-containing effluent. The stream can contain primarily ethylene, primarily propylene, or primarily ethylene and propylene, based on the olefins in the olefin-containing effluent, 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.

[0510] 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:

[0511]

[0512] wherein E is the propylene:ethylene ratio in the cracker effluent produced without using r-pyrolysis oil, calculated in wt.%; Er is the propylene:ethylene ratio in the cracker effluent produced with r-pyrolysis oil, calculated in wt.%.

[0513] 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 total wt.% of propylene and ethylene that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% higher than the propylene and ethylene content of the effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, as determined by:

[0514]

[0515] wherein E is the combined wt.% of propylene and ethylene contents in the cracker effluent produced without using r-pyrolysis oil; Er is the combined wt.% of propylene and ethylene contents in the cracker effluent produced using r-pyrolysis oil, and wherein

[0516] 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.

[0517] 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.

[0518] 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.%, as measured by 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.

[0519] 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%.

[0520] 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., combined propane and ethane amounts) 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.

[0521] For example, the total amount of propane and ethane in the olefin-containing effluent (either or both of the yield or wt.%) 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 propane in the olefin-containing effluent can be reduced by at least 2%, or at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15%, or at least 18%, or at least 20%, and in each case 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.

[0522] 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.

[0523] In one embodiment or in combination with one or more embodiments mentioned herein, when 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 amount of C6+ products in the olefin-containing effluent can be increased if such products are desired, for example for a BTX stream to prepare its derivatives. When r-pyrolysis oil and steam are fed downstream of the inlet of the convection box, the amount of C6+ products in the olefin-containing effluent can be increased by 5%, or 10%, or 15%, or 20%, or 30% when measured relative to feeding r-pyrolysis oil at the inlet of the convection box, all other conditions being the same. The increase % can be calculated as:

[0524]

[0525] Wherein Ei is the C6+ content in the olefin-containing cracker effluent prepared by introducing r-pyrolysis oil at the inlet of the convection box; Ed is the C6+ content in the olefin-containing cracker effluent prepared by introducing pyrolysis oil and steam downstream of the convection box inlet.

[0526] 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, 1, 2 or 2.5 weight percent, and / or no more than about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 weight percent of aromatic hydrocarbons, based on the total weight of the stream. We have found that the C6+ material level in the olefin-containing effluent can be no more than 5wt.%, or no more than 4wt.%, or no more than 3.5wt.%, or no more than 3wt.%, or no more than 2.8wt.%, or no more than 2.5wt.%. 6+ The substances include all aromatic hydrocarbons, as well as all alkanes and cyclic compounds having 6 or more carbon atoms. As used throughout the text, the amount of aromatic hydrocarbons referred to can be determined by C 6+ The amount of substance is expressed because the amount of aromatic hydrocarbons will not exceed the amount of C6+ substance.

[0527] 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.

[0528] 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 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. 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.

[0529] 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.

[0530] 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.

[0531] Olefin-containing compositions can also include trace aromatic hydrocarbons.For example, composition can have at least 0.25,0.3,0.4,0.5 weight percent, and / or be no more than about 2,1.7,1.6,1.5 weight percent benzene content.Additionally or alternatively, composition can have at least 0.005,0.010,0.015 or 0.020 and / or be no more than 0.5,0.4,0.3 or 0.2 weight percent toluene content.Two percentages are all based on the gross weight of composition.Alternatively or additionally, the benzene content of effluent can be at least 0.2,0.3,0.4,0.5 or 0.55 weight percent, and / or be no more than about 2,1.9,1.8,1.7 or 1.6 weight percent, and / or toluene content can be at least 0.01,0.05 or 0.10 weight percent, and / or be no more than 0.5,0.4,0.3 or 0.2 weight percent.

[0532] 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 having been 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 the same cracker feed stream under the same conditions and at the same mass feed rate but without r-pyrolysis oil processing by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85%. 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:

[0533]

[0534] wherein E is the wt.% of the components in the cracker effluent prepared without using r-pyrolysis oil; Er is the wt.% of the components in the cracker effluent prepared with r-pyrolysis oil.

[0535] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream may include 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.

[0536] 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.

[0537] 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 an amount of carbon dioxide 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 amount of carbon dioxide in wt.%, or not higher than 2%, or the same amount as the comparative effluent stream without r-pyrolysis oil. Alternatively or additionally, the olefin-containing effluent stream may have an amount of 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.

[0538] Now go to Fig. 9 , a block diagram illustrating the main elements of the furnace effluent treatment section is shown. 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.

[0539] 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.

[0540] 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.

[0541] 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.

[0542] 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 of the embodiments 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 bonds are methane. Similarly, "deethanizer" and "depropanizer" refer to towers with ethane and propane as light bond components, respectively.

[0543] 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 to 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 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 of the total amount of C2 and lighter components introduced into the column in the top stream. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 816 removed from the deethanizer comprises at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case weight percent ethane and ethylene, based on the total weight of the overhead stream.

[0544] 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 top of the column, while ethane and any remaining heavier components are removed in a bottoms stream 824. The ethylene fractionator 830 can 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 overhead stream 822 can contain 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 ethylene, based on the total weight of the stream, and can be sent to downstream processing units for further processing, storage or sale. The overhead ethylene stream 822 produced during cracking of a cracker feed containing r-pyrolysis oil is an r-ethylene composition or stream. In one embodiment or in combination with any of the embodiments mentioned herein, the r-ethylene stream can be used to prepare one or more petrochemical products.

[0545] 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.

[0546] 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.10In the depropanizer 840, C3 and lighter components are removed as an overhead vapor stream 826, while C4 and heavier components may leave the column in a liquid bottoms stream 828. The depropanizer 840 may be operated at an overhead temperature 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 at an overhead 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 collects 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, a percentage of the total amount of C3 and lighter components introduced into the column in the overhead stream 826. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 826 removed from the depropanizer 840 comprises 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 weight percent of propane and propylene, based on the total weight of the overhead stream 826.

[0547] 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 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 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, propylene weight percent, based on the gross 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.

[0548] 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.

[0549] Refer again Fig.10 The bottom stream 828 from the depropanizer 840 can be sent to the debutanizer 850 for separating the C4 components, including butenes, butanes and butadiene, from the C 5+ Component separation. The debutanizer can be operated at a tower top temperature 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 no more than 60, or no more than 65, or no more than 60, or no more than 55, or no more than 50, in each case ° C, and a tower top pressure of at least 2, or at least 3, or at least 4, or at least 5, in each case barg, and / or no more than 8, or no more than 6, or no more than 4, or no more than 2, in each case barg. The debutanizer recovers 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 a percentage of the total amount of C4 and lighter components introduced into the tower in the tower top stream 836. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 836 removed from the debutanizer contains 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 weight percent butadiene, 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 bottoms stream 838 from the debutanizer mainly contains at least 50, or at least 60, or at least 70, or at least 80, or at least 90, or at least 95 weight percent of C5 and heavier components, based on the total weight of the stream. The debutanizer bottoms stream 838 can be sent for further separation, processing, storage, sale or use.

[0550] 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.

[0551] Recovered component (C4) alkanal and preparation method

[0552] In an embodiment, a method for preparing a recovery component (C4) alkanoic acid product (r-(C4) alkanoic acid) is provided. An example of such a method includes a carboxylation process, wherein r-propylene is fed into a reaction vessel and reacted to produce a carboxylation effluent comprising r-(C4) alkanoic acid. This method for preparing (C4) alkanoic acid includes contacting propylene with water, CO and a catalyst, or CO2 and a catalyst in a reaction zone at temperature and pressure for a sufficient time to allow propylene, water and CO, or propylene and CO2 to form (C4) alkanoic acid, and it can be carried out by methods known in the art. The (C4) alkanoic acid recovery component or quota (e.g., an allocation or credit) derived from r-propylene can be determined in a manner similar to that described above for (C4) alkanal.

[0553] Another example of a method for preparing (C4) alkanoic acid includes an oxidation process, wherein a (C4) alkanal (as described herein) is fed to a reaction vessel and reacted to produce an oxidation effluent comprising the (C4) alkanoic acid. This method for preparing (C4) alkanoic acid includes contacting the (C4) alkanal with oxygen and a catalyst in a reaction zone at temperature and pressure for a sufficient time to allow the (C4) alkanal and oxygen to form the (C4) alkanoic acid, and can be performed by methods known in the art. Similarly, the (C4) alkanoic acid recovery component or quota (e.g., allocation or credit) derived from r-propylene can be determined in a manner similar to that described above for (C4) alkanal, taking into account the stoichiometry, conversion, yield, etc. in the overall scheme from r-propylene to r-(C4) alkanal to r-(C4) alkanoic acid.

[0554] While any process for converting r-propylene to (C4)alkanals may be used, rhodium catalyzed processes or low pressure hydroformylation processes are ideal synthetic routes due to their high catalyst activity and selectivity and low pressure and temperature requirements.

[0555] More specifically, the hydroformylation process for preparing r-(C4)alkanal comprises contacting propylene with synthesis gas (H2, CO) and a catalyst complex in a reaction zone at high temperature and pressure for a sufficient time to react propylene with the synthesis gas to form (C4)alkanal. Suitable methods for preparing (C4)alkanal include high pressure and low pressure carbonyl synthesis processes, wherein r-propylene is hydroformylated to prepare (C4)alkanal. The hydroformylation reaction temperature can be any temperature from 50°C to about 250°C, and the reaction pressure can be from 15 psig to about 5100 psig.

[0556] The hydroformylation process can be a high pressure or low pressure process. For high pressure processes, examples of hydroformylation reaction pressure (in the reaction zone in the hydroformylation reactor) or the ethylene pressure fed to the reactor include at least 550 psig, or at least 600 psig, or at least 800 psig, or at least 1000 psig, or at least 1500 psig, or at least 2000 psig, or at least 2500 psig, or at least 3000 psig, or at least 3500 psig, or at least 4000 psig. The pressure can be up to 5100 psig, or up to 4800 psig, or up to 4500 psig.

[0557] In a high pressure hydroformylation process, the temperature in the reaction zone may be at least 140° C., or at least 150° C., or at least 160° C., or at least 170° C. Additionally or alternatively, the temperature may be up to 250° C., or up to 240° C., or up to 230° C., or up to 220° C., or up to 210° C., or up to 200° C.

[0558] In low pressure processes, the hydroformylation reaction pressure (in the reaction zone in the hydroformylation reactor) or the propylene pressure fed to the reactor comprises at least 15psig, or at least 30psig, or at least 70psig, or at least 100psig, or at least 125psig, or at least 150psig, or at least 175psig, or at least 200psig, or at least 225psig, or at least 250psig, or at least 275psig, or at least at least 300psig. The pressure can be less than 550psig, or up to 530psig, or up to 500psig, or up to 450psig, or up to 400psig, or up to 350psig, or up to 300psig, or up to 285psig. Typically, the reaction pressure is at least 200psig, or at least 250psig, and at most 400psig. In one embodiment, the pressure in the reaction zone is enough to maintain the vapor-liquid equilibrium in the reaction zone.

[0559] Typically, the molar ratio of hydrogen and carbon monoxide (which is not necessarily the ratio of synthesis gas) introduced into the reactor or the molar ratio in the reactor is maintained at about 0.1: 1 to about 10: 1, or 0.5: 1 to 4: 1, or 0.9: 1 to 4: 1, or 1: 1 to 4: 1. In many hydroformylations, the reaction rate and the productivity of (C4) alkanal can be increased to more than 4.0 by the molar ratio of hydrogen and carbon monoxide, and at most about 10.0 or higher to improve. In one embodiment, the sum of the absolute partial pressures of hydrogen and carbon monoxide can be in the range of 15psig to 430psig. The hydrogen partial pressure in the reactor can be maintained at 35psig to about 215psig. The carbon monoxide partial pressure in the reactor can be maintained at 35psig to 215psig, or 40psig to 110psig.

[0560] In one embodiment, the ratio of H2 to CO is 0.9:1-1.1:1, which is particularly suitable for hi...

Claims

1. A method for preparing and recovering C4 alkanoic acid, i.e., r-C4 alkanoic acid, comprising: Carboxylation recovers a propylene composition, i.e., r-propylene, to thereby produce a carboxylation effluent comprising C4 alkanoic acids, wherein the r-propylene is derived directly or indirectly from a cracked recovered pyrolysis oil composition, i.e., 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, Based on the weight of the r-pyrolysis oil, the r-pyrolysis oil contains 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 not more than 35 wt.% of aromatic hydrocarbons, The cracking device for carrying out the cracking is a gas furnace, The feed stream containing r-pyrolysis oil comprises at least 50 wt.% propane and at least 5 wt.% and not more than 50 wt.% r-pyrolysis oil, based on the total weight of the feed stream, The r-pyrolysis oil is not hydrotreated before the cracking, In the radiant section of the cracker, the feed stream comprising r-pyrolysis oil is thermally cracked, the residence time of the feed stream in the radiant section is at least 0.25 seconds and not more than 1 second, the temperature at the inlet of the radiant section is at least 500° C. and not more than 650° C., the coil outlet temperature of the radiant section is at least 640 and not more than 870° C., Cracking occurs in the presence of steam with a steam to hydrocarbon ratio in the range of 0.2 to 0.

8.

2. The method according to claim 1, wherein: The r-propylene is derived directly or indirectly from cracking r-pyrolysis oil in a cracking furnace or a hot steam-gas furnace.

3. A method for preparing and recovering C4 alkanoic acid, i.e., r-C4 alkanoic acid, comprising: Oxidatively recover C4 alkanals, i.e., r-C4 alkanals, to thereby produce an oxidation effluent comprising C4 alkanoic acids, wherein the r-C4 alkanals are produced from a recovered propylene composition, i.e., r-propylene, and the r-propylene is derived directly or indirectly from a cracked recovered pyrolysis oil composition, i.e., 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, Based on the weight of the r-pyrolysis oil, the r-pyrolysis oil contains 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 not more than 35 wt.% of aromatic hydrocarbons, The cracking device for carrying out the cracking is a gas furnace, The feed stream containing r-pyrolysis oil comprises at least 50 wt.% propane and at least 5 wt.% and not more than 50 wt.% r-pyrolysis oil, based on the total weight of the feed stream, The r-pyrolysis oil is not hydrotreated before the cracking, In the radiant section of the cracker, the feed stream comprising r-pyrolysis oil is thermally cracked, the residence time of the feed stream in the radiant section is at least 0.25 seconds and not more than 1 second, the temperature at the inlet of the radiant section is at least 500° C. and not more than 650° C., the coil outlet temperature of the radiant section is at least 640 and not more than 870° C., Cracking occurs in the presence of steam with a steam to hydrocarbon ratio in the range of 0.2 to 0.

8.

4. The method according to claim 3, wherein: The r-propylene is derived directly or indirectly from cracking r-pyrolysis oil in a cracking furnace or a hot steam-gas furnace.

5. The method according to claim 4, wherein: The cracking facility in which r-propylene is produced is in continuous or intermittent fluid communication with the C4 alkanal forming facility.

6. The method according to claim 5, wherein: The C4 Alkanal Manufacturer has obtained: a. Based on the certified or stated amount of propylene produced from r-pyrolysis oil, or b. has transferred to the C4 alkanal manufacturer a credit for the supply of propylene sufficient to allow the C4 alkanal manufacturer to meet the certification requirements or make its representation, or c. The propylene has been allocated to its recovery component, where the allocated amount is obtained from a cracked propylene amount obtained at least in part by cracking r-pyrolysis oil via one or more intermediate entities.

7. The method according to claim 6, wherein: The r-pyrolysis oil is liquid at 25°C and 1 atm and contains at least 95 wt.% of C5 to C 25 hydrocarbon.

8. The method according to claim 7, wherein: The r-pyrolysis oil comprises: (1) C4-C 12 Aliphatic compounds and C 13 -C 22 aliphatic compounds in a weight ratio greater than 1:1 based on the weight of the r-pyrolysis oil; (2)C 13 -C 22 Aliphatic compounds and C4-C 12 aliphatic compounds in a weight ratio greater than 1:1 based on the weight of the r-pyrolysis oil; (3) paraffins in an amount of 5 wt.%, based on the weight of the r-pyrolysis oil; (4) cycloalkanes in an amount of 0-35 wt.%, based on the weight of the r-pyrolysis oil composition; (5) no more than 30 wt.% aromatic hydrocarbons, based on the total weight of the r-pyrolysis oil; or (6) Oxygen-containing compounds or polymers in an amount ranging from 0 to 20 wt. %, based on the weight of the r-pyrolysis oil.

9. The method according to claim 8, wherein: (1) the amount of oxygen atoms in the r-pyrolysis oil is 0-8 wt.%, based on the weight of the r-pyrolysis oil; (2) the amount of heteroatoms in the r-pyrolysis oil does not exceed 5 wt.%, based on the weight of the r-pyrolysis oil; or (3) The sulfur content of the r-pyrolysis oil does not exceed 2.5 wt.%, based on the weight of the r-pyrolysis oil.

10. The method according to claim 9, wherein: The solubility of water in the r-pyrolysis oil at 1 atm and 25° C. is less than 2 wt. % water, based on the weight of the r-pyrolysis oil.

11. The method according to claim 10, wherein: The r-pyrolysis oil has the following component contents: a. a carbon atom content of at least 75wt.%; b. The hydrogen atom content is at least 10wt.%, c. The oxygen atom content is not more than 10wt.%, In each case based on the weight of the r-pyrolysis oil.

12. The method according to claim 11, wherein: The weight ratio of paraffins to cycloparaffins is at least 1:1, based on the weight of the r-pyrolysis oil.

13. The method according to claim 12, wherein: The r-pyrolysis oil, cracker feed stream to the cracker furnace or composition has a 90% boiling point not exceeding 350°C, wherein at least 90 weight percent of the composition boils at this boiling point.

14. The method according to claim 13, wherein: The r-pyrolysis oil is present in an amount not exceeding 40 weight percent, based on the total weight of the combined stream with the propane.

15. The method according to claim 14, wherein: The r-pyrolysis oil is fed to at least one coil in a furnace receiving or being operated to receive a feed that is primarily in the gas phase, wherein more than 50% of the feed weight is steam, at a coil inlet at the inlet of the convection zone in the furnace, the coil being a gas coil.

16. The process of claim 15 having at least one coil receiving more than 50% propane based on the weight of the cracker feed to the coil or based on the weight of the cracker feed to the convection zone.

17. A method for obtaining a recovery component in a C4 alkanoic acid, comprising: Method 1: a. obtaining a propylene composition designated as having a recycled content, and b. feeding the propylene to a reactor under conditions effective to produce C4 alkanoic acid, and wherein at least a portion of the propylene composition is directly or indirectly derived from a cracked recovered pyrolysis oil composition, i.e., r-pyrolysis oil; or Method 2: a. obtaining a C4 alkanal designated as having a recovered component, and b. feeding the C4 alkanal to a reactor under conditions effective to produce a C4 alkanoic acid, and wherein at least a portion of the C4 alkanals are produced from a recovered propylene composition derived directly or indirectly from a cracked recovered pyrolysis oil composition, i.e., r-pyrolysis oil; Among them, in method 1 or method 2: 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, Based on the weight of the r-pyrolysis oil, the r-pyrolysis oil contains 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 not more than 35 wt.% of aromatic hydrocarbons, The cracking device for carrying out the cracking is a gas furnace, The feed stream containing r-pyrolysis oil comprises at least 50 wt.% propane and at least 5 wt.% and not more than 50 wt.% r-pyrolysis oil, based on the total weight of the feed stream, The r-pyrolysis oil is not hydrotreated before the cracking, In the radiant section of the cracker, the feed stream comprising r-pyrolysis oil is thermally cracked, the residence time of the feed stream in the radiant section is at least 0.25 seconds and not more than 1 second, the temperature at the inlet of the radiant section is at least 500° C. and not more than 650° C., the coil outlet temperature of the radiant section is at least 640 and not more than 870° C., Cracking occurs in the presence of steam with a steam to hydrocarbon ratio in the range of 0.2 to 0.8.

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