Recycled ingredients mixed esters and solvents

Abstract

The mixed ester composition having recycled content value is obtained by reacting recycled content feedstock to prepare recycled content mixed esters or by deducting the recycled content value applied to the mixed ester composition from recycled stock. At least a portion of the recycled content value in the feedstock or quota obtained from the mixed ester manufacturer is derived from recycled waste and / or pyrolysis of recycled waste and / or thermal steam cracking of recycled content pyrolysis oil.

Description

Technical Field

[0001] The present invention relates to a recycled component in an ester composition, and more particularly to a recycled component in an ester composition such as isobutyl isobutyrate, ethyl acetate and / or ethyl isobutyrate, wherein the recycled component is directly or indirectly obtained from pyrolysis of recycled waste and thermal cracking of the resulting recycled pyrolysis oil or from generating and using the effluent generated by the pyrolysis gas from the pyrolysis recycled waste. Background Art

[0002] Certain mixed esters, particularly isobutyl isobutyrate, ethyl acetate and ethyl isobutyrate, can be used as important solvent products in the production of various chemical components and products. These esters are commonly used in many applications, such as pharmaceuticals, crop protection (pesticides and insecticides), surfactants and detergents, food processing, solvents, fuel additives, oil and gas treatment, hardeners for epoxy resins, catalysts for polyurethanes, intermediates, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries, dyes, solvents, neutralizers, biocides, vulcanization accelerators and / or emulsifiers.

[0003] Solid waste, especially non-biodegradable recycled waste, can have a negative impact on the environment when disposed of in landfill after a single use. Therefore, from an environmental point of view, it is desirable to recycle as much waste as possible. However, from an economic point of view, recycling waste is challenging.

[0004] While some waste materials are relatively easy and inexpensive to recycle, other waste materials require extensive and expensive processing before they can be reused. In addition, different types of waste materials generally require different types of recycling processes.

[0005] In order to maximize recycling efficiency, it is desirable for large-scale production facilities to be able to process feedstocks with recycled content derived from various recycled waste materials. Commercial facilities involved in the production of non-biodegradable products or products whose final destination is a landfill can greatly benefit from using feedstocks with recycled content.

[0006] Some recycling efforts involve complex and detailed separation of recycled waste streams, which results in increased costs for obtaining recycled waste stream components. For example, conventional methanolysis technology requires a high purity PET stream. Some downstream products are also very sensitive to dyes and inks present on the recycled products, and their pretreatment and removal also increase the cost of the raw materials manufactured from these recycled waste materials. It is desirable to establish recycled components without being classified as a single type of plastic or recycled waste, or it can tolerate multiple impurities in the recycled waste stream flowing through the raw material.

[0007] In some cases, it may be difficult to dedicate a product with recycled content to a specific customer or downstream synthesis process for making a product derivative, especially when the recycled product is a gas or is difficult to separate. With respect to gases, because gas infrastructure is continuous flow and often mixes gas streams from a variety of sources, there is a lack of infrastructure to separate and distribute gases made specifically from recycled content feedstocks.

[0008] Additionally, it is recognized that some regions wish to move away from reliance on natural gas, ethane or propane as the sole source for manufacturing feedstock products such as ethylene and propylene and their downstream derivatives, and wish to utilize alternative or supplemental feedstocks for cracking.

[0009] It would also be desirable to synthesize mixed esters using existing equipment and processes and without the need to invest in additional and expensive equipment to establish a recycled component in the manufacture of the compound or polymer.

[0010] It is also desirable to continue to purchase feedstocks for the preparation of mixed esters from aldehydes and alcohols prepared from olefins obtained from cracking facilities that are struggling due to the lack of economic attractiveness of production from natural gas fields or petroleum.

[0011] Additionally, it is desirable for manufacturers of blended esters to not rely solely on credits to determine the recycled content in blended esters, thereby providing blended ester manufacturers with multiple options for determining recycled content.

[0012] It is also desirable that the mixed ester manufacturer be able to determine the amount and timing of establishing recycled content. The mixed ester manufacturer may wish to establish more or less recycled content or no recycled content at certain times or for different batches. This method is desirable with flexibility and without requiring a large increase in investment. Summary of the invention

[0013] There is now provided a method of treating a composition derived directly or indirectly from pyrolysis recovery waste ("pr-AD"), the method comprising feeding the pr-AD into a reactor for producing alcohol.

[0014] There is now provided a method for treating a composition derived directly or indirectly from pyrolysis recycled waste ("pr-ROH"), the method comprising feeding the pr-ROH into a reactor for producing mixed esters.

[0015] Also provided is a method of preparing a recycled component alcohol composition ("r-ROH"), the method comprising subjecting an aldehyde composition to a synthesis process to produce an alcohol effluent comprising r-ROH, at least a portion of which is derived directly or indirectly from pyrolysis recycled waste ("pr-AD").

[0016] Also provided is a method of preparing a recycled content mixed ester composition ("r-EC") comprising reacting an alcohol composition at least a portion of which is derived directly or indirectly from pyrolysis recycled waste ("pr-ROH") with an acid to produce a mixed ester effluent comprising r-EC.

[0017] Also provided is a method for preparing alcohol, comprising:

[0018] a. An alcohol manufacturer, which obtains the aldehyde composition from a supplier and:

[0019] i. also obtain a pyrolysis recovery component quota or

[0020] ii. receiving a pyrolysis recovery component quota from any person or entity without supplying an alcohol composition from the person or entity that transferred the pyrolysis recovery component quota; and

[0021] b. depositing at least a portion of the pyrolysis recovery quota obtained in step a(i) or step a(ii) into a recovery inventory, and

[0022] c. Preparation of mixed ester compositions from any alcohol composition obtained from any source.

[0023] Also provided is a method for preparing a mixed ester, comprising:

[0024] a. A mixed ester manufacturer, which obtains the alcohol composition from a supplier and:

[0025] i. also obtain a pyrolysis recovery component quota or

[0026] ii. receiving a pyrolysis recovery component quota from any person or entity without supplying an alcohol composition from the person or entity that transferred the pyrolysis recovery component quota; and

[0027] b. depositing at least a portion of the pyrolysis recovery quota obtained in step a(i) or step a(ii) into a recovery inventory, and

[0028] c. Preparation of mixed ester compositions from any alcohol composition obtained from any source.

[0029] Also provided is a method for preparing alcohol, the method comprising:

[0030] a. An alcohol manufacturer, which obtains the aldehyde composition from a supplier and:

[0031] i. also obtain a pyrolysis recovery component quota or

[0032] ii. receiving a pyrolysis recovery component quota from any person or entity without supplying an alcohol composition from the person or entity that transferred the pyrolysis recovery component quota; and

[0033] b. the alcohol manufacturer prepares an alcohol composition from any aldehyde composition obtained from any source ("ROH"); and

[0034] c. Or:

[0035] i. applying the pyrolysis recovery component quota to OH prepared by supplying the aldehyde obtained in step (a); or

[0036] ii. applying the pyrolysis recovery component quota to EC which is not prepared by supplying the aldehyde obtained in step (a), or

[0037] iii. depositing the pyrolysis recovery component credit into a recovery inventory, deducting the recovery component value from the recovery inventory, and applying at least a portion of the value to:

[0038] 1.EC, thereby obtaining r-EC, or

[0039] 2. Compounds or compositions other than EC, or

[0040] 3. Both;

[0041] Regardless of whether the recovery component value is obtained from the pyrolysis recovery component quota obtained in step a(i) or step a(ii).

[0042] Also provided is a method for preparing a mixed ester, the method comprising:

[0043] a. A mixed ester manufacturer, which obtains the alcohol composition from a supplier and:

[0044] i. also obtain a pyrolysis recovery component quota or

[0045] ii. receiving a pyrolysis recovery component quota from any person or entity without supplying an alcohol composition from the person or entity that transferred the pyrolysis recovery component quota; and

[0046] b. the mixed ester manufacturer prepares a mixed ester composition ("EC") from any alcohol composition obtained from any source; and

[0047] c. Or:

[0048] i. applying the pyrolysis recovery component quota to EC prepared by supplying the alcohol obtained in step (a); or

[0049] ii. applying the pyrolysis recovery component quota to EC which is not produced by supplying the alcohol obtained in step (a), or

[0050] iii. depositing the pyrolysis recovery component credit into a recovery inventory, deducting the recovery component value from the recovery inventory, and applying at least a portion of the value to:

[0051] 1.EC, thereby obtaining r-EC, or

[0052] 2. Compounds or compositions other than EC, or

[0053] 3. Both;

[0054] Regardless of whether the recovery component value is obtained from the pyrolysis recovery component quota obtained in step a(i) or step a(ii).

[0055] In another method, a method of preparing a recycled content mixed ester composition ("r-EC") is provided, the method comprising:

[0056] a. reacting any alcohol composition in a synthesis process to prepare a mixed ester composition ("EC"); and

[0057] b. applying the recycled content value to at least a portion of the EC to obtain a recycled content mixed ester composition ("r-EC"); and

[0058] c. Optionally, the recovered component value is obtained by deducting at least a portion of the recovered component value from the recovered inventory, and further optionally, the recovered inventory also contains a pyrolysis recovered component quota or a pyrolysis recovered component quota deposit that has been performed in the recovered inventory before the deduction; and

[0059] d. Optionally communicate to a third party that the r-EC has recycled content or was obtained or derived from recycled waste.

[0060] Also provided is a method of changing the recycled content value in a recycled content mixed ester composition ("r-EC"), the method comprising:

[0061] a. Any of the following:

[0062] i. reacting a recycled content alcohol composition ("r-ROH") to produce a recycled content mixed ester composition ("r-EC") having a first recycled content value ("first r-EC"); or

[0063] ii. having a recycled content mixed ester composition ("r-EC") having a first recycled content value (also a "first r-EC"); and

[0064] b. transferring recycled content value between the recycled stock and the first r-EC to obtain a second recycled content mixed ester composition having a second recycled content value ("second r-EC"), the second recycled content value being different from the first recycled content value, wherein the transferring optionally comprises:

[0065] i. deducting the recycled content value from the recycled stock and applying the recycled content value to the first r-EC to obtain the second r-EC having a second recycled content value, the second recycled content value being higher than the first recycled content value; or

[0066] ii. subtracting the recycled content value from the first r-EC and adding the subtracted recycled content value to the recycled stock to obtain the second r-EC having a second recycled content value, the second recycled content value being lower than the first recycled content value.

[0067] Also provided is another method for preparing a recycled content mixed ester composition ("r-EC"), the method comprising:

[0068] a. pyrolyzing a pyrolysis feed comprising recycled waste material to form a pyrolysis effluent comprising recycled pyrolysis oil (r-pyrolysis oil) and / or recycled pyrolysis gas ("r-pyrolysis gas");

[0069] b. optionally cracking a cracker feed comprising at least a portion of r-pyrolysis oil to produce a cracker effluent comprising r-olefins; or optionally cracking a cracker feed not containing r-pyrolysis oil to produce olefins and applying the recovery component value to the olefins so produced to produce r-olefins by deducting the recovery component value from the recovery inventory and applying it to the olefins; and

[0070] c. reacting any olefin volume in a synthesis process to produce an aldehyde composition and / or an alcohol composition; and

[0071] d. Optionally, reacting at least a portion of any aldehyde composition in a synthesis process to produce the alcohol composition;

[0072] e. reacting at least a portion of any alcohol composition in a synthesis process to produce a mixed ester composition; and

[0073] f. applying a recovery content value to at least a portion of the mixed ester composition based on:

[0074] i. Feed pyrolysis recovery component mixed ester composition ("pr-EC") as raw material or

[0075] ii. depositing at least a portion of the allowances obtained from any one or more of steps a) or b) into a recycled stock and deducting a recycled content value from said stock and applying at least a portion of said value to EC, thereby obtaining said r-EC.

[0076] Also provided is a direct method for preparing recycled content mixed esters ("r-EC"), the method comprising:

[0077] a. obtaining a pyrolysis recovery component aldehyde composition, at least a portion of which is directly derived from cracked r-pyrolysis oil or obtained from r-pyrolysis gas ("dr-ROH"),

[0078] b. preparing a mixed ester composition from a raw material comprising said dr-ROH,

[0079] c. applying a recycled content value to at least a portion of any mixed ester composition prepared by an entity that is the same entity as the mixed ester composition prepared in step b), wherein the recycled content value is based at least in part on the amount of recycled content contained in the dr-ROH.

[0080] Various uses are provided. Uses of a recycled aldehyde composition ("r-AD") derived directly or indirectly from pyrolysis recycled waste are provided, including converting r-AD in a synthetic process to produce an alcohol composition.

[0081] Various uses are provided. Uses of recycled alcohol compositions ("r-ROH") derived directly or indirectly from pyrolysis recycled waste are provided, including converting r-ROH in a synthetic process to prepare a mixed ester composition.

[0082] It also provides for the use of recovered stocks, including:

[0083] a. converting any alcohol composition in a synthetic process to prepare a mixed ester composition ("EC"); and

[0084] b. applying a recycled content value to the EC based at least in part on a deduction from a recycled inventory, wherein at least a portion of the inventory includes a recycled content allowance.

[0085] Also provided is an integrated process for preparing a recycled content mixed ester composition ("r-EC"), the process comprising:

[0086] a. Optionally, providing an aldehyde manufacturing facility that at least partially produces an aldehyde composition ("AD");

[0087] b. providing an alcohol manufacturing facility that at least partially produces an alcohol composition ("ROH"), the facility comprising a reactor configured to receive AD; and

[0088] c. providing a mixed ester manufacturing facility that prepares a mixed ester composition ("EC") and includes a reactor configured to receive ROH; and

[0089] d. feeding at least a portion of the ROH from an alcohol manufacturing facility to a mixed ester manufacturing facility by providing a supply system that provides fluid communication between the facilities;

[0090] wherein any one or all of the aldehyde manufacturing facility, alcohol manufacturing facility or mixed ester manufacturing facility respectively produces or supplies r-ROH or recycled component mixed esters (r-EC), and optionally, wherein the alcohol manufacturing facility supplies r-ROH to the mixed ester manufacturing facility via the supply system.

[0091] Another integrated system is provided, comprising:

[0092] a. an olefin manufacturing facility configured to produce an output composition comprising recycled content propylene or recycled content ethylene or both ("r-olefins");

[0093] b. an optional aldehyde manufacturing facility configured to receive an olefin stream from the olefin manufacturing facility and to produce an output composition comprising an aldehyde composition;

[0094] c. an alcohol production facility configured to receive an olefin stream from an olefin production facility and / or an aldehyde stream from an aldehyde production facility and to produce an output composition comprising an alcohol composition;

[0095] d. a mixed esters manufacturing facility having a reactor configured to receive an alcohol composition and produce an output composition comprising recycled component mixed esters ("r-EC"); and

[0096] e. 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 of the one or more manufacturing facilities.

[0097] An integrated system is also provided, comprising:

[0098] a. an olefin manufacturing facility configured to produce an output composition comprising recycled content propylene or recycled content ethylene or both ("r-olefins");

[0099] b. an optional aldehyde manufacturing facility configured to receive an olefin stream from the olefin manufacturing facility and to produce an output composition comprising an aldehyde composition;

[0100] c. an alcohol production facility configured to receive an olefin stream from an olefin production facility and / or an aldehyde stream from an aldehyde production facility and to produce an output composition comprising an alcohol composition;

[0101] d. a mixed esters manufacturing facility having a reactor configured to receive an alcohol composition and produce an output composition comprising recycled component mixed esters ("r-EC"); and

[0102] e. A piping system interconnecting at least two of the facilities, optionally with an intermediate processing facility or a storage facility, 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.

[0103] Also provided is a system or package comprising:

[0104] a. mixed esters, and

[0105] b. An identifier associated with the mixed ester, the identifier being an indication that the mixed ester has recycled content or is made from a source having a recycled content value.

[0106] Also provided is a method of offering for sale or selling recovered mixed esters, comprising:

[0107] a. converting an aldehyde composition in a synthetic process to prepare a mixed ester composition ("EC"),

[0108] b. applying a recycled content value to at least a portion of the EC, thereby obtaining a recycled content EC (r-EC), and

[0109] c. Offering to sell or selling said r-EC having recycled content or obtained or derived from recycled waste.

[0110] Also provided are recycled content mixed esters having monomers derived from the r-AD composition, and any articles made from the recycled content mixed esters. BRIEF DESCRIPTION OF THE DRAWINGS

[0111] 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).

[0112] 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.

[0113] Figure 3 is a schematic diagram of a pyrolysis process to produce an olefin-containing product.

[0114] 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.

[0115] Figure 5 is a schematic diagram of a cracking furnace suitable for receiving r-pyrolysis oil.

[0116] Figure 6 A furnace coil configuration with multiple tubes is shown.

[0117] Figure 7 Various feed positions of r-pyrolysis oil into the cracking furnace are shown.

[0118] Figure 8 A cracking furnace with a vapor liquid separator is shown.

[0119] Fig. 9 is a block diagram showing the process of recovering constituent furnace effluent.

[0120] 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.

[0121] Fig.11 A laboratory scale cracking unit design is shown.

[0122] Fig.12 Design features for a plant-based experimental feeding of r-pyrolysis oil to a gas-fed cracking furnace are described.

[0123] 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% paraffins and 13.73% unidentified components.

[0124] Fig.14 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0125] Fig.15 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0126] Fig.16 The boiling point curve of r-pyrolysis oil obtained by distillation in the laboratory and chromatography analysis.

[0127] Fig.17is 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] Fig. 22 is a boiling point graph of r-pyrolysis oil distilled in the laboratory with 34.7% aromatic content.

[0133] Fig.23 This is a boiling point curve of the r-pyrolysis oil used in the factory trial experiment.

[0134] Fig.24 is a graph of the carbon distribution of the pyrolysis oil used in the plant experiments.

[0135] Fig.25 is a plot of the cumulative weight percent carbon distribution of the pyrolysis oil used in the plant experiments. DETAILED DESCRIPTION

[0136] The words "containing" and "including" are synonymous with comprising. When indicating a numerical sequence, it should be understood that each number is modified to be the same as the first or last number in the numerical sequence or sentence, for example, each number is "at least" or "up to" or "not more than" as the case may be; and each number is 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 ...", etc. ” 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 no 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 no more than 99 wt.%, or no more than 95 wt.%, or no 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.

[0137] 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.

[0138] As used herein, "containing" and "including" are open ended and synonymous with "comprising."

[0139] The term "recycled content" is used herein as a noun to i) refer to a physical component (e.g., a compound, molecule, or atom), at least a portion of which is derived directly or indirectly from recycled waste, or ii) as an adjective modifying a specific composition (e.g., a compound, polymer, feedstock, product, or stream), at least a portion of which is derived directly or indirectly from recycled waste.

[0140] As used herein, "recycled content composition," "recycled composition," and "r-composition" refer to a composition having recycled content.

[0141] The term "pyrolysis recovery component" is used herein as a noun, i) to refer to a physical component (e.g., a compound, molecule, or atom) at least a portion of which is derived directly or indirectly from the pyrolysis of recovery waste, or ii) as an adjective modifying a specific composition (e.g., a feedstock, a product, or a stream) at least a portion of which is derived directly or indirectly from the pyrolysis of recovery waste. For example, the pyrolysis recovery component can be derived directly or indirectly from the cracking of the recovery component pyrolysis oil, the recovery component pyrolysis gas, or the recovery component pyrolysis oil, such as by a thermal steam cracker or a fluid catalytic cracker.

[0142] As used herein, "pyrolysis recycled content composition", "pyrolysis recycled composition" and "pr-composition" refer to a composition (e.g., compound, polymer, feedstock, product or stream) having pyrolysis recycled content. The pr-composition is a subset of the r-composition, wherein at least a portion of the recycled content of the r-composition is derived directly or indirectly from the pyrolysis of recycled waste.

[0143] As used herein, a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "directly derived" or "derived directly" from recycled waste has at least one physical component traceable to recycled waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from recycled waste has a recycled content quota associated with it and may or may not contain physical components traceable to recycled waste.

[0144] As used herein, a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "directly derived" or "derived directly" from the pyrolysis of recycled waste has at least one physical component traceable to the pyrolysis of recycled waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from the pyrolysis of recycled waste has a recycled component quota associated therewith and may or may not contain a physical component traceable to the pyrolysis of recycled waste.

[0145] As used herein, "pyrolysis oil" or "pyoil" refers to a composition of matter that is liquid when measured at 25°C and 1 atm and at least a portion of which is obtained by pyrolysis.

[0146] As used herein, "recovered content pyrolysis oil," "recovered pyrolysis oil," "pyrolysis recovered content pyrolysis oil," and "r-pyrolysis oil" refer to a pyrolysis oil at least a portion of which is obtained from pyrolysis and has a recovered content.

[0147] As used herein, "pyrolysis gas" and "pyrolysis gas" refer to a composition of matter that is a gas when measured at 25°C and 1 atm and at least a portion of which is obtained from pyrolysis.

[0148] As used herein, "recycled content pyrolysis gas," "recycled pyrolysis gas," "pyrolysis content pyrolysis gas," and "r-pyrolysis gas" refer to pyrolysis gas that is at least partially obtained from pyrolysis and has recycled content.

[0149] As used herein, "pyrolysis recovery component pyrolysis gas", "pyrolysis recovery pyrolysis gas" and "pr-pyrolysis gas" refer to r-pyrolysis gas with pyrolysis recovery components.

[0150] As used herein, "AD" is an aldehyde composition (eg, feedstock, product, or stream).

[0151] As used herein, "recovered content aldehyde" and "r-AD" refer to AD having a recovered content.

[0152] As used herein, "pyrolysis recovered component aldehyde" and "pr-AD" refer to r-AD having a pyrolysis recovered component.

[0153] As used herein, "ROH" is an alcohol composition (eg, feedstock, product, or stream).

[0154] As used herein, "recycled content alcohol" and "r-ROH" refer to ROH having a recycled content.

[0155] As used herein, "pyrolysis recovered component alcohol" and "pr-ROH" refer to r-ROH having a pyrolysis recovered component.

[0156] As used herein, "EC" is a mixed ester composition (eg, feedstock, product, or stream).

[0157] As used herein, "recycled content mixed esters" and "r-EC" refer to EC with recycled content.

[0158] As used throughout, the general description of a compound, composition, or stream does not require the presence of its substance, but does not exclude and may include its substance. For example, "EC" or "any EC" may include mixed esters prepared by any method, and may or may not contain recycled components, and may or may not be prepared from non-recycled component raw materials or from recycled component raw materials, and may or may not include r-EC or pr-EC. Similarly, r-EC may include or exclude pr-EC, although reference to r-EC does require it to have recycled components. In another example, "AD" or "any AD" may include aldehydes prepared by any method, and may or may not have recycled components, and may or may not include r-AD or pr-AD. Similarly, r-AD may include or exclude pr-AD, although reference to r-AD does require it to have recycled components.

[0159] As used herein, "pyrolyzed component mixed esters" and "pr-EC" refer to r-EC having a pyrolyzed recovered component.

[0160] As used herein, "Et" is the ethylene component (eg, feedstock, product, or stream), and "Pr" is the propylene component (eg, feedstock, product, or stream).

[0161] As used herein, "recycled content ethylene", "r-ethylene" and "r-Et" refer to Et with recycled content; "recycled content propylene", "r-propylene" and "r-Pr" refer to Pr with recycled content.

[0162] As used herein, "pyrolysis recovered ethylene" and "pr-Et" refer to r-Et with pyrolysis recovered components; "pyrolysis recovered propylene" and "pr-Pr" refer to r-Pr with pyrolysis recovered components.

[0163] As used herein, "EO" is an ethylene oxide composition (eg, feedstock, product, or stream).

[0164] As used herein, "recycled content ethylene oxide" and "r-EO" refer to EO having a recycled content.

[0165] As used herein, "pyrolyzed component ethylene oxide" and "pr-EO" refer to r-EO having a pyrolyzed recovered component.

[0166] As used throughout, a general description of a compound, composition, or stream does not require the presence of its substance, but does not exclude and may include its substance. For example, "EC" or "any EC" may include mixed esters prepared by any method, and may or may not contain recycled components, and may or may not be prepared from non-recycled component raw materials or from recycled component raw materials, and may or may not include r-EC or pr-EC. Similarly, r-EC may or may not include pr-EC, although reference to r-EC does require that it has recycled components. In another example, "AD" or "any AD" may include ethylene prepared by any method, and may or may not have recycled components, and may or may not include r-AD or pr-AD. Similarly, r-AD may or may not include pr-AD, although reference to r-AD does require that it has recycled components.

[0167] "Pyrolytic recycled content" is a specific subset / type (kind) of "recycled content" (genus). Wherever "recycled content" and "r-" are used herein, such use should be interpreted as explicitly disclosing and providing claim support for "pyrolytic recycled content" and "pr-", even if not explicitly stated as such. For example, whenever the term "recycled content ethylene oxide" or "r-EO" is used herein, it should be interpreted as also explicitly disclosing and providing claim support for "pyrolytic recycled content ethylene oxide" and "pr-EO".

[0168] As used throughout, whenever reference is made to cracking of r-pyrolysis oil, such cracking may be carried out by a thermal cracker or a hot steam cracker in a liquid feed furnace or in a gas feed furnace or in any cracking process. In one embodiment or in combination with any of the embodiments mentioned, the cracking is not catalytic or is carried out in the absence of an added catalyst, or is not a fluid catalytic cracking process.

[0169] As used throughout, whenever reference is made to pyrolysis of recycled waste or r-pyrolysis oil, all embodiments also include the option of (i) cracking the effluent of the pyrolysis recycled waste or cracking the r-pyrolysis oil and / or (ii) using the cracked effluent or r-pyrolysis oil as a feed to a gas feed furnace or tubes of a gas furnace / cracker.

[0170] As used throughout, a "family of entities" means at least one person or entity that directly or indirectly controls, is controlled by, or is under common control with another person or entity, where control means ownership of at least 50% of the voting stock, or shared management, common use of facilities, equipment, and employees, or family interests. As used throughout, references to persons or entities provide claim support to, and include, any person or entity in the family of entities.

[0171] In one embodiment or in combination with any other mentioned embodiment, reference to r-AD also includes pr-AD, or pr-AD obtained directly or indirectly from the cracking of r-pyrolysis oil or from r-pyrolysis gas; r-ROH also includes pr-ROH or pr-ROH obtained directly or indirectly from the cracking of r-pyrolysis oil or from r-pyrolysis gas, and r-AD also includes pr-AD or pr-AD obtained directly or indirectly from the cracking of r-pyrolysis oil or from r-pyrolysis gas.

[0172] In one embodiment or in combination with any of the mentioned embodiments, a method for preparing an r-AC composition by reacting AD with an acid in the presence of a catalyst is provided. The ROH can be r-Et or pr-Et or dr-Et. In one embodiment, the method for preparing r-EC starts with feeding r-ROH to a reactor for preparing EC.

[0173] Figure 1 The present invention 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 recycled waste) or in combination with any embodiment mentioned herein.

[0174] 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 embodiment mentioned herein, or in combination with any of the mentioned embodiments, 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.

[0175] 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 5As shown, the convection box 312 is integrated with the combustion chamber 322 .

[0176] Unless otherwise indicated, all component amounts provided herein (eg, for feeds, materials, streams, compositions, and products) are expressed on a dry basis.

[0177] 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, and at least a portion of which is obtained from pyrolysis, and has recycled content. In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the composition is obtained from pyrolysis of recycled waste (e.g., waste plastic or waste stream).

[0178] In one embodiment or in combination with any of the mentioned embodiments, "r-ethylene" can be a composition comprising: (a) ethylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) ethylene having a recovery content value attributable to at least a portion of the ethylene; and "r-propylene" can be a composition comprising (a) propylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) propylene having a recovery content value attributable to at least a portion of the propylene.

[0179] References to "r-ethylene molecules" refer to ethylene molecules derived directly or indirectly from recycled waste and references to "pr-ethylene molecules" refer to ethylene molecules derived directly or indirectly from r-pyrolysis oil effluent (r-pyrolysis oil or r-pyrolysis gas).

[0180] As used herein, "site" means the largest contiguous geographic boundary owned by a mixed esters manufacturer, or by a person or entity, or a combination of persons or entities within its family of entities, wherein the geographic boundary contains one or more manufacturing facilities, at least one of which is a mixed esters manufacturing facility.

[0181] 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.

[0182] 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.

[0183] As used herein, "recycled content value" and "r-value" refer to a unit of measurement representing the amount of material that is derived from recycled waste. The r-value can be derived from any type of recycled waste processed in any type of process.

[0184] As used herein, the terms "pyrolysis recovery content value" and "pr value" refer to a unit of measurement representing the amount of material derived from the pyrolysis of recycled waste. The pr value is a specific subset / type of r-values ​​associated with the pyrolysis of recycled waste. Therefore, the term r-value includes but does not require a pr value.

[0185] Specific recovery component value (r-value or pr value) can be by mass or percentage or any other measurement unit, and can be determined according to the standard system for tracing back, allocating and / or depositing and lending the recovery component in various compositions. Recovery component value can be deducted from the recovery component inventory and applied to product or composition, to attribute the recovery component to product or composition. Unless otherwise stated, recovery component value is not necessarily derived from manufacturing or cracking r-pyrolysis oil. In one embodiment or in combination with any mentioned embodiment, at least a portion of the r-pyrolysis oil from which a quota is obtained is also cracked in the cracking furnace as described in one or more embodiments throughout this paper.

[0186] 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:

[0187] a. Quota, or

[0188] b. deposited into recycled content inventory, or

[0189] c. The recycled content value in the recycled content inventory, or

[0190] 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.

[0191] A recycled PIA or r-PIA is a product, intermediate or article that may include a compound or a composition containing a compound or polymer, and / or an article with an associated recycled content value. A PIA does not have a recycled content value associated with it. PIAs include, but are not limited to, ethylene oxide or alkylene glycols (e.g., ethylene glycol).

[0192] As used herein, "recycled content quota" or "quota" means a recycled content value of:

[0193] a. from a starting composition (e.g., a compound, polymer, feedstock, product or stream) at least a portion of which is obtained from recycled waste, or has at least a portion of recycled content value derived from recycled waste, optionally from r-pyrolysis oil, to a receiving composition (receiving a quota of the composition, such as a compound, polymer, feedstock, product or stream), the starting composition having at least a portion thereof obtained from recycled waste, or having at least a portion of recycled content value derived from recycled waste, optionally derived from r-pyrolysis oil, the receiving composition may or may not have physical components traceable to a composition at least a portion of which is obtained from recycled waste; or

[0194] b. Depositing into a recycling stock a starting composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which is obtained from, or has at least a portion of, a recycled content value or pr value derived from recycled waste.

[0195] As used herein, "pyrolysis recovery component quota" and "pyrolysis quota" or "pr-quota" means a recovery component value of:

[0196] a. from a starting composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which was obtained from the pyrolysis of recycled waste, or has at least a portion of its recycled content value derived from the pyrolysis of recycled waste, to a receiving composition (e.g., a compound, polymer, feedstock, product, or stream), which may or may not have physical components traceable to a composition at least a portion of which was obtained from the pyrolysis of recycled waste; or

[0197] b. Deposited into a recycling inventory from a starting composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which was obtained from, or has at least a portion of its recycled component value derived from, pyrolysis of recycling waste.

[0198] A pyrolysis recovery content quota is a specific type of recovery content quota associated with the pyrolysis of recovered waste. Thus, the term recovery content quota includes a pyrolysis recovery content quota.

[0199] In one embodiment or in combination with any of the mentioned embodiments, the thermal pyrolysis recovery component quota or pyrolysis quota can have a recovery component value of:

[0200] a. from a starting composition (e.g., a compound, polymer, feedstock, product or stream) which is at least partially obtained from the cracking of r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), or is transferred from recycled waste used to prepare cracked r-pyrolysis oil, or is transferred from cracked or to be cracked r-pyrolysis oil, or which has at least a portion of its recovered component value derived from the cracking of r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), to a receiving composition (e.g., a compound, polymer, feedstock, product or stream or PIA), the starting composition being at least in part obtained from the cracking of r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), or is transferred from recycled waste used to prepare cracked r-pyrolysis oil, or is transferred from cracked or to be cracked r-pyrolysis oil, or which has at least a portion of its recovered component value derived from the cracking of r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), the receiving composition may or may not have physical components traceable to a composition at least in part of which is obtained from the cracking of r-pyrolysis oil; or

[0201] b. deposited into the recovery inventory and obtained from a composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which was obtained from, or has at least a portion of its recovery component value derived from, the cracking (e.g., liquid or gaseous thermal steam cracking) of an r-pyrolysis oil (regardless of whether the r-pyrolysis oil was cracked when the allowance was deposited into the recovery component inventory, provided that the r-pyrolysis oil from which the allowance was withdrawn was ultimately cracked).

[0202] A quota can be an allotment or a credit.

[0203] The recycled content quota may include a recycled content allocation or a recycled content credit obtained by diverting or using raw materials. In one embodiment or in combination with any of the mentioned embodiments, the composition receiving the recycled content quota may be a non-recycled composition, thereby converting the non-recycled composition into an r-composition.

[0204] As used herein, "non-recycled" refers to a composition (eg, compound, polymer, feedstock, product, or stream) that is not derived directly or indirectly from recycled waste.

[0205] As used herein, "non-recycled feed" in the context of a feed to a cracker or furnace refers to a feed that is not obtained from a recycled waste stream. Once the non-recycled feed obtains a recycled component quota (e.g., through a recycled component credit or recycled component allocation), the non-recycled feed becomes a recycled component feed, composition, or recycled PIA.

[0206] As used herein, term " reclaimed component allocation " refers to a type of reclaimed component quota, wherein the entity or individual of supplying composition sells or transfers composition to receiving individual or entity, and the individual or entity of preparing composition has quota, and at least a portion of this quota can be related to the composition that supplies individual or entity sells or transfers to receiving individual or entity. Supply entity or individual can be controlled by same entity or individual or entity family or different entity families. In one embodiment or with any embodiment combination mentioned, reclaimed component allocation is advanced together with composition and downstream derivative of said composition. In one embodiment or with any embodiment combination mentioned, allocation can be deposited in the reclaimed component stock, and is taken out from the reclaimed component stock as allocation, and is applied to composition to prepare r-composition or reclaim PIA.

[0207] As used herein, "recovered content credit" and "credit" means a recovered content 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 derived 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 compositions made from a process other than cracking a feedstock in a furnace through one or more intermediate feedstocks, or (iii) may be sold or transferred to a person or entity other than the owner of the quota, or (iv) may be sold or transferred by a person other than the supplier of the composition to which it is transferred. For example, a quota can be a credit when it is taken from r-pyrolysis oil and applied by the quota owner to a BTX composition or fraction thereof that is manufactured by the owner or within its family of entities and is obtained through the refining and fractionation of petroleum rather than through cracker effluent products; or it can be a credit if the quota owner sells the quota to a third party to allow the third party to resell the product or apply the credit to one or more components of the third party.

[0208] Credits may be available for sale, transfer or use, or may be sold, transferred or used, or:

[0209] a. not sell the composition, or

[0210] b. sell or transfer the Composition, but the Quota is not related to the sale or transfer of the Composition, or

[0211] 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.

[0212] In one embodiment or in combination with any of the embodiments mentioned, a quota can be deposited into a recycling component inventory, and a credit or allocation can be extracted from the inventory and applied to a composition. This will be the case where a first composition is prepared by pyrolysis of recycled waste, or by cracking of r-pyrolysis oil or r-pyrolysis oil, or by any other method of preparing the first composition from recycled waste, a quota is generated, and the allocation associated with the first component is deposited into a recycling component inventory, and the recycling component value is deducted from the recycling component inventory and applied to a second composition, which is not a derivative of the first composition or is not actually prepared as a raw material by the first composition. In this system, there is no need to track the source of the reactant to any atom contained in the cracking of the pyrolysis oil or the olefin-containing effluent, but any reactant made by any process can be used and a recycling component quota can be associated with such a reactant.

[0213] 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:

[0214] a. Obtaining r-pyrolysis oil,

[0215] b. Obtaining recovery component value (or quota) from r-pyrolysis oil and

[0216] i. Deposit into recycled content stock, withdraw quota (or credit) from recycled content stock

[0217] and apply it to any composition to obtain an r-composition, or

[0218] ii. Direct application to any composition without depositing into the stock of recycled components to obtain

[0219] r-composition; and

[0220] 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

[0221] 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.

[0222] 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.

[0223] 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.

[0224] 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 EO or AD) can be traced back to an r-composition prepared from recycled waste.

[0225] Determining whether a PR composition is derived directly or indirectly from the pyrolysis of recycled waste (e.g., derived from the cracking of r-pyrolysis oil or derived from r-pyrolysis gas) is not based on the presence or absence of intermediate steps or entities in the supply chain, but rather on whether at least a portion of the PR composition fed to the reactor used to prepare the final product (e.g., EO) can be traced back to a PR composition prepared from the pyrolysis of recycled waste.

[0226] As described above, a final product is considered to be directly derived from cracked r-pyrolysis oil or recycled waste if at least a portion of the atoms or molecules in the reactant feedstocks used to prepare the product can be traced, optionally via one or more intermediate steps or entities, to constituting at least a portion of an r-composition produced by cracking of recycled waste or r-pyrolysis oil fed to a cracking furnace or as an effluent from a cracking furnace.

[0227] The r-composition as an effluent may be in the form of a crude product that requires refining to isolate a specific r-composition. The r-composition manufacturer may sell such r-composition to an intermediate entity, typically after refining and / or purifying and compressing to produce a desired grade of a specific r-composition, which then sells the r-composition or one or more derivatives thereof to another intermediate entity for the preparation of an intermediate product, or directly to a product manufacturer. Any number of intermediates and intermediate derivatives may be prepared before the final product is prepared.

[0228] The actual volume of r-composition, whether condensed as a liquid, supercritical or stored as a gas, may remain in the facility where it was prepared, or may be transported to a different location, or held in an off-site storage facility prior to use by an intermediate or product manufacturer. For tracking purposes, once an r-composition made by recycling waste (e.g., by cracking r-pyrolysis oil or from r-pyrolysis gas) is mixed with another volume of composition (e.g., r-ethylene mixed with non-recycled ethylene) in, for example, a storage tank, salt dome or cave, then the entire tank, dome or cave becomes the source of r-composition at that time, and for tracking purposes, withdrawals from such storage facilities are withdrawn 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. Likewise, this also applies to any downstream storage facilities for storing derivatives of r-compositions, such as r-EC, r-ROH, r-AD, pr-AD, r-Et and pr-Et compositions.

[0229] An R-composition is considered to be indirectly derived from recycled waste or pyrolysis or cracking of R-pyrolysis oils if the R-composition is associated with a recycled content quota and may or may not contain physical components of the R-composition that are traceable to the cracking of R-pyrolysis or R-pyrolysis oils obtained from recycled waste or pyrolysis of recycled waste. For example, (i) a product manufacturer may operate within a legal framework, or an association framework, or an industry-recognized framework to require recycled content through a system of credits that are transferred to the product manufacturer, such as credits, regardless of where or from whom the R-composition, or derivatives thereof, or reactant feedstocks for making the product are purchased or transferred, or (ii) a supplier of the R-composition or derivatives thereof ("supplier") operates within a quota framework that allows a recycled content value or PR value to be associated with or applied to a portion or all of the compounds in the olefin-containing effluent or derivatives thereof to prepare the R-composition and transfer that recycled content value or quota to the manufacturer of the product or any intermediary that obtains a supply of the R-composition from the supplier. In this system, there is no need to trace the r-AD and / or r-ROH volumes back to the source of the r-composition or its derivatives made from recycled waste / pyrolyzed recycled waste, but rather any aldehyde composition prepared by any process can be used and have a recycled component quota associated with such aldehyde composition.

[0230] Examples of how to obtain recycled content from AD compositions used to prepare ROH and EC include:

[0231] (i) a cracker facility, wherein propylene and / or r-ethylene produced in the facility, by cracking r-pyrolysis oil or obtained from r-pyrolysis gas, may be in fluid communication with an AD forming facility (which may be a storage vessel to an AD facility or directly to an AD forming reactor) continuously or intermittently and through an intermediate facility (e.g. an AD facility) via interconnected pipelines, optionally through one or more storage vessels and valves or interlocks, directly or indirectly, and the r-propylene and / or r-ethylene feedstock is supplied via interconnected pipelines:

[0232] a. withdrawn from a cracker facility during the production of r-propylene and / or r-ethylene or thereafter during the time that r-propylene and / or r-ethylene are transported by pipeline to an AD formation facility; or

[0233] b. withdrawn from one or more storage tanks at any time, provided that at least one storage tank is fed with r-propylene and / or r-ethylene, as long as the entire volume of the one or more storage tanks is replaced by feed containing no r-propylene and / or r-ethylene; or

[0234] (ii) transporting from a storage vessel, vault or facility, or in an isotainer, by truck or rail or ship or by means other than pipeline, the propylene and / or ethylene feedstock containing or having been fed with r-propylene and / or r-ethylene until the entire volume of the vessel, vault or facility has been replaced by propylene and / or ethylene feedstock that does not contain r-propylene and / or r-ethylene; or

[0235] (iii) an AD manufacturer certifies, represents or advertises to its consumers or the public that its AD contains recycled content or is derived from a feedstock obtained from recycled content, where such recycled content claim is based in whole or in part on obtaining an r-propylene and / or r-ethylene feedstock associated with a quota of r-propylene and / or r-ethylene produced from cracked r-pyrolysis oil or obtained from r-pyrolysis gas) or

[0236] (iv) The AD manufacturer has obtained:

[0237] a. Based on the volume of propylene and / or ethylene produced from r-pyrolysis oil as certified, represented or advertised, or

[0238] b. has transferred credits or allocations for propylene and / or ethylene supply to an AD manufacturer to meet certification requirements or make representations or advertising thereof, or

[0239] c. Propylene and / or ethylene have an associated recovered content value, wherein the recovered content value is obtained from cracked propylene and / or ethylene / r-pyrolysis oil or an ethylene volume obtained at least in part from cracked r-pyrolysis oil or from r-pyrolysis gas via one or more intermediate independent entities.

[0240] As mentioned above, the recycled content may be a pyrolysis recycled content derived directly or indirectly from recycled waste, for example from cracked r-pyrolysis oil or from r-pyrolysis gas.

[0241] In one embodiment or in combination with any of the mentioned embodiments, various methods are provided for allocating recovered components between various olefin-containing effluent volumes or compounds thereof made from any one or combination of entities in a family of olefin-containing effluent entities. For example, a cracking furnace owner or operator of an olefin-containing effluent, or any one of a family of entities, or a site thereof, may:

[0242] a. A symmetrical distribution of recovery component values ​​between at least two compounds in the olefin-containing effluent or between PIAs based on the same fractional percentage of recovery component in one or more feedstocks or based on the quota amount received. For example, if 5 wt% of the total cracker feedstock 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

[0243] 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 PIA can exceed the recovery component value associated with other compounds or PIAs. For example, one 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 PIA 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.

[0244] 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.

[0245] In one embodiment or in combination with any of the mentioned embodiments, a recycled content input or generation (recycled content feedstock or quota) can be to or at a first site, and recycled content values ​​from the input are transferred to a second site and applied to one or more compositions prepared at the second site. The recycled content values ​​can be applied to the compositions symmetrically or asymmetrically at the second site.

[0246] A recovered component value that is "derived from cracked r-pyrolysis oil" or a recovered component value that is "obtained from cracked r-pyrolysis oil" or that originates from cracked r-pyrolysis oil, directly or indirectly, does not imply when the recovered component value or quota is taken, captured, deposited into a recovered component inventory, or transferred. The timing of depositing a quota or recovered component value into a recovered component inventory or realizing, identifying, capturing, or transferring it is flexible and can be done as early as receiving the r-pyrolysis oil at a site within the family of entities that owns it or by bringing the r-pyrolysis oil into the inventory or within the family of entities by an entity or individual that owns or operates a cracking facility. Thus, a quota or recovered component value for a volume of r-pyrolysis oil that can be obtained, captured, deposited into a recovered component inventory, or transferred to a product, without that volume being fed to a cracking furnace and cracked. The quota can also be obtained during the feeding of the r-pyrolysis oil to the cracker, during cracking, or when preparing an r-composition. An allowance taken when r-pyrolysis oil is owned, possessed or received and deposited into recovered content inventory is an allowance associated with, obtained from or derived from cracked r-pyrolysis oil, even if the r-pyrolysis oil has not been cracked at the time the allowance is taken or deposited, provided that the r-pyrolysis oil is cracked at some point in the future.

[0247] In one embodiment or in combination with any of the mentioned embodiments, 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 %, or at least 40wt.%, or at least 45wt.%, or at least 50wt.%, or at least 55wt.%, or at least 60wt.%, or at least 65wt.% and / or the amount may be at most 100wt.%, or at most 95wt.%, or at most 90wt.%, or at most 80wt.%, or at most 70wt.%, or at most 60wt.%, or at most 50wt.%, or at most 40wt.%, or at most 30wt.%, or at most 25wt.%, or at most 22wt.%, or At most 20wt.%, or at most 18wt.%, or at most 16wt.%, or at most 15wt.%, or at most 14wt.%, or at most 13wt.%, or at most 11wt.%, or at most 10wt.%, or at most 8wt.%, or at most 6wt.%, or at most 5wt.%, or at most 4wt.%, or at most 3wt.%, or at most to 2wt.%, or at most 1wt.%, or at most 0.9wt.%, or at most 0.8wt.%, or at most 0.7wt.%. The recycled component value associated with the r-composition, r-compound or its downstream reaction product can be associated by applying a quota (credit or allocation) to any manufactured or sold composition, compound, or PIA. The quota can be included in a quota inventory created, maintained or operated by or for the recovery of PIA or r-composition manufacturers. The quota can be obtained from any source along any manufacturing chain of the product, as long as it comes from cracking a raw material containing r-pyrolysis oil.

[0248] In one embodiment or in combination with any of the mentioned embodiments, a recycled PIA manufacturer can manufacture a recycled PIA, or process reactants (e.g., any compound of an olefin-containing cracker effluent) from any source obtained from a supplier (e.g., a cracker manufacturer or one of its family of entities), whether or not such reactants have any recycled content, to manufacture a recycled PIA, and:

[0249] i. also receive a recycling quota for that reactant from the same reactant supplier, or

[0250] 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.

[0251] 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 connected with the amount of the recovery component in the supplied reactant or the reactant for preparing the recovery PIA, containing olefin effluent. This makes the recovery component flexibly distributed between the various products prepared by them separately between the reactant supplier and the recovery PIA manufacturer. However, in each of these situations, the recovery component quota is associated with cracking r-pyrolysis oil.

[0252] 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.

[0253] 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 rather than requiring the PIA manufactured by the reactants provided.

[0254] The quota can be deposited into a recycled content 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 olefins. The manufacturer can also manufacture a PIA, whether or not the recycled content is applied to the PIA, and whether or not the recycled content (if applied to the PIA) is taken from the recycled content inventory. For example, a manufacturer of an olefin-containing effluent containing olefins can:

[0255] a. deposit the allowance into the stock and store it only; or

[0256] b. the olefin-containing effluent deposits the quota into an inventory and applies the quota from the inventory to one or more compounds in the olefin-containing effluent or to any PIA produced by the manufacturer, or

[0257] c. Selling or transferring the allowance 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.

[0258] 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.

[0259] 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.

[0260] As used in the full text, the recovery component inventory can be owned by the owner of the cracking furnace of the 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. Equally, 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.

[0261] 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:

[0262] a. Applied to PIA prepared by supplying reactants;

[0263] 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

[0264] 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

[0265] d. Deposit into inventory and store.

[0266] It is not necessary in all embodiments to use r-reactants to prepare the recovered PIA, or to obtain the recovered PIA from a recovered component quota associated with the reactants. In addition, it is not necessary to apply a quota to a feedstock to prepare the recovered PIA to which the recovered component is applied. Instead, as described above, the quota may be deposited into the electronic inventory even if it is associated with the reactants when they are obtained. However, in one embodiment or in combination with any of the mentioned embodiments, the reactants associated with the quota are used to prepare the recovered PIA. In one embodiment or in combination with any of the mentioned embodiments, the recovered PIA is obtained from a recovered component quota associated with the r-reactants or r-pyrolysis oil or with cracked r-pyrolysis oil. In one embodiment or in combination with any of the mentioned embodiments,

[0267] 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:

[0268] 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

[0269] b. applying the quota to any PIA not produced directly or indirectly from cracked r-pyrolysis oil olefin-containing effluent, such as where the PIA has already been produced and stored in inventory or is produced in the future; or

[0270] 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

[0271] d. is deposited into inventory and stored for later use.

[0272] There is also now provided a package or combination of a recycled PIA and a recycled content identifier associated with the recycled PIA, wherein the identifier is or contains an indication that the recycled PIA contains or is derived from or is associated with recycled content. The package may 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, jerry can, plastic bag, spool, roving, wrap 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.

[0273] 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.

[0274] In one embodiment or in combination with any of the mentioned embodiments, there is provided a system or package comprising:

[0275] a. Reclaim PIA, and

[0276] 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.

[0277] The system can be a physical combination, such as a package with at least some recycled PIA as its contents, and the package has a label, such as a logo, which identifies the component with or 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 procedure. The identifier does not have to be physically on the recycled PIA or on the package, 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 the 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, the article manufactured by the recycled 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.

[0278] A recycled PIA may be made from a reactant, whether or not the reactant is a recycled component reactant. Once a PIA is prepared, it may be designated as having a recycled component based on and derived from at least a portion of a quota. The quota may be taken or deducted from the recycled component stock. The amount deducted and / or applied to the PIA may correspond to any method, such as a mass balance method.

[0279] 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.

[0280] The following are examples of the application of recycled content to PIA or to effluents or compounds containing non-recycled olefins therein:

[0281] 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

[0282] 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

[0283] 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:

[0284] a. Apply all the recovered components in the r-pyrolysis oil to determine the amount of recovered components in the recovered PIA, or

[0285] 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

[0286] 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

[0287] 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

[0288] 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

[0289] 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

[0290] 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

[0291] 8. Recycling PIA manufacturers obtain quotas derived from r-pyrolysis oil, and:

[0292] 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

[0293] 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.

[0294] 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.

[0295] 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.

[0296] 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:

[0297] 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,

[0298] b. converting a reactant in a synthetic process to prepare PIA, and the reactant may be any reactant or r-reactant,

[0299] 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

[0300] d. Offering or selling a recycled PIA containing or obtained with the following recycled content, which 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.

[0301] 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.

[0302] As used throughout, the step of deducting a quota from the inventory of recycled components does not need to be applied to the recycled PIA product. Deduction does not mean that the quantity disappears or is removed from the inventory log. Deduction can be an adjustment entry, a withdrawal, an addition as a debit entry, or any other algorithm, which is based on the amount of recycled components associated with the product and one or the accumulated deposit quota amount in the inventory to adjust input and output. For example, deduction can be a simple step of deducting / debiting entries from one column and adding / crediting to another column within the same program or book, or an algorithm that automates deductions and entries / additions and / or applies or is assigned to a product information board. The step of applying quotas to PIA (wherein such quotas are deducted from the inventory) does not need to physically apply quotas to recycled PIA products or to any documents associated with the recycled PIA products sold. For example, a recycled PIA manufacturer can ship recycled PIA products to customers, and the "application" of the quota for recycled PIA products is met by electronically transmitting the recycled component credit to the customer.

[0303] 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 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.

[0304] 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.

[0305] 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.

[0306] 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:

[0307] a. cracking r-pyrolysis oil to produce an olefin-containing effluent; and

[0308] b. separating the compounds in the olefin-containing effluent to obtain separated compounds; and

[0309] c. reacting any reactants in the synthesis process to prepare PIA;

[0310] d. depositing the quota into the quota stock, the quota being derived from r-pyrolysis oil; and

[0311] e. Apply any allowance from the stock to the PIA, thereby obtaining a recycled PIA.

[0312] 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:

[0313] a. providing an olefin-containing effluent manufacturing facility configured to produce reactants;

[0314] b. providing a PIA manufacturing facility having a reactor configured to receive reactants from the olefin-containing effluent manufacturing facility; and

[0315] 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, wherein the olefin-containing effluent production facility generates or participates in the process of generating quota and cracked r-pyrolysis oil, and:

[0316] i. applying the quota to the reactants or to the PIA, or

[0317] ii. Deposit the quota into a quota stock and optionally extract a share from the stock and apply to reactants or to PIA.

[0318] A recovered PIA manufacturing facility may prepare recovered PIA by receiving 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.

[0319] In one embodiment or in combination with any of the mentioned embodiments, there is also provided a system for producing recycled PIA as follows:

[0320] a. providing an olefin-containing effluent manufacturing facility configured to produce an output composition comprising an olefin-containing effluent;

[0321] 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;

[0322] c. Providing a PIA manufacturing facility having a reactor configured to receive reactants and produce an output composition comprising PIA;

[0323] 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.

[0324] 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,

[0325] 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.

[0326] 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.

[0327] In one embodiment, an integrated recycling PIA production and consumption system is also provided. The system includes:

[0328] a. providing an olefin-containing effluent manufacturing facility configured to produce an output composition comprising an olefin-containing effluent;

[0329] 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;

[0330] c. Providing a PIA manufacturing facility having a reactor configured to receive reactants and produce an output composition comprising PIA;

[0331] 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.

[0332] 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).

[0333] A ring manufacturing method is also provided, the method comprising:

[0334] 1. Provide r-pyrolysis oil, and

[0335] 2. cracking the r-pyrolysis oil to produce an olefin-containing effluent, and

[0336] i. reacting compounds separated from the olefin-containing effluent to produce recovered PIA, or ii. combining a recovered component quota obtained from the r-pyrolysis oil with PIA prepared from compounds separated from a non-recovered olefin-containing effluent to produce recovered PIA; and

[0337] 3. Removing at least a portion of any of the recycled PIA or any other product, compound or polymer produced from the recycled PIA as a feedstock to produce the r-pyrolysis oil.

[0338] In the above process, a fully circular or closed loop process is provided, wherein the recovered PIA can be recycled multiple times.

[0339] Examples of articles included in the PIA are fibers, yarns, tows, continuous filaments, staple fibers, rovings, fabrics, textiles, foils, films (eg, polyolefin films), sheets, composite sheets, plastic containers, and consumer articles.

[0340] In one embodiment or in combination with any of the mentioned embodiments, the recovered PIA is of the same family or class of polymers or articles as the polymers or articles used to prepare the r-pyrolysis oil.

[0341] The terms "recycled waste," "waste stream," and "recycled waste stream" are used interchangeably to refer to any type of waste or waste-containing stream that is reused in a production process rather than permanently disposed of (e.g., in a landfill or incinerator).

[0342] A recycled waste stream is a flow or accumulation of recycled waste from industrial and consumer sources that is at least partially recycled. A recycled waste stream includes materials, products, and articles (collectively referred to as "materials" when used alone). Recycled waste materials can be solid or liquid. Examples of solid recycled waste streams include plastics, rubber (including tires), textiles, wood, biowaste, modified cellulose, wet laid products, and any other material capable of pyrolysis. Examples of liquid waste streams include industrial sludge, oils (including those derived from plants and petroleum), recycled lubricating oils, or vegetable or animal oils, and any other chemical streams from industrial plants.

[0343] In one embodiment or in combination with any of the mentioned embodiments, the recycled waste stream that is pyrolyzed comprises a stream that contains at least in part post-industrial material, or post-consumer material, or both post-industrial material and post-consumer material. In one embodiment or in combination with any of the mentioned embodiments, post-consumer material is material that has been used at least once for its intended application for any duration regardless of wear and tear, or material that has been sold to an end-use consumer, or material that has been discarded into a recycling bin by any person or entity other than the manufacturer or business engaged in the manufacture or sale of the material.

[0344] In one embodiment or in combination with any of the mentioned embodiments, post-industrial materials are materials that have been manufactured and not used for their intended application, or not sold to an end-use customer, or discarded by the manufacturer or any other entity involved in the sale of the material. Examples of post-industrial materials include reprocessing, regrind, scrap, off-cuts, 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.

[0345] The form of the recycled waste stream that can be fed to the pyrolysis unit is not limited and can include any form of article, product, material or part thereof. A portion of the article can take the form of a sheet, extruded profile, molded article, film, laminate, foam sheet, fragment, flake, granule, fiber, agglomerate, briquette, powder, fragment, strip, or any shaped piece having various shapes, or any other form other than the original form of the article, and suitable for feeding to the pyrolysis unit.

[0346] In one embodiment or in combination with any of the mentioned embodiments, the recycled waste is reduced in size. The reduction can be performed by any means including shredding, shredding, harrowing, grinding, pulverizing, cutting the stock, molding, compressing or dissolving in a solvent.

[0347] The recycled waste plastics can be separated as one type of polymer stream, or can be a stream of mixed recycled waste plastics. Plastics can be any organic synthetic polymer that is solid at 25°C and 1 atm. Plastics can be thermosetting, thermoplastic or elastomeric plastics. Examples of plastics include high density polyethylene and its copolymers, low density polyethylene and its copolymers, polypropylene and its copolymers, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyesters (including polyethylene terephthalate), copolyesters and terephthalate copolyesters (e.g., containing residues of TMCD, CHDM, propylene glycol or NPG monomers), polyethylene terephthalate, polyamides, poly(methyl methacrylate), polytetrafluoroethylene, acrylonitrile-butadiene-styrene (ABS), polyurethanes, cellulose and its derivatives, such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate; regenerated cellulose products such as viscose and rayon, epoxy resins, polyamides, phenolic resins, polyacetals, polycarbonates, polyphenyl alloys, polypropylene and its copolymers, polystyrene, styrene compounds, vinyl compounds, styrene-acrylonitrile, thermoplastic elastomers, urea-based polymers and melamine-containing polymers.

[0348] Suitable recycled waste plastics also include any of those with resin ID codes 1-7 within the chasing arrow triangle established by SPI. In one embodiment or in combination with any of the embodiments mentioned, r-pyrolysis oil is made from a recycled waste stream, at least a portion of which contains plastics that are not normally recycled. These include plastics with the numbers 3 (polyvinyl chloride), 5 (polypropylene), 6 (polystyrene), and 7 (others). In one embodiment or in combination with any of the embodiments mentioned, the recycled waste stream that is pyrolyzed contains less than 10 weight percent, or no more than 5 weight percent, or no more than 3 weight percent, or no more than 2 weight percent, or no more than 1 weight percent, or no more than 0.5 weight percent, or no more than 0.2 weight percent, or no more than 0.1 weight percent, or no more than 0.05 weight percent of No. 3 plastic (polyvinyl chloride), or alternatively No. 3 and No. 6 plastics, or alternatively No. 3, 6, and No. 7 plastics.

[0349] Examples of recycled rubber include natural and synthetic rubber. The form of the rubber is not limited, including tires.

[0350] Examples of recycled waste wood include softwood and hardwood, chipped wood, pulp or finished products. A large amount of recycled waste wood comes from industry, construction or demolition.

[0351] Examples of recycled biorecyclable waste include household biorecyclable waste (eg food), green or garden biorecyclable waste, and biorecyclable waste from the industrial food processing industry.

[0352] 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.

[0353] 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.

[0354] 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.

[0355] 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.

[0356] 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.

[0357] 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.

[0358] Examples of recycled vegetable or animal oils include oils recycled from animal processing facilities and recycled waste from restaurants.

[0359] The sources of post-consumer or post-industrial recycled waste from which recycling is obtained are not limited and may include recycled waste present in and / or separated from a municipal solid recycled waste stream ("MSW"). For example, a 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.

[0360] In one embodiment or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit may contain at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99 weight percent of at least one, or at least two, or at least three, or at least four, or at least five, or at least six different kinds of recycled waste. Reference to "kind" is determined by resin ID code 1-7. In one embodiment or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit contains less than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 1 weight percent of polyvinyl chloride and / or polyethylene terephthalate in each case. In one embodiment or in combination with any of the embodiments mentioned, the recycled waste stream contains at least one, two or three plasticized plastics.

[0361] 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.

[0362] 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 the drawings, the pyrolysis system 110 may also include additional sources of other types of recycled waste, which may be used to provide other feed types to the system 110 .

[0363] 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.

[0364] 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.

[0365] 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.

[0366] 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%.

[0367] 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.

[0368] 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.

[0369] 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.

[0370] 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.

[0371] 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.

[0372] 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.

[0373] In one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be at least 1 second, or at least 2 seconds, or at least 3 seconds, or at least 4 seconds, or at least 10, or at least 20 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes, or at least 75 minutes, or at least 90 minutes. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be no more than 6 hours, or no more than 5 hours, or no more than 4 hours, or no more than 3 hours, or no more than 2 hours, or no more than 1 hour, or no more than 0.5 hours. In one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be in the range of 30 minutes to 4 hours, or 30 minutes to 3 hours, or 1 hour to 3 hours, or 1 hour to 2 hours.

[0374] 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.

[0375] 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 or in combination with any mentioned embodiment, 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) combinations thereof.

[0376] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 occurs substantially in the 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.

[0377] 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.

[0378] 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).

[0379] 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.

[0380] 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.

[0381] 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.

[0382] 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 r-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.

[0383] In one embodiment or in combination with any of the mentioned embodiments, the r-pyrolysis oil is free of r-catalytic pyrolysis oil.

[0384] 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.

[0385] 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.

[0386] 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.

[0387] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, at least a portion of the pyrolysis oil vapor stream 136 can be introduced into a hydroprocessing unit 142 for further refining. The hydroprocessing unit 142 may include a hydrocracker, a catalytic cracker operated using a hydrogen feed stream, a hydroprocessing unit and / or a hydrogenation unit. In the hydroprocessing unit 142, the pyrolysis oil vapor stream 136 can be treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil and remove undesirable by-products from the pyrolysis oil. The resulting hydrotreated pyrolysis oil vapor stream 144 can be removed and introduced into a quenching unit 138. Alternatively, the pyrolysis oil vapor can be cooled, liquefied, and then treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil. In this case, hydrogenation or hydroprocessing is performed in the liquid phase pyrolysis oil. In this embodiment, post-hydrogenation or post-hydroprocessing does not require a quenching step.

[0388] 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.

[0389] The pyrolysis oil may mainly contain hydrocarbons having 4 to 30 carbon atoms per molecule (e.g., C 4 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, paraffins, aromatic hydrocarbons, and isomers having that number of carbon atoms. For example, each of the n-, iso-, and tert-butane and butene and butadiene molecules would fall within the general description "Cx". 4 ”.

[0390] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil fed to the cracking furnace may have a C 20 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, in each case. 4 -C 30 Hydrocarbon content, based on the weight of the pyrolysis oil.

[0391] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the furnace may comprise primarily C 5 -C 25 , C 5 -C 2 2 or C5 -C 2 0 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 C 5 -C 25 , C 5 -C 22 or C 5 -C 20 Hydrocarbons, based on the weight of the pyrolysis oil.

[0392] 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 C 5 -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).

[0393] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a C 2+ content of at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, in each case by weight. 6 -C 12The 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 C content of no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, in each case by weight. 6 -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 C 6 -C 12 Hydrocarbon content.

[0394] 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.

[0395] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil or r-pyrolysis oil fed to the cracking furnace, or the feed to the cracking furnace receiving a predominantly C 2 -C 4 The raw material r-pyrolysis oil (and reference to r-pyrolysis oil or pyrolysis oil throughout includes 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 C 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.

[0396] 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.

[0397] 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.

[0398] 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.

[0399] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a paraffin content of at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a paraffin content of no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a paraffin content of 25 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.

[0400] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an n-paraffin content of at least 5, or at least 10, or at least 15, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an n-paraffin content of no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an n-paraffin 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.

[0401] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin to olefin weight ratio of at least 0.2: 1, or at least 0.3: 1, or at least 0.4: 1, or at least 0.5: 1, or at least 0.6: 1, or at least 0.7: 1, or at least 0.8: 1, or at least 0.9: 1, or at least 1: 1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin to olefin weight ratio of no more than 3: 1, or no more than 2.5: 1, or no more than 2: 1, or no more than 1.5: 1, or no more than 1.4: 1, or no more than 1.3: 1. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin to olefin weight ratio of 0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1:4.5:1, or 0.2:1 to 4:1, or 0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

[0402] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of no more than 100:1, 7, or no more than 5:1, or no more than 50:1, or no more than 40:1, or no more than 30:1. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a normal-to-isoparaffin weight ratio in the range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0403] It should be noted that all of the above hydrocarbon weight percentages can be determined using gas chromatography-mass spectrometry (GC-MS).

[0404] 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 .

[0405] 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.

[0406] 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.

[0407] 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.

[0408] 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.

[0409] 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.

[0410] 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.

[0411] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil of the present invention can be a recycled content pyrolysis oil composition (r-pyrolysis oil).

[0412] 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.

[0413] 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.

[0414] 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.

[0415] In one embodiment or in combination with any of the embodiments mentioned herein, the C 4 -C 7The light fraction may include at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% C8+ content. 3 and lighter (C 3- ) or C 7 and lighter (C 7- ) content. In some embodiments, the separator can concentrate the desired components into the heavy fraction, so that the heavy fraction can have a C content higher than that of the pyrolysis oil taken out from the pyrolysis zone. 4 -C 7 Content or C 8+ The content of C is at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 7, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150% 4 -C 7 Content or C 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.

[0416] 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.

[0417] 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 amount of r-pyrolysis oil and non-recovered hydrocarbons can be within one or more ranges described herein.

[0418] At least a portion of the r-olefins may be derived directly or indirectly from the cracking of the r-pyrolysis oil. The process for obtaining r-olefins by cracking (r-pyrolysis oil) may be as follows and as Figure 4 As described in.

[0419] 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.

[0420] 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.

[0421] 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.

[0422] 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.

[0423] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can comprise 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 C 4 -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 C 5 -C 25 , C 5 -C 22 or C 5 -C 20 hydrocarbons, or may contain at least 55, 60, 65, 70, 75, 80, 85, 90 or 95 weight percent C 5 -C 25 , C 5 -C 22 or C 5 -C 20 hydrocarbon.

[0424] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil composition can comprise C 4 -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.

[0425] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil composition can comprise C 13 -C 22 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and alicyclic hydrocarbons) and C 4 -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.

[0426] In one embodiment, the two aliphatic hydrocarbons (branched or unbranched alkanes and alkenes, and alicyclic compounds) with the highest concentration in r-pyrolysis oil are C 5 -C 18 , or C 5 -C 16 , or C 5 -C 14 , or C 5 -C 10 , or C 5 -C 8 (including the end value).

[0427] The r-pyrolysis oil may include one or more of paraffinic, cycloparaffinic or cycloaliphatic hydrocarbons, aromatic hydrocarbons, aromatic-containing hydrocarbons, olefins, oxygen-containing compounds and polymers, heteroatom compounds or polymers, and other compounds or polymers.

[0428] For example, in one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can contain at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, and / or no more than 99, or no more than 97, or no more than 98 weight percent in each case. More than 95, or not more than 93, or not more than 90, or not more than 87, or not more than 85, or not more than 83, or not more than 80, or not more than 78, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, not more than 25, not more than 30, or not more than 20, or not more than 15 of paraffins (either straight or branched) based on the total weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin content of 25 to 90, 35 to 90, or 40 to 80, or 40 to 70, or 40 to 65 weight percent, or 5 to 50, or 5 to 40, or 5 to 35, or 10 to 35, or 10 to 30, or 5 to 25, or 5 to 20, in each case as wt. % based on the weight of the r-pyrolysis oil composition.

[0429] 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.

[0430] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a paraffin to olefin weight ratio of at least 0.2: 1, or at least 0.3: 1, or at least 0.4: 1, or at least 0.5: 1, or at least 0.6: 1, or at least 0.7: 1, or at least 0.8: 1, or at least 0.9: 1, or at least 1: 1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a paraffin to olefin weight ratio of no more than 3: 1, or no more than 2.5: 1, or no more than 2: 1, or no more than 1.5: 1, or no more than 1.4: 1, or no more than 1.3: 1. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can have a paraffin to olefin weight ratio in the range of 0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1 to 4.5:1, or 0.2:1 to 4:1, or 0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

[0431] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of no more than 100:1, or no more than 50:1, or no more than 40:1, or no more than 30:1. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a normal-to-isoparaffin weight ratio in the range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0432] 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.

[0433] 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.

[0434] 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.

[0435] 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.

[0436] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, 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.

[0437] 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 percent, 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.

[0438] In one embodiment or in combination with any embodiment mentioned herein 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 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 the wt.% water based on the weight of the r-pyrolysis oil.

[0439] In one embodiment or in combination with any embodiment mentioned herein 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.

[0440] In one embodiment or in combination with any embodiment mentioned herein 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.

[0441] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have the following component contents:

[0442] 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

[0443] 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.%,

[0444] 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.

[0445] In each case based on the weight of the r-pyrolysis oil.

[0446] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, 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.

[0447] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the metal content of the r-pyrolysis oil is desirably low, for example, no more than 2 wt.%, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, in each case wt.% based on the weight of the r-pyrolysis oil.

[0448] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the alkali and alkaline earth metal or mineral content of the r-pyrolysis oil is desirably low, for example not more than 2 wt.%, or not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.2, or not more than 0.15, or not more than 0.1, or not more than 0.05, in each case wt.% based on the weight of the r-pyrolysis oil.

[0449] In one embodiment or in combination with any of the embodiments mentioned herein or in combination with any of the embodiments mentioned herein, the weight ratio of paraffins to cycloalkanes in the r-pyrolysis oil can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.25:1, or at least 4.5:1, or at least 4.75:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 13:1, or at least 15:1, or at least 17:1, based on the weight of the r-pyrolysis oil.

[0450] In one embodiment or in combination with any of the embodiments mentioned herein or in combination with any of the embodiments mentioned herein, the weight ratio of the combination of paraffins and cycloalkanes to aromatics can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.5:1, or at least 5:1, or at least 7:1, or at least 10:1, or at least 15:1, or at least 20:1, or at least 25:1, or at least 30:1, or at least 35:1, or at least 40:1, based on the weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the ratio of the combination of paraffins and cycloalkanes to aromatics in the r-pyrolysis oil can be in the range of 50:1-1:1, or 40:1-1:1, or 30:1-1:1, or 20:1-1:1, or 30:1-3:1, or 20:1-1:1, or 20:1-5:1, or 50:1-5:1, or 30:1-5:1, or 1:1-7:1, or 1:1-5:1, 1:1-4:1, or 1:1-3:1.

[0451] 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, the x weight percentage of the composition boils at the boiling point.

[0452] 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.

[0453] 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.

[0454] In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed stream may comprise a predominantly C 2 -C 4 The composition of hydrocarbons, or mainly containing C 5 -C 22 As used herein, the term "mainly C 2 -C 4 "Hydrocarbon" means a hydrocarbon containing at least 50 weight percent of C 2 -C 4 A stream or combination of hydrocarbon components. 2 -C 4The example of the concrete type of hydrocarbon stream or composition comprises propane, ethane, butane and LPG.In one embodiment or with any embodiment combination mentioned herein, cracker feed can comprise 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, based on the gross weight of feed, wt.%, and / or be no more than 100, or be no more than 99, or be no more than 95, or be no more than 92, or be no more than 90, or be no more than 85, or be no more than 80, or be no more than 75, or be no more than 70, or be no more than 65, or be no more than 60, in each case, be C2-C4 hydrocarbon or linear alkane weight percentage, based on the gross weight of feed. Cracker feed can comprise mainly propane, mainly ethane, mainly butane or the combination of two or more of these components.These components can be non-recovery components. The cracker feed may comprise primarily 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 recycled streams mixed with the fresh feed). The cracker feed may comprise HD5 quality propane as the original 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-recycled components.

[0455] In one embodiment or in combination with any embodiment described herein, the cracker feed stream may comprise a predominantly C 5 -C 22 As used herein, "mainly C 5 -C 22 "Hydrocarbon" means a hydrocarbon containing at least 50 weight percent of C 5 -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 C 5 -C 22 , or C 5 -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.

[0456] 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.

[0457] 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.

[0458] 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.

[0459] 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.

[0460] In one embodiment or in combination with any embodiment mentioned herein 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 is operated 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 or in combination with any mentioned embodiment, the gas coil may receive a feed that is primarily C 2 -C 4 The raw material or mainly C 2 -C 3The gas furnace may have more than one gas coil. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, at least 25% of the coils in the convection zone or in the convection box of the furnace, or at least 50% of the coils, or at least 60% of the coils, or all of the coils are gas coils. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the gas coil receives a vapor-phase feed at the coil inlet at the inlet of the convection zone, in which at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is vapor.

[0461] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil is cracked in a cracking furnace. The cracking furnace is a gas furnace. The cracking furnace comprises at least one gas coil and at least one liquid coil in the same furnace, or in the same convection section, 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 section ("liquid coil"). In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, 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 or in combination with any mentioned embodiment, the liquid coil can receive mainly C 6 -C 22 The raw material or mainly C 7 -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 or in combination with any mentioned embodiment, at least one coil in the convection zone or in the convection box of the furnace and not more than 75% of the coils, or not more than 50% of the coils, or not more than at least 40% of the coils are liquid coils. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the liquid coil receives a vapor phase feed at the coil inlet at the inlet of the convection zone, in which liquid phase feed at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is liquid.

[0462] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil is cracked in a thermal gas cracker.

[0463] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil is cracked in the presence of steam in a hot steam gas cracker. Steam cracking refers to the high temperature cracking (decomposition) of hydrocarbons in the presence of steam.

[0464] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-composition is derived directly or indirectly from cracking r-pyrolysis oil in a gas furnace. The coils in the gas furnace can consist entirely of gas coils, or the gas furnace can be a cracking furnace.

[0465] 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.

[0466] 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.

[0467] In one embodiment or combination of any of the mentioned embodiments, there is provided a method for preparing one or more olefins, comprising:

[0468] (a) feeding a first cracker feed comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to a cracker furnace;

[0469] (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

[0470] (c) cracking said first and said second cracker feeds in respective first and second tubes to form olefin-containing effluent streams.

[0471] 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.

[0472] 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.%.

[0473] 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.

[0474] The second cracker stream may contain no r-pyrolysis oil or contain less r-pyrolysis oil (by weight) than the first cracker feed stream. In addition, the second cracker stream may contain only non-recycled cracker feed in the second coil or tube. The second cracker feed stream may be primarily C 2 To C 4 , 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 at least 10%, 20, 30, 40, 50, 60, 70, 80, 90, 95, 97 or 99% less by weight than the amount of r-pyrolysis oil in the first cracker feed.

[0475] In one embodiment or in combination with any embodiment described herein or in combination with any mentioned embodiment, although not shown, an evaporator may be provided to evaporate C 2 -C 5 The condensed feed of hydrocarbons 350 ensures 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.

[0476] 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.

[0477] 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.

[0478] 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.

[0479] 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.

[0480] 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.

[0481] A single furnace may have at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8 or more, in each case, a coil. Each coil may be 5 to 100, 10 to 75, or 20 to 50 meters long and may include at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 10, or at least 12, or at least 14 or more tubes. The tubes of a single coil may be arranged in many configurations and, in one embodiment or in combination with any of the embodiments mentioned herein, may be connected by one or more 180° ("U" shaped) bends. Figure 6 One example of a furnace coil 410 having a plurality of tubes 420 is shown in FIG.

[0482] The olefin plant can have a single cracking furnace, or it can have at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8 or more cracking furnaces operating in parallel. Any one or each furnace can be a gas cracker or a liquid cracker or a cracking furnace. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the furnace is a gas cracker that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, or at least 90 wt.% of ethane, propane, LPG, or a combination thereof, based on the weight of all cracker feeds to the furnace. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, 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 or in combination with any mentioned embodiment, 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.

[0483] Now turn to Figure 7 , showing several possible locations for introducing the feed stream containing r-pyrolysis oil and the non-recovery cracker feed stream into the cracking furnace.

[0484] In one embodiment or in combination with any embodiment mentioned herein, the feed stream 550 containing r-pyrolysis oil can be combined with the non-recovery cracker feed 552 upstream of the convection section to form a combined cracker feed stream 554, which can then be introduced into the convection section 510 of the furnace. Alternatively or additionally, the feed 550 containing r-pyrolysis oil can be introduced into the first furnace coil, while the non-recovery cracker feed 552 is introduced into a separate or second furnace coil, in the same furnace or in the same convection zone. The two streams can then travel parallel to each other through the convection section 510, the crossover 530, and the radiant section 520 in the radiant box 522, so that each stream is substantially fluidly isolated from the other stream over most or all of the path of travel from the inlet to the outlet of the furnace. The pyrolysis stream introduced into any heating zone in the convection section 510 can flow through the convection section 510 and flow into the radiant box 522 as the vaporized stream 514b. In other embodiments, the feed stream 550 containing r-pyrolysis oil may also be introduced into the non-recovery cracker stream 552 as it flows through the furnace coils in the convection section 510 into the cross section 530 of the furnace to form the combined cracker stream 514a, also as shown in FIG. Figure 7 as shown in .

[0485] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, 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 embodiment mentioned herein or in combination with any of the mentioned embodiments, 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.

[0486] 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.

[0487] 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.

[0488] 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.

[0489] 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.

[0490] 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.

[0491] 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.

[0492] When combined with steam and fed into or near the inlet of convection section 510, the r-pyrolysis oil and / or cracker stream may have a temperature of at least 30, 35, 40, 45, 50, 55, 60 or 65, and / or no more than 100, 90, 80, 70, 60, 50 or 45°C.

[0493] 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, the steam may be used in the same furnace ( Figure 7 Steam 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.

[0494] 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:

[0495] (a) feeding a first cracker stream having r-pyrolysis oil to a first tube inlet in a cracker furnace;

[0496] (b) Containing or mainly containing C 2 -C 4 A second cracker stream of hydrocarbons is fed 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.

[0497] 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., C 2 -C 4 or C 5 -C 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 stream containing r-pyrolysis oil or the first cracker stream and in the second cracker stream or the non-recovery stream, the total molar flow rate of the stream containing r-pyrolysis oil or the first cracker stream (including r-pyrolysis oil and dilution steam) may be at least 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55 or 60% higher than the total molar flow rate (including hydrocarbons and dilution steam) of the non-recovery cracker feed or the second cracker stream (where the percentage is calculated as the difference between the two molar flow rates divided by the flow rate of the non-recovery stream).

[0498] 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., C 2 -C 4 or C 5 -C 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

[0499] 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.

[0500] 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.

[0501] In one embodiment or in combination with any of the embodiments mentioned herein, the temperature of the stream containing r-pyrolysis oil as it passes through the crossover section in the cracking furnace can be different from the temperature of the non-recovery cracker feed as it passes through the crossover section when the streams are introduced separately and passed through the furnace. For example, the temperature of the r-pyrolysis oil stream as it passes through the crossover section can be different from the temperature of the non-recovery hydrocarbon stream (e.g., C pyrolysis oil) as it passes through the crossover section in another coil. 2 -C 4 or C 5 -C 22 ) differs by at least 0.01, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75%. This percentage can be calculated based on the temperature of the non-recycled stream according to the following formula:

[0502] [(r - temperature of pyrolysis oil stream - temperature of non-recovery cracker stream)] / (temperature of non-recovery cracker steam), expressed as a percentage.

[0503] 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.

[0504] 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.

[0505] 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.

[0506] 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).

[0507] 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.

[0508] 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.

[0509] 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 C 2 -C 4 The combined cracker stream can have a vapor fraction of at least 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 0.99 by weight or, in one embodiment or in combination with any of the mentioned embodiments, by volume.

[0510] 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.

[0511] 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 .

[0512] 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.

[0513] 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 a predominantly C 5 -C 22 The hydrocarbon stream or C 2 -C 4 The hydrocarbon stream combination is introduced into the cross section or radiation zone pipe 624 after separation.

[0514] 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.

[0515] The heated cracker stream typically has a temperature of at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case ° C, and / or no more than 850, or no more than 840, or no more than 830, or no more than 820, or no more than 810, or no more than 800, or no more than 790, or no more than 780, or no more than 770 , or not more than 760, or not more than 750, or not more than 740, or not more than 730, or not more than 720, or not more than 710, or not more than 705, or not more than 700, or not more than 695, or not more than 690, or not more than 685, or not more than 680, or not more than 675, or not more than 670, or not more than 665, or not more than 660, or not more than 655°C, or not more than 650°C, in each case °C, or in the range of 500 to 710°C, 620 to 740°C, 560 to 670°C, or 510 to 650°C, and then may pass from the convection section 610 of the furnace via the crossover section 630 to the radiant section 620. In one embodiment or in combination with any embodiment mentioned herein, the feed stream 550 containing r-pyrolysis oil may be added to the cracker stream at the crossover section 530, such as Figure 6When introduced into the furnace at the intersection, the r-pyrolysis oil may be at least partially vaporized or atomized before being combined with the cracker stream at the intersection. The temperature of the cracker stream passing through the intersection 530 or 630 may be at least 400, 425, 450, 475, or at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case ° C, and / or no more than 850, or no more than 840, or no more than 830, or no more than 820, or no more than 8 70, or not more than 760, 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, or 510 to 630°C.

[0516] 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.

[0517] 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.

[0518] 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:

[0519] [(measured value of the operating parameter) - (target value of the operating parameter)] / [(target value of the operating parameter)], expressed as a percentage.

[0520] As used herein, the term "different" means higher or lower.

[0521] 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.

[0522] 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:

[0523] [(measured value of the operating parameter) - (target value of the operating parameter)] / [(target value of the operating parameter)], expressed as a percentage.

[0524] 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.

[0525] 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:

[0526] [(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.

[0527] 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.

[0528] 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:

[0529] [(r - 50% boiling point of pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0530] 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.

[0531] 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.

[0532] 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.

[0533] In one embodiment or in combination with any of the mentioned embodiments, there is provided a process for preparing one or more olefins by:

[0534] (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit;

[0535] (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

[0536] (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.

[0537] The reason or cause of the temperature drop of the second coil outlet temperature (COT2) is not limited, as long as COT2 is lower than the first coil outlet temperature (COT1). In one embodiment or in combination with any of the mentioned embodiments, in one embodiment or in combination with any of the 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).

[0538] In the set mode, COT2 can be set to be at least 5°C lower than COT1. All coils in the furnace can be a feed stream containing r-pyrolysis oil, or at least 1, or at least two coils can be a feed stream containing r-pyrolysis oil. In either case, at least one of the r-pyrolysis oil coils can be in the set mode. By reducing the cracking severity of the combined cracking stream, when its average number average molecular weight is higher than that of the cracker feed stream, such as gaseous C 2 -C 4 When feeding, the lower thermal energy required for cracking r-pyrolysis oil can be utilized. 2 -C 4 ) can reduce the cracking severity, thereby increasing the unconverted C 2 -C 4 The amount of feed in a single pass, but requires a higher amount of unconverted feed (e.g. C 2 -C 4 feed), by making the unconverted C 2 -C 4 The feed is recycled through the furnace, increasing the final yield of olefins such as ethylene and / or propylene in multiple passes. Alternatively, other cracker products such as aromatics and diene content may be reduced.

[0539] 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.

[0540] In set mode, the temperature can be fixed or set by adjusting the furnace to burner fuel ratio.

[0541] In one embodiment or in combination with any of the other mentioned embodiments, COT2 is in free floating mode and is the temperature of the coils of the pyrolysis oil feed due to feeding pyrolysis oil and allowing COT2 to rise or fall without fixing it. In this embodiment, not all coils contain r-pyrolysis oil. The thermal energy provided to the coils containing r-pyrolysis oil can be provided by maintaining a constant temperature of the burners on the coils containing non-recovered cracker feed or the fuel feed rate. Without fixing or setting COT2, when pyrolysis oil is fed to the cracker stream to form a combined cracker stream having a higher hydrocarbon mass flow rate than the hydrocarbon mass flow rate of the cracker stream in step (a), COT2 can be lower than COT1. Adding pyrolysis oil to the cracker feed to increase the hydrocarbon mass flow rate of the combined cracker feed reduces COT2 and can exceed the warming effect of using a higher average molecular weight pyrolysis oil. These effects can be seen while other cracker conditions are kept constant, such as the dilution steam ratio, feed location, composition of cracker feed and pyrolysis oil, and fuel feed rate to the combustor burners in the furnace on tubes containing only cracker feed and no r-pyrolysis oil feed.

[0542] 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.

[0543] 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 combined feed of a pyrolysis oil feed and a pyrolysis oil in operation. Step (b) can be the first time the furnace receives a pyrolysis oil feed or a combined cracker feed containing pyrolysis oil. In one embodiment or in combination with any of the other mentioned embodiments, steps (a) and (b) may be repeated multiple times per year, such as at least 2x / yr, or at least 3x / yr, or at least 4x / yr, or at least 5x / yr, or at least 6x / yr, or at least 8x / yr, or at least 12x / yr, as measured on a calendar year. Formulating the feed of pyrolysis oil represents multiple cycles of steps (a) and (b). When the feed supply of pyrolysis oil is exhausted or shut off, COT1 is allowed to reach a steady-state temperature before engaging step (b).

[0544] Alternatively, the feeding of pyrolysis oil to the cracker feed may be continued throughout the course of at least 1 calendar year or at least 2 calendar years.

[0545] 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.

[0546] 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.

[0547] 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:

[0548] (a) cracking a cracker stream at a first hydrocarbon mass flow rate (MF1) in a cracking unit;

[0549] (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

[0550] (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.

[0551] 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.

[0552] 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:

[0553]

[0554] Among them, mf1 is the combined production of propylene and ethylene content in the cracker effluent without using MF1 made with r-pyrolysis oil; mf2 is the combined production of propylene and ethylene content in the cracker effluent at MF2 made using r-pyrolysis oil.

[0555] 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:

[0556]

[0557] Wherein, O% is the percentage increase (using the above formula) 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; and

[0558] ΔMF% is the percentage of increase of MF2 compared to MF1.

[0559] 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:

[0560]

[0561] Where E mf1 is the combined wt.% of propylene and ethylene content in the cracker effluent under MF1 produced without using r-pyrolysis oil; E mf2 is the combined wt.% of propylene and ethylene content in the cracker effluent at MF2 made using r-pyrolysis oil.

[0562] Also provided is a method for preparing one or more olefins, the method comprising:

[0563] (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);

[0564] (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

[0565] (c) cracking the combined cracker stream in the cracking unit to provide a second olefin-containing effluent exiting the cracking furnace at a second coil outlet temperature (COT2), wherein when the r-pyrolysis oil is heavier than the cracker stream, COT2 is equal to or less than COT1, and wherein when the r-pyrolysis oil is lighter than the cracker stream, COT2 is greater than or equal to COT1.

[0566] In this method, the above embodiments are also applicable here for COT2 which is lower than COT1. COT2 can be in set mode or free floating mode. In one embodiment or in combination with any other mentioned embodiment, COT2 is in free floating mode, and the hydrocarbon mass flow rate of the combined cracker stream in step (b) is higher than the hydrocarbon mass flow rate of the cracker stream in step (a). In one embodiment or in combination with any mentioned embodiment, COT2 is in set mode.

[0567] In one embodiment or in combination with any of the mentioned embodiments, there is provided a process for preparing one or more olefins by:

[0568] (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit;

[0569] (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

[0570] (c) cracking the combined cracker stream in the cracking unit at a second coil outlet temperature (COT2), wherein the second coil outlet temperature is higher than the first coil outlet temperature.

[0571] 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.

[0572] 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.

[0573] 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:

[0574] (i) Lower thermal energy is required to crack the pyrolysis oil in the combined stream.

[0575] (ii) Exothermic reactions occur in the cracking products of the pyrolysis oil, such as the diels-alder reaction.

[0576] 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.

[0577] 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. A higher second coil outlet temperature (COT2) can help to reduce the unconverted lighter cracker feed (e.g., C 2 -C 4feed) and reduced throughput, which can contribute to downstream capacity-constrained fractionators.

[0578] 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.

[0579] 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).

[0580] 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.

[0581] 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.

[0582] 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.

[0583] 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 having 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.

[0584] 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:

[0585]

[0586] Where E is the propylene:ethylene ratio in the cracker effluent produced without using r-pyrolysis oil, in wt.%; E r is the propylene:ethylene ratio in the cracker effluent prepared using r-pyrolysis oil, in wt.%.

[0587] In one embodiment or in combination with any of the embodiments mentioned herein, the amount of ethylene and propylene in the cracked olefin-containing effluent stream can remain essentially unchanged or increase relative to an effluent stream without r-pyrolysis oil. Surprisingly, liquid r-pyrolysis oil can be fed to a gas feed furnace that receives and cracks a predominantly C 2 -C 4 Composition and obtain an olefin-containing effluent stream, which can be in some cases relative to C without r-pyrolysis oil 2 -C 4 The cracker feed remains essentially unchanged or improved. The high molecular weight of r-pyrolysis oil can contribute mainly to the formation of aromatic hydrocarbons, and only a small amount participates in the formation of olefins (especially ethylene and propylene). However, we have found that at the same hydrocarbon mass flow rate, 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, and even the output, does not decrease significantly, and in many cases remains the same or may increase. The olefin-containing effluent stream may have a total wt.% of propylene and ethylene, which is equal to or higher than the propylene and ethylene content of the effluent stream obtained by cracking the same cracker feed but without r-pyrolysis oil by at least 0.5%, or at least 1%, or at least 2%, or at least 2.5%, as determined as follows:

[0588]

[0589] wherein E is the combined wt.% of propylene and ethylene content in the cracker effluent produced without using r-pyrolysis oil; Er is the combined wt.% of propylene and ethylene content in the cracker effluent produced with using r-pyrolysis oil.

[0590] 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.

[0591] 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.

[0592] 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.

[0593] 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%.

[0594] 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.

[0595] 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.

[0596] In one embodiment or in combination with one or more embodiments mentioned herein, the propane:(ethylene and propylene) ratio in the olefin-containing effluent is reduced as the r-pyrolysis oil is added 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. Low ratios represent that high amounts of ethylene+propylene can be achieved or maintained while correspondingly reducing unconverted products such as propane.

[0597] 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:

[0598]

[0599] where Ei is the C in the olefin-containing cracker effluent prepared by introducing r-pyrolysis oil at the inlet of the convection box. 6+ Ed is the C content of the olefin-containing cracker effluent obtained by introducing pyrolysis oil and steam downstream of the convection box inlet. 6+ content.

[0600] 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 paraffins and cyclic compounds having a carbon number of 6 or more. As used throughout the text, the amount of aromatic hydrocarbons referred to can be determined by C 6+ The amount of substance is expressed because the amount of aromatic hydrocarbons will not exceed C 6+ The amount of substance.

[0601] 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, 28:1 1, 20:1, 15:1, 10:1, or 5:1 weight ratio of olefins to aromatics. As used herein, "olefins to aromatics" are C 2 and C 3 In one embodiment or in combination with any embodiment mentioned herein, the effluent stream can have a ratio of at least 2.5:1, 2.75:1, 3.5:1, 4.5:1, 5.5:1, 6.5:1, 7.5:1, 8.5:1, 9.5:1, 10.5:1, 11.5:1, 12.5:1, or 13:5:1 of olefins to aromatics.

[0602] 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 and aromatics" are C 2 and C 3 The ratio of the total weight of olefins to the total weight of aromatics.

[0603] 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.

[0604] 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.

[0605] 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.

[0606] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent taken out from the cracking furnace of the composition containing 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 at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85% higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without r-pyrolysis oil treatment. The total amount 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 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 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:

[0607]

[0608] Where E is the wt.% of the components in the cracker effluent produced without using r-pyrolysis oil; E r is the wt.% of the components in the cracker effluent made with r-pyrolysis oil.

[0609] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream may contain acetylene. The amount of acetylene may be at least 2000ppm, at least 5000ppm, at least 8000ppm, or at least 10,000ppm, based on the total weight of the effluent stream from the furnace. It may also be no more than 50,000ppm, no more than 40,000ppm, no more than 30,000ppm, or no more than 25,000ppm, or no more than 10,000ppm, or no more than 6,000ppm, or no more than 5000ppm.

[0610] 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.

[0611] 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 dio...

Claims

1. A method for treating a pyrolysis recovery component alcohol composition pr-ROH derived directly or indirectly from pyrolysis recovery waste, the method comprising feeding the pr-ROH to a reactor in which mixed esters are prepared to obtain a pyrolysis recovery component mixed ester composition, in, The recycled waste is selected from: high-density polyethylene, low-density polyethylene, polypropylene, polystyrene, other polyolefins other than the above, and any combination thereof, wherein the recycled waste is pyrolyzed to produce recycled pyrolysis oil, i.e., r-pyrolysis oil, and the recycled waste derived from pyrolysis includes cracking of the r-pyrolysis oil to produce olefins, including ethylene or propylene, and the ethylene or propylene is used to prepare the pr-ROH and further produce the pyrolysis recycled component mixed ester, wherein The r-pyrolysis oil is not hydrotreated before the cracking, The cracker for carrying out said cracking is a gas furnace capable of tolerating a wide range of hydrocarbon counts in the pyrolysis oil feedstock, thereby avoiding the necessity of subjecting the pyrolysis oil feedstock to separation techniques to deliver smaller or lighter hydrocarbon fractions to the cracker, In the radiant section of the cracker, a 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 furnace coil 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°C and not more than 850°C, The r-pyrolysis oil-containing feed stream comprises at least 50 wt.% C2-C3 hydrocarbons and at least 5 wt.% and no more than 50 wt.% r-pyrolysis oil, based on the total weight of the feed stream.

2. A method for preparing a recycled content mixed ester composition r-EC, the method comprising reacting an alcohol composition ROH with an acid to produce a mixed ester effluent comprising r-EC, wherein at least a portion of the alcohol composition is directly or indirectly derived from pyrolysis recycled waste, the alcohol composition being a pyrolysis recycled content alcohol composition pr-ROH, in, The recycled waste is selected from: high-density polyethylene, low-density polyethylene, polypropylene, polystyrene, other polyolefins other than the above, and any combination thereof, wherein the recycled waste is pyrolyzed to produce recycled pyrolysis oil, i.e., r-pyrolysis oil, wherein the pyrolysis of the recycled waste is derived from cracking the r-pyrolysis oil to produce olefins, wherein the olefins include ethylene or propylene, and the ethylene or propylene is used to prepare the pr-ROH and further produce the pyrolysis recycled component mixed ester, wherein The r-pyrolysis oil is not hydrotreated before the cracking, The cracker for carrying out said cracking is a gas furnace capable of tolerating a wide range of hydrocarbon counts in the pyrolysis oil feedstock, thereby avoiding the necessity of subjecting the pyrolysis oil feedstock to separation techniques to deliver smaller or lighter hydrocarbon fractions to the cracker, In the radiant section of the cracker, a 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 furnace coil 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°C and not more than 850°C, The r-pyrolysis oil-containing feed stream comprises at least 50 wt.% C2-C3 hydrocarbons and at least 5 wt.% and no more than 50 wt.% r-pyrolysis oil, based on the total weight of the feed stream.

3. A method of preparing a mixed ester, the method comprising a mixed ester manufacturer, i.e., an EC manufacturer or one of its family of entities: a. Obtaining an alcohol composition ROH from a supplier, and: i. also obtain a quota of pyrolysis recovery components from the supplier, or ii. receiving a pyrolysis recovery component quota from any person or entity without supplying an alcohol composition from the person or entity that transferred the pyrolysis recovery component quota; and b. depositing at least a portion of the pyrolysis recovery quota obtained in step a(i) or step a(ii) into a recovery inventory, and c. preparing a mixed ester composition EC from any alcohol composition obtained from any source; in, The pyrolysis recovery component quota comprises a quota derived from the cracking of r-pyrolysis oil, wherein: The r-pyrolysis oil is obtained by pyrolyzing recycled waste, wherein the recycled waste is selected from: high-density polyethylene, low-density polyethylene, polypropylene, polystyrene, other polyolefins other than the above, and any combination thereof, r- Cracking of pyrolysis oil produces olefins including ethylene or propylene, The r-pyrolysis oil is not hydrotreated before the cracking, The cracker for carrying out said cracking is a gas furnace capable of tolerating a wide range of hydrocarbon counts in the pyrolysis oil feedstock, thereby avoiding the necessity of subjecting the pyrolysis oil feedstock to separation techniques to deliver smaller or lighter hydrocarbon fractions to the cracker, In the radiant section of the cracker, a 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 furnace coil 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°C and not more than 850°C, The r-pyrolysis oil-containing feed stream comprises at least 50 wt.% C2-C3 hydrocarbons and at least 5 wt.% and no more than 50 wt.% r-pyrolysis oil, based on the total weight of the feed stream.

4. The method according to claim 2 or 3, wherein: The olefin, alcohol composition or mixed ester composition is derived directly or indirectly from pyrolysis recovery waste, or alternatively is derived from cracked r-pyrolysis oil or obtained from r-pyrolysis gas.

5. The method according to claim 2 or 3, wherein: The olefin, alcohol composition or mixed ester composition is derived directly or indirectly from cracking r-pyrolysis oil in a gas furnace.

6. The method according to claim 2 or 3, wherein: The mixed esters composition has associated therewith, or contains, or is labeled, or certified as containing, a recycled component in an amount of at least 0.01 wt. %, based on the weight of the mixed esters composition.

7. The method according to claim 2 or 3, wherein: The recycled content value is applied to the mixed ester composition EC to produce the recycled content mixed ester composition r-EC by subtracting the recycled content value from the recycled stock or by reacting the recycled content alcohol r-ROH.

8. The method according to claim 2 or 3, wherein: A method for allocating recycled content between products manufactured by an EC manufacturer or by any one entity or combination of entities in a family of entities of which the EC manufacturer is a part, with a symmetrical distribution of recycled content values ​​between its products, and optionally at least one of the products is a mixed ester composition EC.

9. The method according to claim 2 or 3, wherein: A method for allocating recycled content between products manufactured by an EC manufacturer or by any one entity or combination of entities in a family of entities of which the EC manufacturer is a part, wherein the recycled content value is asymmetrically distributed between its products, and optionally at least one of the products is a mixed ester composition EC.

10. The method according to claim 2 or 3, wherein: The ROH supplier transfers the recycling component quota to the EC manufacturer and transfers the ROH supply to the EC manufacturer.

11. The method according to claim 10, wherein: The reclaim component quota is not associated with the supplied ROH.

12. The method according to claim 2 or 3, wherein: The ROH supplier transfers the recycled content quota to the EC manufacturer and transfers the supply of ROH to the EC manufacturer, and the recycled content quota is associated with the ROH produced by the supplier.

13. The method according to claim 12, wherein: The supplied ROH is r-ROH, and at least a portion of the recycled component quota transferred is recycled components in the supplied r-ROH.

14. The method according to claim 3, wherein: The EC manufacturer deposits the allowance into recycling stock.

15. The method according to claim 3, wherein: Any person or entity in the EC Manufacturer or its family of entities: a. Deposit the quota into the recycling stock and store it; or b. depositing the quota into a recycled stock and applying the recycled content value from the recycled stock to products other than ECs manufactured by the EC manufacturer, or c. sell or transfer allowances from said recycling stock, said allowances acquired as described above being deposited into said recycling stock, or d. Apply the recycled content value taken from the recycled stock to the EC.

16. The method according to claim 15, wherein: The recycled content value applied to the EC taken from the recycled stock is derived directly or indirectly from the pyrolysis of the recycled waste.

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