Cellulose esters comprising recovered component butyryl groups

Abstract

A recovery component cellulose ester and a process for preparing a recovery component cellulose ester, wherein the recovery component is derived directly or indirectly from the cracking of recovery component pyrolysis oil and / or gas. The cracking of the pyrolysis oil may be carried out in a gas furnace or a cracking furnace.

Description

[0001] This application is a divisional application of the invention patent application with a priority date of November 7, 2019, an application date of November 6, 2020, an application number of 202080077510.2, and an invention name of "Cellulose ester containing recycled butyryl components". Background Art

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

[0003] To maximize recycling efficiency, it is desirable for large-scale production facilities to be able to process feedstock with recycled content derived from a variety of waste materials. Some recycling efforts involve complex and detailed separation of waste streams, which results in increased costs to obtain recycled waste content from the stream. It is desirable to create recycled content without the need to sort it into a single type of plastic or waste material, or to tolerate a variety of impurities in the waste stream.

[0004] In some cases, it may be difficult to dedicate a product with recycled content to a specific customer or downstream synthesis process for use in making derivatives of the product, particularly if the recycled content product is a gas or difficult to separate. Because gas infrastructure is continuous flow and often mixes gas streams from a variety of sources, separating and allocating a dedicated portion of the gas made specifically from recycled content feedstock can be difficult.

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

[0006] Cellulose esters are used in many commercial products on the market today. Moreover, since the backbone of the molecule is cellulose, cellulose ester is a renewable material. However, the organic acid groups attached to the cellulose backbone that make it an ester and affect the material's properties are usually made from fossil fuels such as oil, natural gas, and coal.

[0007] It would also be desirable to synthesize compounds such as organic acids and aldehydes (eg, for making cellulose esters) using existing equipment and processes without having to invest in additional expensive equipment to build in recycled content into the production of the compounds.

[0008] It is desirable to be able to determine the amount and time of creating recycled content in compounds such as organic acids and aldehydes. Furthermore, it may be desirable to provide organic acids and aldehydes with more or less recycled content or no recycled content at certain times or for different batches. The flexibility of this approach without the need to add significant assets is desirable. Summary of the invention

[0009] Now provided is a method for obtaining a recycled cellulose ester composition, a method for reacting a recycled acid or aldehyde or applying recycled values ​​to produce a recycled cellulose ester, its use, its composition, and its system, which are further described in detail in the claims and the specification, respectively. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] 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).

[0011] 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.

[0012] Figure 3 is a schematic diagram of a pyrolysis process to produce an olefin-containing product.

[0013] 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.

[0014] Figure 5 is a schematic diagram of a cracking furnace suitable for receiving r-pyrolysis oil.

[0015] Figure 6 A furnace coil configuration with multiple tubes is shown.

[0016] Figure 7 Various feed positions of r-pyrolysis oil into the cracking furnace are shown.

[0017] Figure 8 A cracking furnace with a vapor liquid separator is shown.

[0018] Fig. 9 is a block diagram showing the process of recovering constituent furnace effluent.

[0019] 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.

[0020] Fig.11 A laboratory scale cracking unit design is shown.

[0021] Fig.12 Design features for a plant-based experimental feeding of r-pyrolysis oil to a gas-fed cracking furnace are described.

[0022] 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.

[0023] Fig.14 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0024] Fig.15 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0025] Fig.16 The boiling point curve of r-pyrolysis oil obtained by distillation in the laboratory and chromatography analysis.

[0026] Fig.17 is a boiling point graph of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350°C, 50% boils between 95°C and 200°C, and at least 10% boils at 60°C.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] Fig. 22 is a boiling point graph of r-pyrolysis oil distilled in the laboratory with 34.7% aromatic content.

[0032] Fig.23 is a boiling point graph of r-pyrolysis oil having an initial boiling point of about 40°C.

[0033] Fig.24 is a graph of the carbon distribution of the pyrolysis oil used in the plant experiments.

[0034] Fig.25 is a plot of the cumulative weight percent carbon distribution of the pyrolysis oil used in the plant experiments.

[0035] Fig.26 is a schematic diagram showing a schematic process flow of how to prepare r-CE using r-propylene. DETAILED DESCRIPTION

[0036] 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.

[0037] In these aspects, a process for preparing recovered cellulose ester ("r-CE") is configured to begin by feeding a recycled component cellulose reactant composition ("pr-CR") to a reactor to produce a cellulose ester effluent comprising r-CE, wherein at least a portion of the recycled component cellulose reactant composition is directly or indirectly derived from pyrolysis of recycled waste.

[0038] Pyrolysis / cracking systems and methods

[0039] 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.

[0040] As used herein, "containing" and "including" are open ended and synonymous with "comprising."

[0041] 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.

[0042] As used herein, "recycled content composition," "recycled composition," and "r-composition" refer to a composition having recycled content.

[0043] 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.

[0044] 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.

[0045] As used herein, a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "directly derived" or "derived directly" from recycled waste has at least one physical component traceable to recycled waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from recycled waste has a recycled component quota associated with it and may or may not contain physical components traceable to recycled waste.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] As used herein, "pyrolysis gas" and "pyrolysis gas ("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.

[0050] 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.

[0051] As used herein, "Et" is the ethylene component (eg, feedstock, product, or stream), and "Pr" is the propylene component (eg, feedstock, product, or stream).

[0052] 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.

[0053] 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.

[0054] As used herein, "AD" is an aldehyde derivative composition (eg, feedstock, product, or stream), such as a butyraldehyde composition.

[0055] As used herein, "recovered content aldehyde derivative" and "r-AD" refer to an aldehyde derivative having a recovered content, such as butyraldehyde.

[0056] As used herein, "recycled content butyraldehyde" and "r-butyraldehyde" refer to butyraldehyde having a recycled content.

[0057] As used herein, "pyrolysis-recovered component aldehyde derivative" and "pr-AD" refer to r-AD having a pyrolysis-recovered component.

[0058] As used herein, "cellulose reactant" or "CR" refers to a reactant that reacts with cellulose, for example, a carboxylic acid such as butyric acid or an anhydride such as butyric anhydride.

[0059] As used herein, "recycled content cellulose reactant" or "r-cellulose reactant" or "r-CR" refers to a cellulose reactant having recycled content.

[0060] As used herein, "pr-cellulose reactant" or "pr-CR" refers to a cellulose reactant having a pyrolysis recovery component.

[0061] As used herein, "CA" is a carboxylic acid composition (eg, feedstock, product, or stream).

[0062] As used herein, "recycled content carboxylic acid" or "r-CA" refers to CA having recycled content.

[0063] As used herein, "recycled content butyric acid" or "r-butyric acid" refers to butyric acid having a recycled content.

[0064] As used herein, "pyrolysis component carboxylic acid" or "pr-CA" refers to r-CA having a pyrolysis recovered component.

[0065] As used herein, "AA" is an anhydride composition (eg, feedstock, product, or stream).

[0066] As used herein, "recycled content anhydride" and "r-AA" refer to AA having a recycled content.

[0067] As used herein, "recycled content butyric anhydride" and "r-butyric anhydride" refer to butyric anhydride having a recycled content.

[0068] As used herein, "pyrolysis component anhydride" and "pr-AA" refer to r-AA having a pyrolysis recovered component.

[0069] As used herein, "CE" is a cellulose ester composition (eg, feedstock, product, or stream) in which the cellulose ester is substituted.

[0070] As used herein, "recycled content cellulose ester" and "r-CE" refer to CE having recycled content.

[0071] As used herein, "recycled content cellulose acetate butyrate" and "r-CAB" refer to cellulose acetate butyrate having recycled content.

[0072] As used herein, "pyrolyzed component cellulose ester" and "pr-CE" refer to r-CE having a pyrolyzed recovered component.

[0073] 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, "CE" or "any CE" may include cellulose esters prepared by any method, and may or may not include recycled components, and may or may not be prepared from non-recycled component raw materials or from recycled component raw materials, and may or may not include r-CE or pr-CE. Similarly, r-CE may include or exclude pr-CE, although reference to r-CE does require it to have recycled components. In another example, "Pr" or "any Pr" may include propylene prepared by any method, and may or may not have recycled components, and may or may not include r-Pr or pr-Pr. Similarly, r-Pr may include or exclude pr-Pr, although reference to r-Pr does require it to have recycled components.

[0074] "Pyrolytic recycled content" is a specific subset / type (kind) of "recycled content" (genus). Wherever "recycled content" and "r-" are used herein, such usage 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 cellulose ester" or "r-CE" is used herein, it should be interpreted as also explicitly disclosing and providing claim support for "pyrolytic recycled content cellulose ester" and "pr-CE".

[0075] 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.

[0076] 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.

[0077] 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.

[0078] In one embodiment or in combination with any other mentioned embodiment, reference to r-Pr also includes pr-Pr, or pr-Pr obtained directly or indirectly from cracking of r-pyrolysis oil or from r-pyrolysis gas; and r-CE also includes pr-CE, or pr-CE obtained directly or indirectly from cracking of r-pyrolysis oil or from r-pyrolysis gas.

[0079] In one embodiment or in combination with any of the mentioned embodiments, a method for preparing an r-CE composition by reacting CR (e.g., a CR composition) with cellulose or a cellulose ester (a cellulose composition, such as cellulose acetate) is provided. CR may be r-CR or pr-CR or dr-CR. In one embodiment, the method for preparing r-CE starts with feeding r-CR to a reactor for preparing CE. In an embodiment, the CR composition may be made by first reacting syngas (CO and hydrogen) with Pr (forming an aldehyde derivative), and then reacting the aldehyde derivative with oxygen (forming a carboxylic acid); or reacting CO and water with Pr (directly forming a carboxylic acid). In certain embodiments, CR may be prepared by reacting a carboxylic acid with another anhydride to form the desired anhydride (e.g., butyric acid reacts with acetic anhydride to form butyric anhydride) by transesterification. Pr may be r-Pr or pr-Pr or dr-Pr. In one embodiment, CR is r-CR prepared by feeding r-Pr to a reactor for making CR. In certain embodiments, CR may be prepared by a reaction scheme that may also include reacting an anhydride with oxygen to form a carboxylic acid.

[0080] Figure 1 is a schematic diagram illustrating an embodiment of a process for preparing one or more recycled component compositions (e.g., ethylene, propylene, butadiene, hydrogen and / or pyrolysis gasoline) (r-composition) using a recycled component pyrolysis oil composition (r-pyrolysis oil) or in combination with any embodiment mentioned herein.

[0081] like Figure 1 As shown in , the recycled waste can be subjected to pyrolysis in a pyrolysis unit 10 to produce a pyrolysis product / effluent containing a recycled component pyrolysis oil composition (r-pyrolysis oil). The r-pyrolysis oil can be fed to a cracker 20 together with a non-recycled cracker feed (e.g., propane, ethane and / or natural gasoline). A recycled component cracking effluent (r-cracked effluent) can be produced from the cracker and then separated in a separation train 30. In one embodiment, or in combination with any of the embodiments mentioned herein, the r-composition can be separated and recovered from the r-cracked effluent. The r-propylene stream can contain primarily propylene, while the r-ethylene stream can contain primarily ethylene.

[0082] As used herein, a furnace includes a convection zone and a radiant zone. The convection zone includes tubes and / or coils inside the convection box, which may also continue outside the convection box downstream of the coil inlet at the inlet of the convection box. For example, Figure 5 As shown, the convection zone 310 includes coils and ducts within the convection box 312, and may optionally extend outside the convection box 312 and return to or interconnect with ducts 314 within the convection box 312. The radiant zone 320 includes radiant coils / tubes 324 and burners 326. The convection zone 310 and the radiant zone 320 may be contained in a single integral box, or in separate discrete boxes. The convection box 312 does not have to be a separate discrete box. As shown in FIG. Figure 5 As shown, the convection box 312 is integrated with the combustion chamber 322 .

[0083] Unless otherwise indicated, all component amounts provided herein (eg, for feeds, materials, streams, compositions, and products) are expressed on a dry basis.

[0084] 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 embodiments, at least a portion of the composition is obtained from pyrolysis of recycled waste (e.g., waste plastic or waste streams).

[0085] In an embodiment, "r-ethylene" can be a composition comprising: (a) ethylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) ethylene having a recovery content value attributed 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 attributed to at least a portion of the propylene.

[0086] 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).

[0087] As used herein, "site" means the largest contiguous geographic boundary owned by a CE 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 CE manufacturing facility.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the recovery component quota or quota or recovery component worth is deposited in a recovery component inventory obtained from r-pyrolysis oil. Desirably, at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or up to 100% of the following are obtained from r-pyrolysis oil:

[0094] a. Quota, or

[0095] b. Amounts deposited into the stock of recycled content, or

[0096] c. The recycled content value in the recycled content inventory, or

[0097] d. The recycled content value applied to a composition to prepare a recycled content product, intermediate or article (recycled PIA).

[0098] A recycled PIA is a product, intermediate or article that may include a compound or composition containing a compound or polymer and / or article with an associated recycled component value. A PIA does not have a recycled component value associated with it. PIAs include, but are not limited to, AD, or CE, or AA, or CA, or CE (e.g., CAB).

[0099] As used herein, "recycled content quota" and "quota" means a recycled content value of:

[0100] 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

[0101] b. Depositing into a recycling inventory a starting composition (eg, 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 content value derived from, recycled waste.

[0102] As used herein, "pyrolysis recovery component quota" and "pyrolysis quota" or "p-quota" means a recovery component value of:

[0103] 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

[0104] 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.

[0105] 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.

[0106] In one embodiment or in combination with any of the mentioned embodiments, the thermal pyrolysis recovery component quota or pyrolysis quota may have a recovery component value of:

[0107] a. from a starting composition (e.g., a compound, polymer, feedstock, product or stream) at least a portion of which was obtained from the cracking of r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), or from recycled waste used to prepare cracked r-pyrolysis oil, or from cracked or to be cracked r-pyrolysis oil, or which has at least a portion of its recycled 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 at least a portion of which was obtained from the cracking of r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), or from recycled waste used to prepare cracked r-pyrolysis oil, or from cracked or to be cracked r-pyrolysis oil, or which has at least a portion of its recycled 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 a portion of which was obtained from the cracking of r-pyrolysis oil; or

[0108] 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).

[0109] c. A quota can be an allotment or a credit.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] As used herein, the term "recovery component allocation" refers to a type of recovery component quota, wherein the entity or individual supplying the composition sells or transfers the composition to a receiving individual or entity, and the individual or entity preparing the composition has a quota, at least a portion of which can be related to the composition sold or transferred to the receiving individual or entity by the supplying individual or entity. The supplying entity or individual can be controlled by the same entity or individual or entity family, or different entity families. In an embodiment, the recovery component allocation proceeds with the composition and the downstream derivatives of the composition. In an embodiment, the allocation can be deposited in the recovery component stock, and taken out from the recovery component stock as the allocation, and applied to the composition to prepare the r-composition or reclaim PIA.

[0114] 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.

[0115] Credits may be available for sale, transfer or use, or may be sold, transferred or used, or:

[0116] a. not sell the composition, or

[0117] b. sell or transfer the Composition, but the Quota is not related to the sale or transfer of the Composition, or

[0118] 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.

[0119] 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.

[0120] In one embodiment or in combination with any of the mentioned embodiments, the composition receiving the 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:

[0121] a. Obtaining r-pyrolysis oil,

[0122] b. obtaining recycled content value (or credit) from r-pyrolysis oil and (i) depositing it into a recycled content stock, taking the credit (or credit) from the recycled content stock and applying it to any composition to obtain an r-composition, or (ii) applying it directly to any composition without depositing it into a recycled content stock to obtain an r-composition; and

[0123] 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

[0124] 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.

[0125] 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.

[0126] 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, or six (6) months, or three (3) months, or one (1) month of achieving a deficit. The timing of depositing the quota into the recovered 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 recovered component value or quota from the volume of r-pyrolysis oil is deposited into the recovered component inventory. In addition, the quota or recovered component value taken from the recovered component inventory does not need to be traceable to r-pyrolysis oil or cracked r-pyrolysis oil, but can be obtained from any waste recovery stream and from any method of processing a recovered waste stream. Desirably, at least a portion of the recovered component value in the recovered 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 recovered component value is deposited into the recovered component inventory) is also processed by any one or more of the cracking processes described herein.

[0127] Determining whether an r-composition is directly or indirectly derived 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 CR or CE) can be traced back to an r-composition prepared from recycled waste.

[0128] 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., CE) can be traced back to a PR composition prepared from the pyrolysis of recycled waste.

[0129] 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.

[0130] 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.

[0131] 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-composition, such as r-Et and pr-Et compositions.

[0132] 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 source of the olefin volume for making the r-composition from recycled waste / pyrolyzed recycled waste, but rather any olefin composition produced by any process can be used and have a recycled component quota associated with such olefin composition, or the r-AD or r-CR or r-CE manufacturer does not need to trace the source of the r-olefin, or r-AD, or r-CR, or r-CE feedstock to the composition obtained by cracking r-pyrolysis oil or pyrolyzing recycled waste, respectively, but rather any corresponding olefin, or AD, or CR obtained from any source of feedstock for making CR or CE and have a recycled component quota associated with such CR or CE can be used to make r-CR or r-CE.

[0133] Examples of how the Pr composition used to prepare the CR (and ultimately the CE) can obtain recycled content include:

[0134] (i) a cracker facility in which the pyrolysis oil or the product obtained from the pyrolysis is cracked in the facility

[0135] The invention relates to a process for producing r-olefins (e.g., r-propylene) from a raw material, which may be continuously or intermittently and directly or indirectly fluidly connected through an interconnected pipeline, optionally through one or more storage vessels and valves or interlocks, to an olefin-derived petrochemical (e.g., AD or CR or CE) forming facility (which may be a storage vessel at the olefin-derived petrochemical facility or directly into an olefin-derived petrochemical forming reactor).

[0136] and r-olefin (e.g. r-propylene) feedstock through interconnected pipelines:

[0137] Ar-olefin (such as r-propylene) is prepared during or after the r-olefin (such as r-propylene)

[0138] is withdrawn from a cracker facility within the time period of being transported by pipeline to an olefin-derived petrochemical product (e.g. AD or CR or CE) forming facility; or

[0139] b. withdrawn from one or more storage tanks at any time, provided that at least one storage tank is fed with r-olefin (e.g. r-propylene), which may be continued as long as the entire volume of the one or more storage tanks is replaced with feed that does not contain r-olefin (e.g. r-propylene); or (ii) from a storage vessel, vault or facility, or in an isotainer,

[0140] transporting the olefin containing or having been fed with r-olefins (e.g., r-propylene) by truck or rail or ship or other means other than pipeline until the entire volume of the vessel, dome or facility has been replaced by olefin (e.g., r-propylene) feedstock that does not contain r-olefin (e.g., r-propylene); or (iii) a manufacturer of olefin-derived petrochemical products (e.g., AD or CR or CE) to its consumers

[0141] A person or the public certifies, represents, or advertises that its olefin-derived petrochemical products contain recycled content or are obtained from feedstocks containing or obtained from recycled content, where such recycled content is claimed to be based in whole or in part on obtained r-olefins (e.g., propylene feedstocks associated with an allotted amount made from cracked r-pyrolysis oil or obtained from r-

[0142] or (iv) an olefin-derived petrochemical product (e.g., AD or CR or CE) where the manufacturer has obtained:

[0143] a. Based on the certified, stated or advertised volume of olefins (e.g. ethylene or propylene) produced from r-pyrolysis oil or recycled waste, or

[0144] b. has transferred to the olefins-derived petrochemical product (e.g., AD or CR or CE) manufacturer credits or allocations for olefin supply sufficient to allow the olefins-derived petrochemical product (e.g., AD or CR or CE) manufacturer to meet the certification requirements or make representations or advertising thereof, or

[0145] c. Olefins having an associated recovery component value, wherein such recovery component value is obtained from r-pyrolysis oil, or cracked r-pyrolysis oil, or olefins obtained from cracked r-pyrolysis oil or from r-pyrolysis gas through one or more intermediate independent entities.

[0146] 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.

[0147] In one embodiment or in combination with the embodiments mentioned, the input or generation of the recovery component (recovery component raw material or quota) can be to or at the first site, and the recovery component value from the input is transferred to the second site and applied to one or more compositions prepared at the second site. The recovery component value can be applied to the composition symmetrically or asymmetrically at the second site. The recovery component value of "derived from cracked r-pyrolysis oil" or "obtained from cracked r-pyrolysis oil" or the recovery component value derived from cracked r-pyrolysis oil directly or indirectly does not imply the time when the recovery component value or quota is taken, captured, deposited in the recovery component inventory or transferred. The timing of depositing the quota or recovery component value in the recovery component inventory or realizing, identifying, capturing or transferring it is flexible, and can be carried out as early as receiving the r-pyrolysis oil at a site within the entity family that owns it or by an entity or individual that owns or operates a cracking facility to bring the r-pyrolysis oil into the inventory or within the entity family. Thus, a quota or recovered component value for a volume of r-pyrolysis oil may be obtained, captured, deposited into an inventory, or transferred to a product, without that volume having been fed to a cracking furnace and cracked. The quota may also be obtained during the feeding of r-pyrolysis oil to a cracker, during cracking, or when preparing an r-composition. The quota taken when r-pyrolysis oil is owned, possessed, or received and deposited into a recovered component inventory is a quota associated with, obtained from, or derived from cracked r-pyrolysis oil, even if the r-pyrolysis oil has not yet been cracked when the quota is taken or deposited, provided that the r-pyrolysis oil is cracked at some point in the future.

[0148] In one embodiment or in combination with any of the mentioned embodiments, the olefin-containing effluent manufacturer generates an allowance from r-pyrolysis oil, and:

[0149] a. applying the quota to any PIA made directly or indirectly (e.g. via a reaction scheme with several intermediates) from cracked r-pyrolysis oil; or

[0150] b. applying the quota to any PIA not produced directly or indirectly from cracked r-pyrolysis oil, such as where the PIA has already been produced and stored in a stockpile or is produced in the future; or

[0151] 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

[0152] d. is deposited into inventory and stored for later use.

[0153] In one embodiment or in combination with any of the embodiments mentioned, the recycled component information about the recycled PIA can be communicated to a third party, wherein such recycled component 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 communication can be electronic, by document, by advertisement or any other communication means.

[0154] In one embodiment or in combination with any of the mentioned embodiments, there is provided a system or package comprising:

[0155] a. Reclaim PIA, and

[0156] b. an identifier, such as a credit, tag or certificate associated with the PIA, wherein

[0157] The identifier is an indication that the PIA has or is derived from recycled content (it does not necessarily identify the source of the recycled content or allowance);

[0158] Provided that the recovered PIA thus produced has a quota, or is produced from the reactants, at least in part associated with the r-pyrolysis oil.

[0159] As used throughout, the step of deducting quotas from the inventory of recycled components does not need to be applied to the recycled PIA products. Deduction does not mean that the quantity disappears or is removed from the inventory log. Deduction can be an adjustment entry, a withdrawal, an addition as a debit entry, or any other algorithm that adjusts input and output based on the amount of recycled components associated with the product and one or the accumulated deposited quota amount in the inventory. For example, deduction can be a simple step of deducting / debiting entries from one column and adding / crediting to another column within the same program or book, or an algorithm that automates deductions and entries / additions and / or applies or is assigned to a product information board. The step of applying quotas to PIA (where such quotas are deducted from the inventory) does not need to physically apply quotas to recycled PIA products or to any documents issued in association with the recycled PIA products sold. For example, a recycled PIA manufacturer can ship recycled PIA products to customers, and the "application" of quotas to recycled PIA products is met by electronically transmitting recycled component credits to customers.

[0160] Also provided is a use of r-pyrolysis oil, the use comprising converting the r-pyrolysis oil in a gas cracking furnace to produce an olefin-containing effluent. Also provided is a use of r-pyrolysis oil, comprising converting reactants in a synthesis process to produce PIA, and applying at least a portion of a quota to the PIA, wherein the quota is associated with the r-pyrolysis oil or its source is a quota stock, wherein at least one of the deposits into the stock is associated with the r-pyrolysis oil.

[0161] 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.

[0162] 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:

[0163] a. cracking r-pyrolysis oil to produce an olefin-containing effluent; and

[0164] b. separating the compounds in the olefin-containing effluent to obtain separated compounds; and

[0165] c. reacting any reactants in the synthesis process to prepare PIA;

[0166] d. depositing the quota into the quota stock, the quota being derived from r-pyrolysis oil; and

[0167] e. Apply any allowance from the stock to the PIA, thereby obtaining a recycled PIA.

[0168] 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:

[0169] a. providing an olefin-containing effluent manufacturing facility configured to produce reactants;

[0170] b. providing a PIA manufacturing facility having a reactor configured to receive reactants from the olefin-containing effluent manufacturing facility; and

[0171] 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,

[0172] wherein the olefin-containing effluent production facility generates or participates in the generation of quota and cracked r-pyrolysis oil, and:

[0173] (i) applying the quota to the reactants or to the PIA, or

[0174] (ii) depositing the quota into a quota stock and optionally withdrawing a share from the stock and applying it to the reactants or to the PIA.

[0175] A recovered PIA manufacturing facility may prepare recovered PIA by accepting any reactants from an olefin-containing effluent manufacturing facility and applying the recovered components to the recovered PIA made with the reactants by deducting allowances from their inventory and applying them to the PIA.

[0176] In one embodiment or in combination with any of the mentioned embodiments, there is also provided a system for producing recycled PIA as follows:

[0177] a. providing an olefin-containing effluent manufacturing facility, which is configured to produce an output composition comprising an olefin-containing effluent;

[0178] 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;

[0179] c. providing a PIA manufacturing facility having a reactor configured to receive reactants and produce an output composition comprising PIA;

[0180] 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.

[0181] PIA manufacturing facilities can prepare recycled PIA. In this system, the olefin-containing effluent manufacturing facility can have its output connected to the reactant composition manufacturing facility fluid, and in turn, the reactant compound or composition manufacturing facility can have its output connected to the PIA manufacturing facility fluid. Alternatively, the manufacturing facilities of a) and b) can be connected to the fluid separately, or only b) and c) are connected to the fluid. 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 above methods.

[0182] 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.

[0183] 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.

[0184] A cyclic manufacturing method is also provided, the method comprising:

[0185] a. Providing r-pyrolysis oil, and

[0186] b. cracking an r-pyrolysis oil to produce an olefin-containing effluent, and (i) reacting compounds separated from said olefin-containing effluent to produce recovered PIA, or (ii) combining a recovered component quota obtained from said r-pyrolysis oil with PIA prepared from compounds separated from a non-recovered olefin-containing effluent to produce recovered PIA; and

[0187] c. the recycled PIA or any other product prepared from the recycled PIA,

[0188] At least a portion of any of the compounds or polymers is taken out as a feedstock to produce the r-pyrolysis oil.

[0189] In the above process, a fully cyclic or closed loop process is provided, wherein the recovered PIA can be recycled multiple times.

[0190] 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.

[0191] 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.

[0192] The terms "recycled waste," "waste stream," and "recycled waste stream" are used interchangeably and refer to any type of waste or waste-containing stream that is reused in a production process rather than permanently disposed of (e.g., in a landfill or incinerator). A recycled waste stream is a flow or accumulation of recycled waste from industrial and consumer sources that is at least partially recycled.

[0193] Recycled waste streams include materials, products, and articles (collectively referred to as "materials" when used alone). Recycled waste materials can be solid or liquid. Examples of solid recycled waste streams include plastics, rubber (including tires), textiles, wood, biowaste, modified cellulose, wet laid products, and any other material capable of pyrolysis. Examples of liquid waste streams include industrial sludge, oils (including those derived from plants and petroleum), recovered lubricating oils, or vegetable or animal oils, and any other chemical streams from industrial plants.

[0194] In one embodiment or in combination with any of the mentioned embodiments, the recycled waste stream that is pyrolyzed includes 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 that manufactures or sells the material.

[0195] 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, offcuts, substandard materials, and finished materials that have been transferred from a manufacturer to any downstream customer (e.g., manufacturer to wholesaler to distributor) but have not yet been used or sold to an end-use customer.

[0196] 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.

[0197] 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 material, molding, compressing or dissolving in a solvent.

[0198] 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.

[0199] 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 mentioned embodiments, 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 mentioned embodiments, the pyrolyzed recycled waste stream contains less than 10 weight percent, or no more than 5 weight percent, or no more than 3 weight percent, or no more than 2 weight percent, or no more than 1 weight percent, or no more than 0.5 weight percent, or no more than 0.2 weight percent, or no more than 0.1 weight percent, or no more than 0.05 weight percent of No. 3 plastic (polyvinyl chloride), or alternatively No. 3 and No. 6 plastics, or alternatively No. 3, 6, and No. 7 plastics.

[0200] Examples of recycled rubber include natural and synthetic rubber. The form of the rubber is not limited, including tires.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] Examples of recycled vegetable or animal oils include oils recycled from animal processing facilities and recycled waste from restaurants.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] like Figure 2 As shown, the pyrolysis system 110 may include a waste plastic source 112 for supplying one or more waste plastics to the system 110. The plastic feedstock 112 may be, for example, a hopper, a storage bin, a rail car, a long-haul trailer, or any other device that can hold or store waste plastics. In one embodiment or in combination with any of the embodiments described herein, the waste plastics supplied by the plastic source 112 may be in the form of solid particles, such as chips, flakes, or powder. Although in Figure 2 Not depicted in FIG. 1 , pyrolysis system 110 may also include additional sources of other types of recycled waste, which may be used to provide other feed types to system 110 .

[0214] 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.

[0215] 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.

[0216] In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastic may contain at least one, two, three or four different types of waste plastic in an amount of at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99 weight percent in each case.

[0217] In one embodiment or in combination with any embodiment mentioned herein, the plastic waste may contain 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 of polyvinyl chloride and / or polyethylene terephthalate in each case. In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastic may contain at least one, two or three plasticized plastics. References to "types" are identified by resin ID codes 1-7.

[0218] 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%.

[0219] 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.

[0220] When in the pyrolysis reactor 118, at least a portion of the plastic feed can be subjected to a pyrolysis reaction that produces a pyrolysis effluent comprising 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, a membrane reactor, or a combination of these reactors.

[0221] 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.

[0222] 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.

[0223] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis process can be carried out in the presence of an inert gas, such as nitrogen, carbon dioxide and / or steam, consisting essentially of, or consisting of an inert gas. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis process can be carried out in the presence of a reducing gas such as hydrogen and / or carbon monoxide.

[0224] 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.

[0225] 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.

[0226] In one embodiment or in combination with any embodiment mentioned herein, the pressure within the pyrolysis reactor 118 can be maintained at a pressure of at least 0.1 bar, or at least 0.2 bar, or at least 0.3 bar, and / or no more than 60 bar, or no more than 50 bar, or no more than 40 bar, or no more than 30 bar, or no more than 20 bar, or no more than 10 bar, or no more than 8 bar, or no more than 5 bar, or no more than 2 bar, or no more than 1.5 bar, or no more than 1.1 bar. In one embodiment or in combination with any embodiment mentioned herein, the pressure within the pyrolysis reactor 118 can be maintained at 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.

[0227] In one embodiment or in combination with any of the embodiments mentioned herein, a pyrolysis catalyst can be introduced into the plastic feed prior to introduction into the pyrolysis reactor 118 and / or introduced directly into the pyrolysis reactor 118 to produce r-catalyzed pyrolysis oil or r-pyrolysis oil prepared by a catalytic pyrolysis process. In one embodiment or in combination with any embodiment mentioned herein, the catalyst may comprise: (i) a solid acid such as a zeolite (e.g., ZSM-5, mordenite, beta, ferrierite, and / or zeolite-Y); (ii) a superacid such as sulfonated, phosphated, or fluorinated forms of zirconium oxide, titania, alumina, silica-alumina, and / or clay; (iii) a solid base such as a metal oxide, mixed metal oxide, metal hydroxide, and / or metal carbonate, particularly those of alkali metals, alkaline earth metals, transition metals, and / or rare earth metals; (iv) hydrotalcites and other clays; (v) metal hydrides, particularly those of alkali metals, alkaline earth metals, transition metals, and / or rare earth metals; (vi) alumina and / or silica-alumina; (vii) a homogeneous catalyst such as a Lewis acid, a metal tetrachloroaluminate, or an organic ionic liquid; (viii) activated carbon; or (ix) a combination thereof.

[0228] 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.

[0229] 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.

[0230] 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).

[0231] 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.

[0232] 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.

[0233] 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.

[0234] In one embodiment or in any combination of the embodiments mentioned, a cracker feedstock composition comprising 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). 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.

[0235] In one embodiment or in combination with any of the mentioned embodiments, the r-pyrolysis oil is free of r-catalytic pyrolysis oil.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the pyrolysis oil vapor stream 136 can be introduced into a hydroprocessing unit 142 for further refining. The hydroprocessing unit 142 can include a hydrocracker, a catalytic cracker operated using a hydrogen feed stream, a hydroprocessing unit and / or a hydrogenation unit. In the hydroprocessing unit 142, the pyrolysis oil vapor stream 136 can be treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil and remove undesirable byproducts from the pyrolysis oil. The resulting hydrotreated pyrolysis oil vapor stream 144 can be removed and introduced into a quenching unit 138. Alternatively, the pyrolysis oil vapor can be cooled, liquefied, and then treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil. In this case, hydrogenation or hydroprocessing is carried out in the liquid phase pyrolysis oil. In this embodiment, post-hydrogenation or post-hydroprocessing does not require a quenching step.

[0240] 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.

[0241] The pyrolysis oil may mainly contain hydrocarbons having 4 to 30 carbon atoms per molecule (e.g., C4 to C 30 As used herein, the term "Cx" or "Cx hydrocarbons" refers to hydrocarbon compounds that include x total carbons per molecule, and includes all olefins, paraffins, aromatic hydrocarbons, and isomers having that number of carbon atoms. For example, each of normal, iso-, and tert-butane and butene and butadiene molecules would fall within the general description "C4".

[0242] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the cracking furnace may have a C4-C50 weight percent of at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent in each case. 30 Hydrocarbon content, based on the weight of the pyrolysis oil.

[0243] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the furnace may comprise primarily C5-C 25 、C5-C 22 or C5-C 20hydrocarbons, or may contain at least about 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent of C5-C 25 、C5-C 22 or C5-C 20 Hydrocarbons, based on the weight of the pyrolysis oil.

[0244] The gas furnace can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock, thereby avoiding the necessity to subject the pyrolysis oil feedstock to separation techniques to deliver smaller or lighter hydrocarbon fractions to the cracking furnace. In one embodiment or in any of the mentioned embodiments, after delivery from the pyrolysis manufacturer, the pyrolysis oil does not undergo a separation process for separating the heavy hydrocarbon fraction from the lighter hydrocarbon fraction relative to each other before feeding the pyrolysis oil to the cracker furnace. Feeding the pyrolysis oil to the gas furnace allows the use of pyrolysis oil containing heavy tails or higher carbon numbers equal to or higher than 12. In one embodiment or in any of the mentioned embodiments, the pyrolysis oil fed to the cracking furnace is C5-C 25 A hydrocarbon stream containing at least 1 wt.%, 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).

[0245] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55 weight percent C6-C 12 The hydrocarbon content is based on the weight of the pyrolysis oil. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a C6-C ... 12In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have 10 to 95 weight percent, 20 to 80 weight percent, or 35 to 80 weight percent C6-C 12 Hydrocarbon content.

[0246] 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.

[0247] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil or r-pyrolysis oil fed to the cracking furnace, or the r-pyrolysis oil fed to the cracking furnace that receives a predominantly C2-C4 feedstock prior to feeding the pyrolysis oil (and references to r-pyrolysis oil or pyrolysis oil throughout include any of these embodiments) may have at least 1, or at least 2, or at least 3, or at least 4, or at least 5 weight percent of C2-C4 in each case. 24+ Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a C content of no more than 15, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6. 24+ In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have 1 to 15 weight percent, 3 to 15 weight percent, 2 to 5 weight percent, or 5 to 10 weight percent of C 24+ Hydrocarbon content.

[0248] 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.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] 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.

[0253] 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.

[0254] 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.

[0255] It should be noted that all of the above hydrocarbon weight percentages can be determined using gas chromatography-mass spectrometry (GC-MS).

[0256] 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 .

[0257] 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.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] 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.

[0262] 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.

[0263] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil of the present invention may be a recycled content pyrolysis oil composition (r-pyrolysis oil).

[0264] 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.

[0265] Now go to Figure 3 , shows a schematic diagram of a pyrolysis oil processing zone according to one embodiment or in combination with any embodiments described herein.

[0266] like Figure 3 As shown in the processing area 220 shown, at least a portion of the r-pyrolysis oil 252 produced by the recycled waste stream 250 in the pyrolysis system 210 can pass through the processing area 220, such as a separator, which separates the r-pyrolysis oil into a light pyrolysis oil fraction 254 and a heavy pyrolysis oil fraction 256. The separator 220 used for 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 internals, and may or may not use reflux and / or boiling flow.

[0267] In one embodiment or in combination with any embodiment mentioned herein, the C4-C7 content or C8+ content of the heavy fraction can be at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 weight percent. The light fraction can include at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% C3 and lighter (C 3- ) or C7 and lighter (C 7- In some embodiments, the separator can concentrate the desired components into the heavy fraction, so that the heavy fraction can have a C4-C7 content or C7 content higher than the pyrolysis oil taken out from the pyrolysis zone. 8+ The C4-C7 content or C4-C7 content is at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 70, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150% greater. 8+ Content. Figure 3 As shown, at least a portion of the heavy fraction may be sent to a cracking furnace 230 to be cracked as an r-pyrolysis oil composition or as a portion of a pyrolysis oil composition to form an olefin-containing effluent 258, as discussed in further detail below.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] 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.

[0274] 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.

[0275] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can contain at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent C4-C 30 Hydrocarbons, and as used herein, hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic compounds. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may mainly contain C5-C 25 、C5-C 22 or C5-C 20 hydrocarbons, or may contain at least 55, 60, 65, 70, 75, 80, 85, 90 or 95 weight percent C5-C 25 、C5-C 22 or C5-C 20 hydrocarbon.

[0276] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the r-pyrolysis oil composition may comprise C4-C 12 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and alicyclic hydrocarbons) and C 13 -C 22 aliphatic compounds in a weight ratio greater than 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on the weight of the r-pyrolysis oil.

[0277] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the r-pyrolysis oil composition may include C 13 -C 22 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and alicyclic hydrocarbons) and C4-C 12 aliphatic compounds in a weight ratio greater than 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on the weight of the r-pyrolysis oil.

[0278] In one embodiment, the two aliphatic hydrocarbons (branched or unbranched alkanes and alkenes, and alicyclic compounds) with the highest concentration in the r-pyrolysis oil are in the C5-C 18 , or C5-C 16 , or C5-C 14 , or C5-C 10, or in the range of C5-C8 (including the end values).

[0279] 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.

[0280] 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.

[0281] 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.

[0282] 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.

[0283] 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.

[0284] 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.

[0285] 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.

[0286] 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.

[0287] 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.

[0288] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the amount of oxygen atoms in the r-pyrolysis oil may be 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.

[0289] 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.

[0290] In one embodiment or in combination with any embodiment mentioned herein, the solubility of water in r-pyrolysis oil at 1 atm and 25° C. is less than 2 wt.%, water, or no more than 1.5, or no more than 1, or no more than 0.5, or no more than 0.1, or no more than 0.075, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, in each case wt.% water based on the weight of the r-pyrolysis oil. Desirably, the solubility of water in r-pyrolysis oil is no more than 0.1 wt.%, based on the weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil contains no more than 2 wt.% water, or no more than 1.5, or no more than 1, or no more than 0.5, desirably or no more than 0.1, or no more than 0.075, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, in each case as wt.% water based on the weight of the r-pyrolysis oil.

[0291] In one embodiment or in combination with any embodiment mentioned herein, the solids content in the r-pyrolysis oil is no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, or no more than 0.001, in each case as wt.% solids based on the weight of the r-pyrolysis oil.

[0292] In one embodiment or in combination with any embodiment mentioned herein, the sulfur content of the r-pyrolysis oil is no more than 2.5 wt.%, or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.1, or no more than 0.05, desirably or no more than 0.03, or no more than 0.02, or no more than 0.01, or no more than 0.008, or no more than 0.006, or no more than 0.004, or no more than 0.002, or no more than 0.001, in each case wt.% based on the weight of the r-pyrolysis oil.

[0293] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have the following component contents:

[0294] 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

[0295] 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.%,

[0296] 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.

[0297] In each case based on the weight of the r-pyrolysis oil.

[0298] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the amount of hydrogen atoms in the r-pyrolysis oil 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.

[0299] In one embodiment or in combination with any embodiment mentioned herein, the metal content of the r-pyrolysis oil is desirably low, e.g., no more than 2 wt.%, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, in each case wt.% based on the weight of the r-pyrolysis oil.

[0300] In one embodiment or in combination with any embodiment mentioned herein, the alkali and alkaline earth metal or mineral content of the r-pyrolysis oil is desirably low, e.g., no more than 2 wt.%, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, in each case wt.% based on the weight of the r-pyrolysis oil.

[0301] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of paraffins to cycloalkanes in the r-pyrolysis oil can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.25:1, or at least 4.5:1, or at least 4.75:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 13:1, or at least 15:1, or at least 17:1, based on the weight of the r-pyrolysis oil.

[0302] In one embodiment 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 conjunction with any of the embodiments mentioned, the ratio of the combination of paraffins and cycloalkanes to aromatic hydrocarbons 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.

[0303] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have a boiling point curve defined by one or more of its 10%, its 50% and its 90% boiling points, as defined below. As used herein, "boiling point" refers to the boiling point of the composition measured by ASTM D2887 or according to the procedure described in the working examples. If the value is obtained in any method, the boiling point with the value is satisfied. In addition, as used herein, "x% boiling point" means that according to any of these methods, x weight percentages of the composition boil at the boiling point.

[0304] 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.

[0305] 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.

[0306] In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed stream may comprise a composition comprising primarily C2-C4 hydrocarbons, or a composition comprising primarily C5-C 22As used herein, the term "primarily C2-C4 hydrocarbons" refers to a stream or composition containing at least 50 weight percent of C2-C4 hydrocarbon components. Examples of specific types of C2-C4 hydrocarbon streams or compositions include propane, ethane, butane, and LPG. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed may contain at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.%, based on the total weight of the feed, and / or no more than 100, or no more than 99, or no more than 95, or no more than 92, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, in each case C2-C4 hydrocarbons or linear alkanes weight percent, based on the total weight of the feed. The cracker feed may comprise mainly propane, mainly ethane, mainly butane or a combination of two or more of these components. These components may be non-recovery components. The cracker feed may comprise mainly propane, or at least 50 mol% propane, or at least 80 mol% propane, or at least 90 mol% propane, or at least 93 mol% propane, or at least 95 mol% propane (including any recovery stream mixed with fresh feed). The cracker feed may comprise HD5 quality propane as raw or fresh feed. The cracker may comprise greater than 50 mol% ethane, or at least 80 mol% ethane, or at least 90 mol% ethane, or at least 95 mol% ethane. These components may be non-recovery components.

[0307] In one embodiment or in combination with any embodiment described herein, the cracker feed stream may comprise a predominantly C5-C 22 As used herein, "primarily C5-C 22 "Hydrocarbon" refers to hydrocarbons containing at least 50 weight percent of C5-C 22 %, or at least 90, or at least 95, or at least 92, or at least 90, or at least 85, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.%, and / or no more than 100, or no more than 99, or no more than 95, or no more than 92, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, in each case C5-C 22 , or C5-C20 The hydrocarbon weight percentage is based on the total weight of the stream or composition. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed can have at least 0.5, or at least 1, or at least 2, or at least 5 C 15 and heavier (C 15+ ) content, in each case as weight percent, and / or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 18, or not more than 15, or not more than 12, or not more than 10, or not more than 5, or not more than 3, in each case as weight percent, based on the total weight of the feed.

[0308] 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.

[0309] 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.

[0310] 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.

[0311] 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.

[0312] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil is cracked in a gas furnace. A gas furnace is a furnace having at least one coil that receives (or operates to receive) a feed that is primarily in the gas phase (more than 50% of the feed weight is vapor) at the coil inlet at the convection zone inlet ("gas coil"). In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any of the mentioned embodiments, the gas coil may receive a primarily C2-C4 feedstock or a primarily C2-C3 feedstock to the inlet of the coil in the convection section, or alternatively, have at least one coil that receives more than 50 wt.% ethane and / or more than 50% propane and / or more than 50% LPG, or in any of these cases, receives at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, based on the weight of the cracker feed to the coil, or alternatively based on the weight of the cracker feed to the convection zone. A gas furnace may have more than one gas coil. In one embodiment or in combination with any embodiment mentioned herein or in conjunction 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 conjunction with any mentioned embodiment, the gas coils receive a vapor-phase feed at the coil inlet at the inlet of the convection zone, in which at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is vapor.

[0313] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any of the embodiments mentioned, the r-pyrolysis oil is cracked in a cracking furnace. The cracking furnace is a gas furnace. The cracking furnace contains at least one gas coil and at least one liquid coil 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 conjunction with any of the embodiments mentioned, 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 conjunction with any of the embodiments mentioned herein, the liquid coil may receive a liquid feedstock of primarily C6-C 22 The raw materials are mainly C7-C 16or alternatively, having at least one coil receiving more than 50 wt. % naphtha, and / or more than 50 wt. % natural gasoline, and / or more than 50 wt. % diesel, and / or more than JP-4, and / or more than 50 wt. % dry cleaning solvent, and / or more than 50 wt. % kerosene, and / or more than 50 wt. % fresh creosote, and / or more than 50 wt. % JP-8 or Jet-A, and / or more than 50 wt. % heating oil, and / or More than 50% heavy fuel oil, and / or more than 50% marine grade C, and / or more than 50% lubricating oil, or in any of these cases at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 98 wt.%, or at least 99 wt.%, based on the weight of the cracker feed to the liquid coils, or alternatively based on the weight of the cracker feed to the convection zone. In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, at least one coil in the convection zone or in the convection box of the furnace and not more than 75% of the coils, or not more than 50% of the coils, or not more than at least 40% of the coils are liquid coils. In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the liquid coil receives a vapor phase feed at the coil inlet at the inlet of the convection zone, 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.

[0314] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any mentioned embodiment, the r-pyrolysis oil is cracked in a thermal gas cracker.

[0315] In one embodiment or in combination with any embodiment mentioned herein or in conjunction 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.

[0316] In one embodiment or in combination with any embodiment mentioned herein or in conjunction 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 may consist entirely of gas coils, or the gas furnace may be a cracking furnace.

[0317] 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.

[0318] 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.

[0319] In one embodiment or combination of any of the embodiments mentioned, a method for preparing one or more olefins is provided, comprising: (a) feeding a first cracker feed comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to a cracker furnace; (b) feeding a second cracker feed to the cracking furnace, wherein the second cracker feed does not contain the r-pyrolysis oil or contains less (by weight) of the r-pyrolysis oil than the first cracker feed stream; and (c) cracking the first and second cracker feeds in respective first and second tubes to form an olefin-containing effluent stream.

[0320] 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.

[0321] 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.%.

[0322] 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.

[0323] The second cracker stream may be free of r-pyrolysis oil or contain less (by weight) of the r-pyrolysis oil than the first cracker feed stream. In addition, the second cracker stream may contain only non-recycled cracker feed in the second coil or tube. The second cracker feed stream may be mainly C2 to C4, or hydrocarbons (e.g., non-recycled components), or ethane, propane or butane, in each case in an amount of at least 55, 60, 65, 70, 75, 80, 85 or at least 90 weight percent, based on the second cracker feed in the second coil or tube. If r-pyrolysis oil is included in the second cracker feed, the amount of such r-pyrolysis oil may be less than the amount of r-pyrolysis oil in the first cracker feed by weight by at least 10%, 20, 30, 40, 50, 60, 70, 80, 90, 95, 97 or 99%.

[0324] 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 the condensed feed of C2-C5 hydrocarbons 350 to ensure that the feed to the coil inlet in the convection box 312 or the inlet of the convection zone 310 is primarily a vapor phase feed.

[0325] 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.

[0326] 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.

[0327] 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.

[0328] 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.

[0329] 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.

[0330] 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.

[0331] 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 conjunction 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 conjunction 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.

[0332] 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.

[0333] 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 .

[0334] In one embodiment or in combination with any embodiment mentioned herein or in conjunction with any of the embodiments mentioned, 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 conjunction with any of the mentioned embodiments, both steam and r-pyrolysis oil may be fed together 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.

[0335] 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.

[0336] 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.

[0337] 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.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] 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.

[0342] 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.

[0343] When the feed stream containing r-pyrolysis oil is introduced into the cracking furnace separately from the non-recovered 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-recovered feed stream. In one embodiment or in combination with any other mentioned embodiment, a method for preparing one or more olefins is provided, which is provided by: (a) feeding a first cracker stream having r-pyrolysis oil to a first tube inlet in a cracking furnace; (b) feeding a second cracker stream containing or mainly containing C2-C4 hydrocarbons to a second tube inlet in a cracking furnace, wherein the second tube is separated from the first tube, and the total molar flow rate of the first cracker stream fed at the first tube inlet is lower than the total molar flow rate of the second cracker stream 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.

[0344] For example, when the r-pyrolysis oil or the first cracker stream passes through the tubes in the cracking furnace, its molar flow rate can be higher than the hydrocarbon components (e.g., C2-C4 or C5-C6) in the non-recycled feed stream or the second cracker stream. 22) component through the other or second tube is at least 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55 or 60% lower. When steam is present in the 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).

[0345] In one embodiment or in combination with any of the embodiments mentioned herein, the molar flow rate of the r-pyrolysis oil in the feed stream containing r-pyrolysis oil in the furnace tubes (the first cracker stream) can be greater than the molar flow rate of the hydrocarbons (e.g., C2-C4 or C5-C6) in the non-recovery cracker stream (the second cracker stream). 22 ) is at least 0.01, 0.02, 0.025, 0.03, 0.035 and / or no more than 0.06, 0.055, 0.05, 0.045 kmol lb / hr lower than the molar flow rate of the cracker feed stream. In one embodiment or in combination with any embodiment mentioned herein, the molar flow rates of the r-pyrolysis oil and the cracker feed stream can be substantially similar such that the two molar flow rates are within 0.005, 0.001 or 0.0005 kmol lb / hr of each other. The molar flow rate of the r-pyrolysis oil in the furnace tubes may be at least 0.0005, 0.001, 0.0025, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15 kmol-lb / hr, and / or no more than 0.25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.08, 0.05, 0.0 25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.19, 0.21, 0.22, 0.23, 0.24, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65

[0346] 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.

[0347] In one embodiment or in combination with any embodiment mentioned herein, the steam to hydrocarbon ratio of the stream or the first cracker stream containing r-pyrolysis oil differs from the steam to hydrocarbon ratio of the non-recovered feed stream or the second cracker stream by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80%. The steam to hydrocarbon ratio can be higher or lower. For example, the steam to hydrocarbon ratio of the stream or the first cracker stream containing r-pyrolysis oil can differ from the steam to hydrocarbon ratio of the non-recovered feed stream or the second cracker stream by at least 0.01, 0.025, 0.05, 0.075, 0.10, 0.125, 0.15, 0.175 or 0.20 and / or no more than 0.3, 0.27, 0.25, 0.22 or 0.20. The steam to hydrocarbon ratio of the r-pyrolysis oil containing stream or the first cracker stream can be at least 0.3, 0.32, 0.35, 0.37, 0.4, 0.42, 0.45, 0.47, 0.5, and / or no more than 0.7, 0.67, 0.65, 0.62, 0.6, 0.57, 0.55, 0.52 or 0.5 and the steam to hydrocarbon ratio of the non-recovery cracker feed or the second cracker stream can be at least 0.02, 0.05, 0.07, 0.10, 0.12, 0.15, 0.17, 0.20, 0.25 and / or no more than 0.45, 0.42, 0.40, 0.37, 0.35, 0.32 or 0.30.

[0348] In one embodiment or in combination with any of the embodiments mentioned herein, the temperature of the stream containing r-pyrolysis oil as it passes through the crossover section in the cracking furnace may be different from the temperature of the non-recovery cracker feed as it passes through the crossover section when the stream is introduced and passed through the furnace separately. For example, the temperature of the r-pyrolysis oil stream as it passes through the crossover section may differ from the temperature of the non-recovery hydrocarbon stream (e.g., C2-C4 or C5-C22) passing through the crossover section in another coil by at least 0.01, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75%. This percentage can be calculated based on the temperature of the non-recovery stream according to the following formula:

[0349] [(r - temperature of pyrolysis oil stream - temperature of non-recovery cracker stream)] / (temperature of non-recovery cracker steam), expressed as a percentage.

[0350] 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.

[0351] 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.

[0352] 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.

[0353] 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).

[0354] 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.

[0355] 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.

[0356] In one embodiment or in combination with any embodiment mentioned herein, the temperature of the atomized or vaporized stream can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350°C cooler than the temperature of the cracker stream to which it is added, and / or no more than 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 75, 70, 60, 55, 50, 45, 40, 30, or 25°C cooler than the temperature of the cracker stream to which it is added. The resulting combined cracker stream comprises a continuous gas phase and a discontinuous liquid phase (or droplets or particles) dispersed therein. The atomized liquid phase may comprise r-pyrolysis oil, while the gas phase may comprise primarily C2-C4 components, ethane, propane, or a combination thereof. The combined cracker stream may have a vapor fraction of at least 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 0.99 by weight or, in one embodiment or in combination with any of the mentioned embodiments, by volume.

[0357] 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.

[0358] 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 .

[0359] 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.

[0360] Within the convection section 610, the temperature of the cracker stream can be increased by at least 50, 75, 100, 150, 175, 200, 225, 250, 275, or 300°C, and / or no more than about 650, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, or 275°C so that the passage of the heated cracker stream exiting the convection section 610 through the vapor liquid separator 640 can be carried out at a temperature of at least 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650°C, and / or no more than 800, 775, 750, 725, 700, 675, 650, 625°C. When heavier components are present, at least a portion or substantially all of the heavier components may be removed in the heavy components as bottom stream 642. At least a portion of the light fraction 644 from separator 640 may be removed alone or with one or more other cracker streams, such as primarily C5-C 22 The hydrocarbon stream or the combination of C2-C4 hydrocarbon streams is introduced into the cross section or radiation zone pipe 624 after separation.

[0361] refer to Figure 5 and 6 , the cracker feed stream (non-recycled cracker feed stream or when combined with an r-pyrolysis oil feed stream) 350 and 650 can be introduced into the furnace coils at or near the entrance of the convection section. The cracker feed stream can then pass through at least a portion of the furnace coils in the convection sections 310 and 610, and dilution steam 360 and 660 can be added at some points to control the temperature and cracking severity in the radiant sections 320 and 620. The amount of steam added can depend on the furnace operating conditions, including the feed type and the desired product distribution, but can be added to achieve a steam to hydrocarbon ratio in the range of 0.1 to 1.0, 0.15 to 0.9, 0.2 to 0.8, 0.3 to 0.75, or 0.4 to 0.6 by weight. In one embodiment or in combination with any embodiment described herein, steam can be used in the same furnace ( Figure 5Steam 360 and 660 may be added to the cracker feed (or any intermediate cracker feed stream within the furnace) when the cracker feed stream has a vapor fraction by weight of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90, or by volume in one embodiment or in combination with any of the mentioned embodiments.

[0362] 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.

[0363] 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.

[0364] 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.

[0365] 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:

[0366] [(measured value of the operating parameter) - (target value of the operating parameter)] / [(target value of the operating parameter)], expressed as a percentage.

[0367] As used herein, the term "different" means higher or lower.

[0368] 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.

[0369] 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:

[0370] [(measured value of the operating parameter) - (target value of the operating parameter)] / [(target value of the operating parameter)], expressed as a percentage.

[0371] 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.

[0372] 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:

[0373] [(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.

[0374] 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.

[0375] 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:

[0376] [(r - 50% boiling point of pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0377] 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.

[0378] 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.

[0379] 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.

[0380] In one embodiment or in combination with any of the mentioned embodiments, a method for preparing one or more olefins is provided, which is provided by: (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit; (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and (c) cracking the combined cracker stream at a second coil outlet temperature (COT2) in the cracking unit, wherein the second coil outlet temperature is lower than the first coil outlet temperature, or at least 3°C ​​lower, or at least 5°C lower.

[0381] 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).

[0382] In the setting mode, COT2 can be set to be at least 5°C lower than COT1. All coils in the furnace can be feed streams containing r-pyrolysis oil, or at least 1, or at least two coils can be feed streams containing r-pyrolysis oil. In either case, at least one of the coils containing r-pyrolysis oil can be in the setting mode. By reducing the cracking severity of the combined cracking stream, when its average number average molecular weight is higher than the cracker feed stream, such as gaseous C2-C4 feed, the lower thermal energy required for cracking r-pyrolysis oil can be utilized. Although the cracking severity of the cracker feed (e.g., C2-C4) can be reduced, thereby increasing the amount of unconverted C2-C4 feed in a single pass, a higher amount of unconverted feed (e.g., C2-C4 feed) is required to increase the final yield of olefins such as ethylene and / or propylene in multiple passes by recycling the unconverted C2-C4 feed through the furnace. Alternatively, other cracker products, such as aromatic hydrocarbons and diene content, can be reduced.

[0383] 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.

[0384] In set mode, the temperature can be fixed or set by adjusting the furnace to burner fuel ratio.

[0385] 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.

[0386] 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.

[0387] Regardless of the reason or cause of the temperature drop in COT2, the time period for engaging step (a) is flexible, but ideally, step (a) reaches a steady state before engaging step (b). In one embodiment or in combination with any of the mentioned embodiments, step (a) operates for at least 1 week, or at least 2 weeks, or at least 1 month, or at least 3 months, or at least 6 months, or at least 1 year, or at least 1.5 years, or at least 2 years. Step (a) can be represented by a cracking furnace that has never received a pyrolysis oil feed or a combination of a pyrolysis oil feed and a pyrolysis oil in operation. Step (b) can be the first time the furnace receives a pyrolysis oil feed or a combined cracker feed containing pyrolysis oil. In one embodiment or in combination with any of the other mentioned embodiments, steps (a) and (b) may be repeated multiple times per year, such as at least 2x / yr, or at least 3x / yr, or at least 4x / yr, or at least 5x / yr, or at least 6x / yr, or at least 8x / yr, or at least 12x / yr, as measured on a calendar year. Formulating the feed of pyrolysis oil represents multiple cycles of steps (a) and (b). When the feed supply of pyrolysis oil is exhausted or shut off, COT1 is allowed to reach a steady-state temperature before engaging step (b).

[0388] 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.

[0389] 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.

[0390] 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.

[0391] 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 producing one or more olefins is now provided by the following steps: (a) cracking a cracker stream in a cracking unit at a first hydrocarbon mass flow rate (MF1); (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 (c) cracking the combined cracker stream in the cracking unit at MF2 to obtain an olefin-containing effluent, the olefin-containing effluent having a combined yield of ethylene and propylene that is the same as or higher than the yield of ethylene and propylene obtained by cracking the cracker stream alone at MF1.

[0392] 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.

[0393] 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:

[0394]

[0395] Among them, mf1 is the combined yield of propylene and ethylene content in the cracker effluent under MF1 produced without using r-pyrolysis oil;

[0396] O mf2 is the combined production of propylene and ethylene content in the cracker effluent at MF2 made using r-pyrolysis oil.

[0397] 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:

[0398]

[0399] Wherein ΔO% 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

[0400] ΔMF% is the percentage of increase of MF2 compared to MF1.

[0401] 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:

[0402]

[0403] Where E mf1 is the combined wt.% of propylene and ethylene content in the cracker effluent under MF1 made without using r-pyrolysis oil;

[0404] E mf2 is the combined wt.% of propylene and ethylene content in the cracker effluent at MF2 made using r-pyrolysis oil.

[0405] Also provided is a method for preparing one or more olefins, the method comprising: (a) cracking a cracker stream in a cracking furnace to provide a first olefin-containing effluent exiting the cracking furnace at a first coil outlet temperature (COT1); (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and (c) cracking the combined cracker stream in the cracking unit to provide a second olefin-containing effluent exiting the cracking furnace at a second coil outlet temperature (COT2), wherein, when the r-pyrolysis oil is heavier than the cracker stream, COT2 is equal to or less than COT1, and wherein, when the r-pyrolysis oil is lighter than the cracker stream, COT2 is greater than or equal to COT1.

[0406] 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.

[0407] In one embodiment or in combination with any of the mentioned embodiments, a method for preparing one or more olefins is provided, which is provided by: (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit; (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and (c) cracking the combined cracker stream at a second coil outlet temperature (COT2) in the cracking unit, wherein the second coil outlet temperature is higher than the first coil outlet temperature.

[0408] 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.

[0409] 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.

[0410] 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:

[0411] (i) Lower thermal energy is required to crack the pyrolysis oil in the combined stream.

[0412] (ii) Exothermic reactions occur in the cracking products of the pyrolysis oil, such as the diels-alder reaction.

[0413] 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.

[0414] In one embodiment or in combination with any of the mentioned embodiments, COT2 may be set or fixed to a higher temperature (set mode) than COT1. This is more applicable when the hydrocarbon mass flow rate of the combined cracker stream is higher than the hydrocarbon mass flow rate of the cracker stream, which would otherwise reduce COT2. The higher second coil outlet temperature (COT2) can help with increased severity and reduced yield of unconverted lighter cracker feeds (e.g., C2-C4 feeds), which can help with downstream capacity-constrained fractionators.

[0415] 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.

[0416] 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).

[0417] 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.

[0418] 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.

[0419] 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.

[0420] 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.

[0421] 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:

[0422]

[0423] wherein E is the propylene:ethylene ratio in the cracker effluent produced without using r-pyrolysis oil, in wt.%;

[0424] E r is the propylene:ethylene ratio in the cracker effluent prepared using r-pyrolysis oil, in wt.%.

[0425] In one embodiment or in combination with any embodiment mentioned herein, relative to the effluent stream without r-pyrolysis oil, the amount of ethylene and propylene in the olefin-containing effluent stream of cracking can remain substantially unchanged or increase. Surprisingly, liquid r-pyrolysis oil can be fed to a gas feed furnace, which is received and cracked mainly as a C2-C4 composition and obtains an olefin-containing effluent stream, which can remain substantially unchanged or improved relative to the C2-C4 cracker feed without r-pyrolysis oil in some cases. The high molecular weight of r-pyrolysis oil can mainly contribute to the formation of aromatic hydrocarbons, and only participates in the formation of olefins (especially ethylene and propylene) in a small amount. However, we find that, under the same hydrocarbon mass flow rate, relative to the cracker feed without r-pyrolysis oil, when r-pyrolysis oil is added to the cracker feed to form a combined cracker feed, the combined weight percentage of ethylene and propylene, even the output does not significantly decline, and in many cases remains the same or may increase. The olefin-containing effluent stream may have a total wt.% of propylene and ethylene that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% higher than the propylene and ethylene content of the effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, as determined by:

[0426]

[0427] wherein E is the combined wt.% of propylene and ethylene content in the cracker effluent produced without using r-pyrolysis oil;

[0428] Er is the combined wt.% of propylene and ethylene content in the cracker effluent produced using r-pyrolysis oil.

[0429] 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.

[0430] 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.

[0431] 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.

[0432] 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%.

[0433] 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.

[0434] 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.

[0435] 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.

[0436] In one embodiment or in combination with one or more embodiments mentioned herein, when the r-pyrolysis oil and steam are fed downstream of the inlet of the convection box, or when one or both of the r-pyrolysis oil and steam are fed at a crossover position, the C 6+ The amount of product can be increased if such product is desired, for example for a BTX stream to prepare its derivatives. When r-pyrolysis oil and steam are fed downstream of the convection box inlet, the C in the olefin-containing effluent is about 1.3 % when measured relative to feeding r-pyrolysis oil at the convection box inlet. 6+ The amount of product may be increased by 5%, or 10%, or 15%, or 20%, or 30%, all other conditions being the same. The % increase may be calculated as:

[0437]

[0438] Where E i The C in the olefin-containing cracker effluent prepared by introducing r-pyrolysis oil at the inlet of the convection box 6+ content;

[0439] E d The C in the olefin-containing cracker effluent is obtained by introducing pyrolysis oil and steam downstream of the convection box inlet. 6+ content.

[0440] 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.

[0441] 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. As used herein, "olefins to aromatics" is the ratio of the total weight of C2 and C3 olefins to the total weight of aromatics as defined above. In one embodiment or in combination with any embodiment mentioned herein, the effluent stream can have 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 olefins to aromatics.

[0442] 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 6+ The ratio is at most 40: 1, or at most 35: 1, or at most 30: 1, or at most 25: 1, or at most 23: 1. As used herein, "olefins to aromatics" is the ratio of the total weight of C2 and C3 olefins to the total weight of aromatics as defined above.

[0443] 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.

[0444] 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.

[0445] 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.

[0446] 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:

[0447]

[0448] wherein E is the wt.% of the components in the cracker effluent prepared without using r-pyrolysis oil;

[0449] E r is the wt.% of the components in the cracker effluent made with r-pyrolysis oil.

[0450] 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.

[0451] 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.

[0452] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream may contain a small amount or no carbon dioxide. The olefin-containing effluent stream may have an amount of carbon dioxide in wt.%, which is no more than the amount of carbon dioxide in the effluent stream obtained by cracking the same cracker feed under equivalent conditions but without r-pyrolysis oil, or an amount not higher than 5% of the amount of carbon dioxide in wt.%, or not higher than 2%, or the same amount as the comparative effluent stream without r-pyrolysis oil. Alternatively or additionally, the olefin-containing effluent stream may have an amount of no more than 1000ppm, or no more than 500ppm, or no more than 100ppm, or no more than 80ppm, or no more than 50ppm, or no more than 25ppm, or no more than 10ppm, or no more than 5ppm of carbon dioxide.

[0453] Now go to Fig. 9, a block diagram illustrating the major elements of the furnace effluent processing section is shown.

[0454] like Fig. 9 As shown, the olefin-containing effluent stream from the cracking furnace 700, which includes the recovered components, is rapidly cooled (e.g., quenched) in a transfer line exchange ("TLE") 680, as shown. Figure 8 As shown, to prevent the production of large amounts of undesirable byproducts and to minimize fouling in downstream equipment, as well as to produce steam. In one embodiment or in combination with any of the embodiments mentioned herein, the temperature of the effluent containing the r-composition from the furnace can be reduced by 35 to 485°C, 35 to 375°C, or 90 to 550°C to a temperature of 500 to 760°C. The cooling step is performed immediately after the effluent stream leaves the furnace, such as within 1 to 30, 5 to 20, or 5 to 15 milliseconds. In one embodiment or in combination with any of the embodiments mentioned herein, the quenching step is performed in the quench zone 710 by heating the effluent in a heat exchanger (sometimes referred to as a transfer line exchanger, such as Figure 5 The TLE 340 is shown in Figure 8 In some embodiments, the quenching step is performed by indirect heat exchange with high pressure water or steam in the effluent (shown as TLE 680 in FIG. 1 ), while in other embodiments, the quenching step is performed by direct contact of the effluent with a quenching liquid 712 (shown as Fig. 9 ). The temperature of the quench liquid may be at least 65, or at least 80, or at least 90, or at least 100, in each case, ° C, and / or no more than 210, or no more than 180, or no more than 165, or no more than 150, or no more than 135, in each case, ° C. When a quench liquid is used, contacting may be conducted in a quench tower, and a liquid stream comprising gasoline and other similar boiling range hydrocarbon components may be removed from the quench tower. In some cases, a quench liquid may be used when the cracker feed is primarily liquid, and a heat exchanger may be used when the cracker feed is primarily vapor.

[0455] The resulting cooled effluent stream is then subjected to vapor-liquid separation, and the vapor is compressed in compression zone 720, such as in a gas compressor having, for example, 1 to 5 compression stages, with optional interstage cooling and liquid removal. The gas stream pressure at the outlet of the first set of compression stages is in the range of 7 to 20 bar gauge (barg), 8.5-18 psig (0.6 to 1.3 barg), or 9.5 to 14 barg.

[0456] The resulting compressed stream is then treated in an acid gas removal zone 722 to remove acid gases, including CO, CO2, and H2S, by contacting with an acid gas removal agent. Examples of acid gas removal agents may include, but are not limited to, caustic amines and various types of amines. In one embodiment or in combination with any of the embodiments mentioned herein, a single contactor may be used, while in other embodiments, a dual tower absorber-stripper configuration may be employed.

[0457] Then, the treated compressed olefin-containing stream can be further compressed via a compressor in another compression zone 724, optionally with interstage cooling and liquid separation. The resulting compressed stream has a pressure of 20 to 50 barg, 25 to 45 barg or 30 to 40 barg. Any suitable dehumidification method can be used, including, for example, molecular sieves or other similar methods to dry the gas in the drying zone 726. Then, the resulting stream 730 can be sent to a fractionation section, where olefins and other components can be separated into various high-purity products or intermediate streams.

[0458] Now go to Fig.10 , a schematic diagram of the main steps of the fractionation section is provided. In one embodiment or in combination with any of the embodiments mentioned herein, the initial tower of the fractionation system may not be a demethanizer 810, but may be a deethanizer 820, a depropanizer 840, or any other type of tower. As used herein, the term "demethanizer" refers to a tower whose light bonds are methane. Similarly, "deethanizer" and "depropanizer" refer to towers with ethane and propane as light bond components, respectively.

[0459] like Fig.10As shown, the feed stream 870 from the quench stage can be introduced into a demethanizer (or other) 810, wherein methane and lighter (CO, CO2, H2) components 812 are separated from ethane and heavier components 814. The demethanizer is operated at a temperature of at least -145, or at least -142, or at least -140, or at least -135, in each case ° C, and / or no more than -120, -125, -130, -135 ° C. The bottoms stream 814 from the demethanizer is then introduced into a deethanizer 820, wherein C2 and lighter components 816 are separated from C3 and heavier components 818 by fractionation, the bottoms stream comprising at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%, in each case as a percentage, of the total amount of ethane and heavier components introduced into the column. The deethanizer 820 may be operated at a top temperature of at least -35, or at least -30, or at least -25, or at least -20, in each case, °C, and / or no more than -5, -10, -10, -20 °C, and a top pressure of at least 3, or at least 5, or at least 7, or at least 8, or at least 10, in each case, barg, and / or no more than 20, or no more than 18, or no more than 17, or no more than 15, or no more than 14, or no more than 13, in each case, barg. The deethanizer 820 recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case, percent of the total amount of C2 and lighter components introduced into the column in the top stream. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 816 removed from the deethanizer comprises at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case weight percent ethane and ethylene, based on the total weight of the overhead stream.

[0460] like Fig.10As shown, the C2 and lighter overhead stream 816 from the deethanizer 820 is further separated in an ethane-ethylene fractionator (ethylene fractionator) 830. In the ethane-ethylene fractionator 830, an ethylene and lighter component stream 822 can be taken from the overhead of the column 830, or as a side stream from the top of the column, while ethane and any remaining heavier components are removed in a bottoms stream 824. The ethylene fractionator 830 can be operated at a top temperature of at least -45, or at least -40, or at least -35, or at least -30, or at least -25, or at least -20, in each case ° C, and / or no more than -15, or no more than -20, or no more than -25, in each case ° C, and a top pressure of at least 10, or at least 12, or at least 15, in each case barg, and / or no more than 25, 22, 20 barg. The ethylene-rich overhead stream 822 can contain at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 98, or at least 99, in each case weight percent ethylene, based on the total weight of the stream, and can be sent to downstream processing units for further processing, storage or sale. The overhead ethylene stream 822 produced during cracking of a cracker feed containing r-pyrolysis oil is an r-ethylene composition or stream. In one embodiment or in combination with any of the embodiments mentioned herein, the r-ethylene stream can be used to prepare one or more petrochemical products.

[0461] The bottoms stream of the ethane-ethylene fractionator 824 can include at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98 weight percent ethane in each case, based on the total weight of the bottoms stream. As previously described, all or a portion of the recovered ethane can be recycled to the cracking furnace as additional feedstock, either alone or in combination with a feed stream containing r-pyrolysis oil.

[0462] The liquid bottoms stream 818 from the deethanizer may be enriched in C3 and heavier components and may be separated in the depropanizer 840, such as Fig.10In the depropanizer 840, C3 and lighter components are removed as an overhead vapor stream 826, while C4 and heavier components may leave the column in a liquid bottoms stream 828. The depropanizer 840 may be operated at an overhead temperature of at least 20, or at least 35, or at least 40, in each case, °C, and / or no more than 70, 65, 60, 55 °C, and at an overhead pressure of at least 10, or at least 12, or at least 15, in each case, barg, and / or no more than 20, or no more than 17, or no more than 15, in each case, barg. The depropanizer 840 recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case, a percentage of the total amount of C3 and lighter components introduced into the column in the overhead stream 826. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 826 removed from the depropanizer 840 comprises at least or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98, in each case weight percent of propane and propylene, based on the total weight of the overhead stream 826.

[0463] The overhead stream 826 from the depropanizer 840 is introduced into a propane-propylene fractionator (propylene fractionator) 860, wherein propylene and any lighter components are removed in an overhead stream 832, while propane and any heavier components exit the column in a bottoms stream 834. The propylene fractionator 860 may be operated at an overhead temperature of at least 20, or at least 25, or at least 30, or at least 35, in each case °C, and / or no more than 55, 50, 45, 40 °C, and an overhead pressure of at least 12, or at least 15, or at least 17, or at least 20, in each case barg, and / or no more than 20, or no more than 17, or no more than 15, or no more than 12, in each case barg. The overhead stream 860 rich in propylene can contain at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 98, or at least 99, in each case, propylene weight percent, based on the gross weight of the stream, and can be sent to a downstream processing unit for further processing, storage or sale. The overhead propylene stream produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-propylene composition or stream. In one embodiment or in combination with any embodiment mentioned herein, the stream can be used to prepare one or more petrochemical products.

[0464] The bottoms stream 834 from the propane-propylene fractionator 860 can include at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98 weight percent propane, in each case based on the total weight of the bottoms stream 834. As previously described, all or a portion of the recovered propane can be recycled to the cracking furnace as additional feedstock, either alone or in combination with the r-pyrolysis oil.

[0465] Refer again Fig.10 The bottom stream 828 from the depropanizer 840 can be sent to the debutanizer 850 for separating the C4 components, including butenes, butanes and butadiene, from the C 5+ Component separation. The debutanizer can be operated at a tower top temperature of at least 20, or at least 25, or at least 30, or at least 35, or at least 40, in each case ° C, and / or no more than 60, or no more than 65, or no more than 60, or no more than 55, or no more than 50, in each case ° C, and a tower top pressure of at least 2, or at least 3, or at least 4, or at least 5, in each case barg, and / or no more than 8, or no more than 6, or no more than 4, or no more than 2, in each case barg. The debutanizer recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case a percentage of the total amount of C4 and lighter components introduced into the tower in the tower top stream 836. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 836 removed from the debutanizer contains at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case weight percent butadiene, based on the total weight of the overhead stream. The overhead stream 836 produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-butadiene composition or stream. The bottoms stream 838 from the debutanizer mainly contains at least 50, or at least 60, or at least 70, or at least 80, or at least 90, or at least 95 weight percent of C5 and heavier components, based on the total weight of the stream. The debutanizer bottoms stream 838 can be sent for further separation, processing, storage, sale or use.

[0466] The overhead stream 836 or C4 from the debutanizer may be subjected to any conventional separation method such as extraction or distillation processes to recover a more concentrated butadiene stream.

[0467] Cellulose ester composition

[0468] Generally, in one aspect, a cellulose ester composition is provided, comprising at least one cellulose ester having at least one substituent on an anhydroglucose unit (AGU) derived from recycled waste component propylene. In one embodiment or in combination with any of the embodiments mentioned, the cellulose ester can be prepared by any process described herein.

[0469] In one embodiment or in combination with any of the embodiments mentioned, the cellulose ester used in the present invention can be any cellulose ester known in the art that contains a butyryl moiety on AU. The cellulose esters useful in the present invention generally contain repeating units of the following structure:

[0470]

[0471] Where R 1 , R 2 and R 3 Independently selected from hydrogen or straight-chain alkanoyl groups having 2 to 10 carbon atoms. For cellulose esters, the substitution level is usually expressed as a degree of substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Typically, conventional cellulose contains three hydroxyl groups in each AGU unit, which can be substituted; therefore, the value of DS can be between zero and three. However, due to the contribution of end groups, low molecular weight cellulose mixed esters can have a total degree of substitution slightly higher than 3. Natural cellulose is a large polysaccharide with a degree of polymerization of 250-5,000 even after pulping and purification, so the assumption that the maximum DS is 3.0 is approximately correct. However, as the degree of polymerization decreases, such as in low molecular weight cellulose mixed esters, the end groups of the polysaccharide backbone become relatively more numerous, resulting in a DS that can exceed 3.0. This disclosure subsequently discusses low molecular weight cellulose mixed esters in more detail. Because DS is a statistical average, a value of 1 does not guarantee that each AGU has a single substituent. In some cases, unsubstituted anhydroglucose units may be present, some with two substituents, some with three substituents, and generally this value will be a non-integer. Total DS is defined as the average of all substituents of each anhydroglucose unit. The degree of substitution of each AGU may also relate to specific substituents, such as hydroxyl, acetyl, butyryl or propionyl. In an embodiment, the degree of polymerization of cellulose ester is lower than that of native cellulose. In an embodiment, n is an integer in the range of 25 to 250, or 25 to 200, or 25 to 150, or 25 to 100, or 25 to 75.

[0472] In one embodiment or in combination with any of the embodiments mentioned, the cellulose ester used can be a cellulose triester or a cellulose diester (secondary cellulose ester) containing a butyryl moiety.

[0473] In one embodiment or in combination with any of the embodiments mentioned, the cellulose ester can be cellulose propionate butyrate (CPB). Examples of such cellulose esters are described in U.S. Pat. Nos. 1,698,049; 1,683,347; 1,880,808; 1,880,560; 1,984,147, 2,129,052; and 3,617,201, the entire disclosures of which are incorporated herein by reference to the extent not inconsistent with the statements herein.

[0474] In one embodiment or in combination with any of the mentioned embodiments, the cellulose ester comprises butyryl moieties.

[0475] In one embodiment of the invention or in combination with any of the embodiments mentioned, the cellulose ester has at least 2 anhydroglucose rings, and may have at least 50 to at most 5,000 anhydroglucose rings. The number of anhydroglucose units per molecule is defined as the degree of polymerization (DP) of the cellulose ester. In one embodiment or in combination with any of the embodiments mentioned, the cellulose ester may have an inherent viscosity (IV) of about 0.2 to about 3.0 deciliters per gram, or about 0.5 to about 1.8, or about 1 to about 1.5, as measured at a temperature of 25°C on a 0.25 gram sample in 100 ml of a 60 / 40 by weight phenol / tetrachloroethane solution. Examples of cellulose esters include, but are not limited to, cellulose butyrate, cellulose propionate butyrate, cellulose acetate butyrate (CAB), and the like. In one embodiment or in combination with any of the embodiments mentioned, the DS / AGU of the cellulose esters useful in the invention is from about 2 to about 2.99, and the substituted esters may include acetyl, propionyl, butyryl, or any combination of these, provided that there is at least some butyryl component. In another embodiment of the present invention, the total DS / AGU is from about 2 to about 2.99, the DS / AGU of acetyl is from about 0 to 2.2, and the remaining ester groups include butyryl or a combination of propionyl and butyryl.

[0476] In one embodiment of the invention or in combination with any of the embodiments mentioned, the total DS / AGU is about 2 to about 2.99, the DS / AGU of acetyl groups is about 0 to 1.2, and the remaining ester groups include butyryl groups. In another embodiment of the invention, the total DS / AGU is about 2 to about 2.99, the DS / AGU of acetyl groups is about 0 to 0.5, and the remaining ester groups include butyryl groups.

[0477] Cellulose esters can be produced by any method known in the art. Methods for producing cellulose esters are taught in Kirk-Othmer, Encyclopedia of Chemical Technology, 5th Edition, Vol. 5, Wiley-Interscience, New York (2004), pp. 394-444. Cellulose is the raw material for producing cellulose esters and can be obtained in different grades and sources, such as cotton linter, softwood pulp, hardwood pulp, corn fiber and other agricultural sources, and bacterial cellulose.

[0478] One method of preparing cellulose esters is to esterify cellulose by mixing cellulose with a suitable organic acid, anhydride and catalyst. The cellulose is then converted into a cellulose triester. The ester is then hydrolyzed by adding a water-acid mixture to the cellulose triester, which can then be filtered to remove any gel particles or fibers. Water is then added to the mixture to precipitate the cellulose ester. The cellulose ester can then be washed with water to remove reaction by-products, then dehydrated and dried.

[0479] The cellulose triester to be hydrolyzed may have three substituents independently selected from alkanoyl groups having 2 to 10 carbon atoms. These cellulose esters may be prepared by many methods known to those skilled in the art. For example, cellulose esters may be prepared by heterogeneous acylation of cellulose in a mixture of carboxylic acid and anhydride in the presence of a catalyst such as H2SO4. Cellulose triesters may also be prepared by homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0480] Those skilled in the art will appreciate that the commercial term cellulose triesters also include cellulose esters that are not fully substituted with acyl groups.

[0481] After esterification of cellulose to triester, some of the acyl substituents can be removed by hydrolysis or alcoholysis to obtain cellulose diester. As previously mentioned, the distribution of acyl substituents can be random or non-random, depending on the particular method used. Cellulose diester can also be prepared directly without hydrolysis by using a limited amount of acylating agent. This process is particularly useful when the reaction is carried out in a solvent that dissolves cellulose. All of these methods can produce cellulose esters that can be used in the present invention.

[0482] In one embodiment or in combination with any of the embodiments mentioned, the absolute weight average molecular weight (Mw) of the cellulose diester that can be used in the present invention (measured by gel permeation chromatography (GPC) according to ASTM D6474) is about 5,000 to about 400,000. The absolute weight average molecular weight (Mw) of CE is calculated using the following method. The solvent is THF stabilized with BHT preservative. The instrument for the THF / cellulose ester method consists of the following Agilent 1200 series components: degasser, isocratic pump, autosampler, column oven, UV / Vis detector, and refractive index detector. The test temperature is 30°C and the flow rate is 1.0 ml / min. A sample solution of 25 mg of cellulose ester in 10 ml of THF is prepared, the solution containing BHT preservative and 10 μl toluene flow rate marker. The injection volume is 50 μl. The column set is Polymer Laboratories 5 μm PLgel, Guard+Mixed C+Oligopore. Detection is performed by refractive index. The calibrants are monodisperse polystyrene standards, Mw=580 to 3,220,000, purchased from Polymer Laboratories. The general calibration parameters are as follows: PS (K=0.0001280 and a=0.7120) and CE (K=0.00007572 and a=0.8424). The general calibration parameters are determined by light scattering and viscometry to obtain the correct weight average molecular weight. In further embodiments, the Mw is from about 15,000 to about 300,000. In still further embodiments, the Mw is: from about 10,000 to about 250,000; from about 15000 to 200000; from about 20,000 to about 150,000; from about 50,000 to about 150,000, or from about 70,000 to about 120,000.

[0483] In one embodiment of the invention or in combination with any of the embodiments mentioned, the polymer-based resin comprises a cellulose ester having an absolute weight average molecular weight ranging from about 40,000 Da to about 200,000 Da as measured according to ASTM D5296 using tetrahydrofuran as solvent and a flow rate of 1 mL / min. In one embodiment or in combination with any of the embodiments mentioned, the cellulose ester has an absolute weight average molecular weight ranging from about 50,000 Da to about 200,000 Da, or from 50,000 Da to about 170,000 Da, or from 50,000 Da to about 120,000 Da, or from 50,000 Da to about 90,000 Da, or from 60,000 Da to about 200,000 Da, or from 60,000 Da to about 170,000 Da, or from 60,000 Da to about 120,000 Da, or from 60,000 Da to about 90,000 Da, or from 90,000 Da to about 170,000 Da, or from 90,000 Da to about 120,000 Da, or from 120,000 Da to about 200,000 Da, according to ASTM D 1478. D5296, measured using tetrahydrofuran as solvent and a flow rate of 1 mL / min.

[0484] The most common commercially available cellulose diesters are prepared by an initial acid-catalyzed heterogeneous acylation of cellulose to form a cellulose triester. After obtaining a homogeneous solution of the cellulose triester in the corresponding carboxylic acid, the cellulose triester can then be hydrolyzed until the desired degree of substitution is obtained. After separation, a random cellulose diester is obtained. That is, the relative degree of substitution (RDS) at each hydroxyl group is approximately equal.

[0485] In one embodiment or in combination with any of the embodiments mentioned, the cellulose ester may contain chemical functional groups and is described herein as a derivatized, modified or functionalized cellulose ester, provided that the cellulose ester contains a butyryl moiety. Functionalized cellulose esters may be prepared by reacting the free hydroxyl groups of the cellulose ester with a bifunctional reactant having a linking group for grafting onto the cellulose ester and a functional group that provides a new chemical group to the cellulose ester. Examples of such bifunctional reactants include succinic anhydride, which is linked by an ester bond and provides an acid functional group; mercaptosilane, which is linked by an alkoxysilane bond and provides a mercapto functional group; isocyanoethyl methacrylate, which is linked by a urethane bond and imparts a methacrylate functional group.

[0486] In one embodiment of the present invention, the functionalized cellulose ester is produced by reacting the free hydroxyl groups of the cellulose ester with a bifunctional reactant to produce a cellulose ester having at least one functional group selected from the group consisting of unsaturated (double bond), carboxylic acid, acetoacetate, acetoacetate imide, mercapto, melamine and long alkyl chain.

[0487] In one embodiment or in combination with any of the embodiments mentioned, the cellulose ester may contain a plasticizer. The plasticizer used in the present invention may be any plasticizer known in the art that can reduce the glass transition temperature and / or melt viscosity of the cellulose ester to improve melt processing characteristics. The plasticizer may be any plasticizer suitable for use with the cellulose ester. The plasticizer level should be lower than the normal (or typical) plasticizer level for the cellulose ester; so that the composition has a higher Tg (or HDT), good toughness and good flowability than a fully plasticized cellulose ester composition. In one embodiment or in combination with any of the embodiments mentioned, the amount of plasticizer present does not substantially reduce the Tg (or HDT) of the cellulose ester composition compared to a similar composition without the plasticizer. In one embodiment or in combination with any of the embodiments mentioned, the change (e.g., decrease) in Tg (or HDT) due to the inclusion of the plasticizer does not exceed 20%, or 15%, or 10%, or 5%, or 2%.

[0488] In one embodiment or in combination with any of the embodiments mentioned, the r-cellulose ester composition is melt processable. Melt processability generally refers to the ability to heat process a material below its degradation temperature to obtain a uniform pellet or plastic article. For example, the composition can be injection molded on a Werner & Pflerderer 30 mm twin screw extruder at a throughput of 35 lbs / hr, a screw speed of 250 rpm, and a barrel temperature of 240° C. on a Toyo 110 injection molding machine, wherein the barrel temperature is 240° C. and the mold temperature is 160° F., with minimal molecular weight or color degradation.

[0489] Cellulose ester compositions can be used as molded plastic parts or as solid plastic objects. Cellulose ester compositions are suitable for any application requiring hard transparent plastics. Examples of these parts include disposable knives, forks, spoons, plates, cups, straws, eyeglass frames, toothbrush handles, toys, car decorations, tool handles, camera parts, electronic device parts, razor parts, ink pen barrels, disposable syringes, bottles, etc. In one embodiment, the composition of the present invention can be used as plastics, films, fibers, and sheets. In one embodiment, the composition can be used as plastics to make bottles, bottle caps, eyeglass frames, tableware, disposable tableware, tableware handles, shelves, shelf dividers, electronic device housings, electronic equipment boxes, computer monitors, printers, keyboards, pipelines, automotive parts, automotive interior parts, automotive decorations, signs, thermoformed letters, siding, toys, thermally conductive plastics, ophthalmic lenses, tool handles, appliances. In another embodiment, the compositions of the present invention are suitable for use as films, sheets, fibers, molded articles, medical devices, packaging, bottles, bottle caps, eyeglass frames, tableware, disposable tableware, tableware handles, shelves, shelf dividers, furniture components, electronic device housings, electronic equipment cases, computer monitors, printers, keyboards, plumbing, toothbrush handles, automotive parts, automotive interior parts, automotive trim, signs, outdoor signs, sunroofs, multilayer films, thermoformed letters, siding, toy parts, thermally conductive plastics, ophthalmic lenses and frames, tool handles and utensils, healthcare products, commercial food service products, boxes, films for graphic arts applications, and plastic films for plastic glass laminates.

[0490] The cellulose ester composition can also be used to form fibers, films, molded articles and sheets. The method of forming the cellulose ester composition into fibers, films, molded articles and sheets can be according to methods known in the art. Examples of possible molded articles include, but are not limited to: medical devices, medical packaging, health care products, commercial food service products, such as food trays, cups and storage boxes, bottles, food processors, blenders and mixer bowls, appliances, water bottles, fresh-keeping trays, washing machine fronts, vacuum cleaner parts and toys. Other possible molded articles may include ophthalmic lenses and frames.

[0491] Further possible uses of cellulose esters are described in WO 2018 / 160588 A1, the disclosure of which is incorporated herein by reference in its entirety.

[0492] In one embodiment or in combination with any of the embodiments mentioned, cellulose esters can be prepared by converting cellulose into cellulose esters using a cellulose reactant obtained from a recycled waste component ethylene source. In one embodiment or in combination with any of the embodiments mentioned, such a reactant can be a cellulose reactant that includes an organic acid and / or anhydride used in an esterification or acylation reaction of cellulose, for example, as discussed herein.

[0493] In one embodiment or in combination with any of the mentioned embodiments, the recycled propylene composition (r-propylene) described herein is used to prepare at least one cellulose reactant in a reaction scheme to prepare cellulose esters.

[0494] In one embodiment or in combination with any of the embodiments mentioned, r-propylene can be a feedstock component (for preparing at least one cellulose reactant) that includes other sources of propylene. Alternatively, in one embodiment or in combination with any of the embodiments mentioned, the only source of propylene used to prepare the cellulose reactant is r-propylene.

[0495] In one embodiment or in combination with any of the embodiments mentioned above, the cellulose reactant prepared using r-propylene can be selected from butyraldehyde, butyric acid, butyric anhydride, and combinations thereof. In one embodiment or in combination with any of the embodiments mentioned above, the cellulose reactant can be at least one reactant or at least one product of one or more of the following reactions: (1) conversion of propylene to butyraldehyde by hydroformylation; (2) conversion of propylene to butyric acid; (3) conversion of butyraldehyde to butyric acid, for example, oxidation of butyraldehyde to butyric acid; (4) conversion of butyric acid to butyric anhydride, for example, esterification of acetic anhydride with butyric acid to produce butyric anhydride and acetic acid.

[0496] In one embodiment or in combination with any of the embodiments mentioned, a cellulose ester composition is provided, comprising at least one cellulose ester comprising at least one substituent derived from r-CR on an anhydroglucose unit (AGU). In one embodiment or in combination with any of the embodiments mentioned, the substituent is a butyryl functional group.

[0497] In one embodiment or in combination with any of the mentioned embodiments, the cellulose ester is cellulose acetate butyrate (CAB), in particular r-CAB.

[0498] In one embodiment or in combination with any of the mentioned embodiments, the cellulose ester is prepared from a CR comprising r-butyric anhydride, which is directly or indirectly derived from r-propylene.

[0499] In one embodiment or in combination with any of the embodiments mentioned, an integrated process for preparing cellulose esters is provided, comprising the following processing steps: (1) preparing a recycled waste component pyrolysis oil (r-pyrolysis oil) using a feedstock containing at least some recycled waste components, such as recycled plastics, in a pyrolysis operation; (2) preparing a recycled component propylene (r-propylene) using a feedstock containing at least some r-pyrolysis oil components in a cracking operation; (3) preparing at least one chemical intermediate from the r-propylene; (4) reacting the chemical intermediate in a reaction scheme to prepare at least one cellulosic reactant for preparing cellulose esters, and / or selecting the chemical intermediate as at least one cellulosic reactant for preparing cellulose esters; and (5) reacting the at least one cellulosic reactant to prepare the cellulose ester; wherein the cellulose ester comprises at least one substituent on an anhydroglucose unit (AGU) derived from recycled waste component propylene.

[0500] In one embodiment or in combination with any of the embodiments mentioned, process steps (1) to (5), or (1) to (4), or (2) to (4), or (2) and (3), or (3) and (4) are carried out in a system in fluid and / or gas communication (i.e., including the possibility of a combination of fluid and gas communication). It should be understood that in one or more reaction schemes for producing cellulose esters starting from recycled plastic component synthesis gas, the chemical intermediates can be temporarily stored in storage containers and subsequently reintroduced into the integrated process system.

[0501] In one embodiment or in combination with any of the embodiments mentioned, the cellulose reactant is selected from butyraldehyde, butyric acid, butyric anhydride, or a combination thereof. In one embodiment or in combination with any of the embodiments mentioned, one chemical intermediate is butyraldehyde, and butyraldehyde is used in the reaction scheme to prepare a second chemical intermediate, which is butyric acid. In one embodiment or in combination with any of the embodiments mentioned, the cellulose reactant is butyric anhydride.

[0502] Cellulose Ester Process and Recycled Content

[0503] In one embodiment or in combination with any of the embodiments mentioned, r-propylene is used (in one or more reactions) to produce at least one cellulose reactant. In one embodiment or in combination with any of the embodiments mentioned, r-propylene is used (in one or more reactions) to produce at least one butyryl-containing cellulose ester.

[0504] In one embodiment or in combination with any of the embodiments mentioned, r-propylene is used in the reaction scheme to make butyric anhydride. In one embodiment or in combination with any of the embodiments mentioned, r-propylene is first converted to butyraldehyde, which is then used in the reaction scheme to make butyric anhydride. In one embodiment or in combination with any of the embodiments mentioned, "r-butyric acid" refers to butyric acid derived from r-propylene, and "r-butyric anhydride" refers to butyric anhydride derived from r-propylene, wherein derived from means that at least some of the raw material source material (which is used in any reaction scheme to make the cellulose reactant or intermediate) has some r-propylene content.

[0505] In one embodiment or in combination with any of the embodiments mentioned, r-butyric acid is used as a CE intermediate reactant for esterification of cellulose to produce cellulose esters, as discussed more fully above. In one embodiment or in combination with any of the embodiments mentioned, r-butyric acid is used as a reactant to produce cellulose butyrate or cellulose acetate butyrate.

[0506] The recycled content of the cellulose ester can be provided by a recycled content cellulose reactant. In one embodiment or in combination with any of the embodiments mentioned, the cellulose reactant is a compound capable of reacting with cellulose (or a cellulose composition) to provide a butyryl moiety on at least one anhydroglucose unit (AGU) of the cellulose. In one embodiment or in combination with any of the embodiments mentioned, the reactant can be butyric acid and / or butyric anhydride.

[0507] A process for producing a recovered component compound that can serve as an intermediate or cellulosic reactant (e.g., butyraldehyde, butyric acid, or butyric anhydride) begins by feeding a recovered propylene composition ("r-propylene") to a reactor in a reaction scheme for producing the intermediate and / or cellulosic reactant, wherein the r-propylene is derived directly or indirectly from cracked r-pyrolysis oil.

[0508] In one embodiment or in combination with any of the embodiments mentioned, there is provided a method for preparing cellulose esters, comprising:

[0509] a. preparing a recovered pyrolysis oil composition by pyrolysis recovery of raw materials (r-pyrolysis oil);

[0510] b. cracking r-pyrolysis oil to produce a first recovered propylene composition, at least a portion of which is obtained from cracking r-pyrolysis oil (r-propylene);

[0511] c. converting at least a portion of the r-propylene in a synthesis process to produce butyric acid and / or to produce butyraldehyde, and converting the butyraldehyde to produce butyric acid;

[0512] d. converting at least a portion of the butyric acid in a synthesis process to produce butyric anhydride; and

[0513] e. reacting at least a portion of the butyric acid and / or the butyric anhydride with cellulose in a synthesis process to produce the cellulose ester.

[0514] In one embodiment or in combination with any of the embodiments mentioned, the CE intermediate prepared using r-propylene can be selected from butyraldehyde, butyric acid, butyric anhydride, and combinations thereof. In one embodiment or in combination with any of the embodiments mentioned, the CE intermediate can be at least one reactant or at least one product of one or more of the following reactions: (1) conversion of propylene to butyraldehyde by hydroformylation; (2) conversion of propylene to butyric acid by hydrocarboxylation; (3) conversion of butyraldehyde to butyric acid, e.g., oxidation of butyraldehyde to butyric acid; and / or (4) conversion of butyric acid to butyric anhydride, e.g., transesterification of acetic anhydride with butyric acid to butyric anhydride and acetic acid.

[0515] In one embodiment or in combination with any of the embodiments mentioned, there is provided a method for processing a recovered propylene composition, at least a portion of which is derived directly or indirectly from a cracked recovered pyrolysis oil composition (r-propylene), comprising producing cellulose esters from a reaction scheme starting with r-propylene.

[0516] In one embodiment or in combination with any of the embodiments mentioned, there is provided a method of preparing a recycled content composition for use as a cellulose reactant or intermediate in a reaction scheme to provide a recycled content cellulose ester product. In one embodiment or in combination with any of the embodiments mentioned, the recycled content of these recycled content compositions is derived from r-propylene, which in turn is derived from r-pyrolysis oil (as described herein).

[0517] In one embodiment or in combination with any of the embodiments mentioned, the recycled content composition can be selected from r-butyraldehyde, r-butyric acid and / or r-butyric anhydride. In addition, in one embodiment or in combination with any of the embodiments mentioned, the recycled compositions can be added to the above-mentioned esterification process to produce cellulose esters.

[0518] Fig.26 Depicted is a schematic flow chart showing how to use r-propylene to produce r-CE, in particular r-CAB. Fig.26 As shown, propylene, especially r-propylene, can be converted to r-butyraldehyde by hydroformylation, or can be directly converted to r-butyric acid by hydrocarboxylation.

[0519] The r-propylene for feeding to the hydroformylation reactor or the hydrocarboxylation reactor can be a purified, partially purified or impure r-propylene stream. The r-propylene can be a purified feedstock and can contain greater than 98 wt.% propylene, or at least 98.2 wt.%, or at least 98.5 wt.%, or at least 98.7 wt.%, or at least 98.9 wt.%, or at least 99.0 wt.%, or at least 99.2 wt.%, or at least 99.5 wt.%, or at least 99.7 wt.% propylene, based on the weight of the r-propylene feedstock.

[0520] In one embodiment or in combination with any of the mentioned embodiments, the process for producing a recovered component butyraldehyde product comprises a hydroformylation process wherein r-propylene is fed into a reaction vessel and reacted to produce a hydroformylation effluent comprising r-butyraldehyde.

[0521] While any process for converting r-propylene to butyraldehyde may be used, rhodium catalyzed processes or low pressure hydroformylation processes are ideal synthetic routes due to their high catalyst activity and selectivity and low pressure and temperature requirements.

[0522] More specifically, the hydroformylation process for producing r-butyraldehyde comprises contacting propylene with synthesis gas (H2, CO) and a catalyst complex in a reaction zone at elevated temperature and pressure for a sufficient time to react the propylene with the synthesis gas to form butyraldehyde. Suitable methods for producing butyraldehyde include high pressure and low pressure oxo processes, wherein r-propylene is hydroformylated to produce butyraldehyde. The hydroformylation reaction temperature may be any temperature from 50°C to about 250°C, and the reaction pressure may be from 15 psig to about 5100 psig.

[0523] The hydroformylation process can be a high pressure or low pressure process. For high pressure processes, examples of hydroformylation reaction pressure (in the reaction zone within the hydroformylation reactor) or propylene pressure fed to the reactor include at least 550 psig or at least 4000 psig. The pressure can be up to 5100 psig or up to 4500 psig.

[0524] In a high pressure hydroformylation process, the temperature within the reaction zone may be at least 140° C. or at least 170° C. Additionally or alternatively, the temperature may be at most 250° C. or at most 200° C.

[0525] In low pressure processes, the hydroformylation reaction pressure (in the reaction zone within the hydroformylation reactor) or the propylene pressure fed to the reactor comprises at least 15 psig or at least 300 psig. The pressure may be less than 550 psig or at most 285 psig. Typically, the reaction pressure is at least 200 psig and at most 400 psig.

[0526] In a low pressure hydroformylation process, the temperature within the reaction zone may be at least 50° C. or at least 90° C. Additionally or alternatively, the temperature may be up to 160° C. or up to 100° C. Typically, the reaction temperature is from 60° C. to 115° C.

[0527] Typically, the molar ratio of hydrogen to carbon monoxide introduced into the reactor (which is not necessarily the ratio of the syngas) or the molar ratio in the reactor is maintained in the range of about 0.1: 1 to about 10: 1, or 0.5: 1 to 4: 1, or 0.9: 1 to 4: 1, or 1: 1 to 4: 1. In many hydroformylations, the reaction rate, as well as the yield of butyraldehyde, can be increased by increasing the molar ratio of hydrogen to carbon monoxide to above 4.0, and up to about 10.0 or more.

[0528] Suitable hydroformylation catalysts include any known catalysts that are effective in catalyzing the conversion of propylene to butyraldehyde. Examples of such catalysts are metals complexed with ligands. Suitable metals include cobalt, rhodium and ruthenium metals.

[0529] The conversion of propylene molecules in r-propylene may be at least 80%, or a...

Claims

1. A method of treating a pyrolysis recycled content cellulose reactant composition ("pr-CR") derived directly or indirectly from the pyrolysis of recycled waste, the method comprising feeding the pr-CR to a reactor in which cellulose esters are produced.

2. A method for preparing a recycled content cellulose ester composition ("r-CE"), the method comprising reacting a recycled content cellulose reactant composition ("pr-CR") with a cellulose composition to produce a cellulose ester effluent comprising r-CE, wherein at least a portion of the recycled content cellulose reactant composition is directly or indirectly derived from pyrolyzed recycled waste, wherein at least one cellulose reactant is selected from butyric acid, butyric anhydride, or a combination thereof.

3. A method for preparing cellulose esters, comprising a cellulose ester manufacturer, or one of a family of entities thereof: a. obtaining a cellulose reactant composition from a supplier, and: i. also obtain a pyrolysis recovery component quota or ii. obtaining a pyrolysis recovery component quota from any person or entity without providing a cellulosic reactant composition from said person or entity to which said pyrolysis recovery component quota is transferred; 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. Preparation of cellulose ester compositions from any cellulose reactant composition obtained from any source.

4. A method for preparing cellulose ester, the method comprising: a. A cellulose ester manufacturer obtains a cellulose reactant composition from a supplier and: i. also obtain a pyrolysis recovery component quota or ii. obtaining a pyrolysis recovery component quota from any person or entity without providing a cellulosic reactant composition from said person or entity to which said pyrolysis recovery component quota is transferred; and b. the cellulose ester manufacturer prepares a cellulose ester composition ("C3OH") from any cellulose reactant composition obtained from any source; and c. One of the following: i. applying the pyrolysis recovery component quota to the CE prepared by supplying the cellulose reactant obtained in step (a); or ii. applying the pyrolysis recovery quota to CE prepared by not supplying the cellulose reactant obtained in step (a), or 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: 1.CE, thereby obtaining r-CE, or 2. Compounds or compositions other than CE, or 3. Both; This is regardless of whether the recovery component value is obtained from the pyrolysis recovery component quota obtained in step a(i) or step a(ii).

5. A method for preparing a recycled content cellulose ester composition ("r-CE"), the method comprising: a. reacting any cellulose reactant composition in a synthesis process to produce a cellulose ester composition ("CE"); as well as b. applying a recycled content value to at least a portion of the CE to obtain a recycled content cellulose ester composition ("r-CE"); and 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 includes a pyrolysis recovered component quota or a pyrolysis recovered component quota deposit that has been performed in the recovered inventory before the deduction; and d. Optionally communicate to a third party that the r-CE has recycled content or is obtained or derived from recycled waste.

6. A method of altering the recycled content value of a recycled content cellulose ester composition ("r-CE"), the method comprising: a. One of the following: i. reacting a recycled content cellulose reactant composition ("r-CR") to produce a recycled content cellulose ester composition ("r-CE") having a first recycled content value ("first r-CE"); or ii. having a recycled content cellulose ester composition ("r-CE") having a first recycled content value (also a "first r-CE"); and b. transferring recycled content value between the recycled stock and the first r-CE to obtain a second recycled content cellulose ester composition having a second recycled content value, the second recycled content value being different from the first recycled content value ("second r-CE"), wherein the transferring optionally comprises: i. deducting the recycled content value from the recycled stock and applying the recycled content value to the first r-CE to obtain the second r-CE having a second recycled content value higher than the first recycled content value; or ii. subtracting the recycled content value from the first r-CE and adding the subtracted recycled content value to the recycled stock to obtain the second r-CE having a second recycled content value lower than the first recycled content value.

7. A method for preparing a recycled content cellulose ester composition ("r-CE"), the method comprising: 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"); 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 by deducting the recovery component value from the recovery inventory and applying it to the olefins to produce the r-olefins; as well as c. reacting any olefin volume in a synthesis process to produce a cellulose reactant composition, wherein the cellulose reactant composition comprises butyraldehyde, butyric acid, butyric anhydride, or a combination thereof; as well as d. reacting at least a portion of any cellulose reactant composition in a synthesis process to produce a cellulose ester composition; and e. applying a recycled content value to at least a portion of the cellulose ester composition based on: i. Using the pyrolysis recovery component cellulose reactant composition ("pr-CR") as a raw material or 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 CE, thereby obtaining said r-CE.

8. A method for preparing recycled content cellulose ester ("r-CE"), the method comprising: a. obtaining a pyrolysis recovery component cellulose reactant composition, at least a portion of which is directly derived from cracked r-pyrolysis oil or obtained from r-pyrolysis gas ("dr-CR"), b. preparing a cellulose ester composition from a raw material comprising said dr-CR, c. applying a recycled content value to at least a portion of any cellulose ester composition prepared by the same entity as the entity that prepared the cellulose ester composition in step b), wherein the recycled content value is based at least in part on the amount of recycled content contained in the dr-CR.

9. Use of a recycled content cellulose reactant composition ("pr-CR") derived directly or indirectly from pyrolysis recycled waste, the use comprising converting the pr-CR in a synthetic process to prepare a cellulose ester composition, wherein the cellulose reactant composition comprises butyraldehyde, butyric acid, butyric anhydride, or a combination thereof.

10. Use of recovered stocks, including: a. converting any cellulose reactant composition in a synthesis process to produce a cellulose ester composition ("CE"); as well as b. applying a recycled content value to the CE 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.

11. A method of preparing a recycled content cellulose ester composition ("r-CE"), the method comprising: a. Providing a cellulose reactant manufacturing facility that at least partially produces a cellulose reactant composition ("CR"), wherein the cellulose reactant comprises butyric acid, butyric anhydride, or a combination thereof; b. providing a cellulose ester manufacturing facility that manufactures a cellulose ester composition ("CE") and includes a reactor configured to receive a CR; as well as c. feeding at least a portion of the CR from a cellulose reactant manufacturing facility to a cellulose ester manufacturing facility via a supply system providing fluid communication between the facilities; Wherein either or both of the cellulose reactant manufacturing facility or the cellulose ester manufacturing facility manufactures or supplies recycled component cellulose reactant (r-CR) or recycled component cellulose ester (r-CE), respectively, and optionally, wherein the cellulose reactant manufacturing facility supplies r-CR to the cellulose ester manufacturing facility via the supply system.

12. A system comprising: a. an olefin manufacturing facility configured to produce an output composition comprising recycled content propylene or recycled content ethylene or both ("r-olefins"); b. a cellulose reactant manufacturing facility configured to receive an olefin stream from the olefin manufacturing facility and to produce an output composition comprising a cellulose reactant composition; c. a cellulose ester manufacturing facility having a reactor configured to receive a cellulose reactant composition and to produce an output composition comprising recycled content cellulose ester ("r-CE"); as well as 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 of the one or more manufacturing facilities.

13. A system or kit comprising: a. cellulose esters, and b. an identifier associated with the cellulose ester, the identifier being an indication that the cellulose ester has recycled content or is made from a source having a recycled content value.

14. A method of offering for sale or selling recovered cellulose esters, comprising: a. converting a cellulose reactant composition in a synthesis process to produce a cellulose ester composition ("CE"), b. applying the recycled content value to at least a portion of the CE to obtain a recycled content CE (r-CE), and c. Offering to sell or selling said r-CE having recycled content or obtained or derived from recycled waste.

15. A recycled content cellulose ester ("r-CE") having a reaction product derived from a recycled content cellulose reactant composition ("r-CR"), wherein the r-CR comprises r-butyric acid, r-butyric anhydride, or a combination thereof.

16. A recycled content cellulose ester composition ("r-CR") obtained by the method or use according to any one of claims 1 to 15.

17. The method, system, use or composition according to any one of claims 1 to 15, wherein: The r-olefins, r-CR or r-CE are derived directly or indirectly from cracked r-pyrolysis oil or obtained from r-pyrolysis gas.

18. The method, system, use or composition according to any one of claims 1 to 15, wherein: The r-olefins, r-CR or r-CE are derived directly or indirectly from cracking r-pyrolysis oil in a gas fed cracker.

19. The method, system, use or composition according to any one of claims 1 to 15, wherein: The CE composition is prepared by reacting r-CR with hydrogen in the presence of a catalyst.

20. The method, system, use or composition according to any one of claims 1 to 15, wherein: At least a portion of the cellulosic reactant composition is derived directly or indirectly from pyrolysis of recycled waste, and / or by cracking r-pyrolysis oil to obtain an r-CR composition.

21. The method, system, use or composition according to any one of claims 1 to 15, wherein: The cellulose reactant composition fed to the reaction vessel contains no recycled content.

22. The method, system, use or composition according to any one of claims 1 to 15, wherein: At least 0.1 wt. % of the CR composition fed to the reaction vessel comprises r-CR derived directly or indirectly from cracked r-pyrolysis oil or from r-pyrolysis gas.

23. The method, system, use or composition according to any one of claims 1 to 15, wherein: The CE composition has associated therewith, or contains, or is labeled, advertised, or certified as containing recycled content in an amount of at least 0.01 wt. %, based on the weight of the CE composition.

24. The method, system, use or composition of any one of claims 1-15, wherein the recycled content value is applied to the CE by subtracting it from a recycled inventory or reacting r-CR to make r-CE.

25. The method, system, use or composition according to any one of claims 1 to 15, wherein: The method for allocating recycled content among products manufactured by a cellulose ester manufacturer or products manufactured by any one entity or combination of entities in a family of entities of which the cellulose ester manufacturer is a part is a symmetrical distribution of recycled content values ​​among its products, and optionally at least one of the products is a cellulose ester.

26. The method, system, use or composition according to any one of claims 1 to 15, wherein: The recycled content input or generation (recycled content feedstock or quota) is to a first site, and the recycled content value from the input is transferred to a second site and applied to one or more products prepared at the second site, and at least one of the products prepared at the second site is a cellulose ester, and optionally at least a portion of the recycled content value is applied to the cellulose ester product prepared at the second site.

27. The method, system, use or composition according to any one of claims 1 to 15, wherein: The method for allocating recycled content between products manufactured by the CE manufacturer or by any one entity or combination of entities in a family of entities of which the CE manufacturer is a part is applied symmetrically or asymmetrically between other products prepared at the CE and the second site.

28. The method, system, use or composition according to any one of claims 1 to 15, wherein: The CR supplier transfers the recycling component quota to the CE manufacturer and transfers the CR supply to the CE manufacturer.

29. The method, system, use or composition according to any one of claims 1 to 15, wherein: The recycling component quota is not associated with the supplied CR.

30. The method, system, use or composition according to any one of claims 1 to 15, wherein: Said recycled content quota transferred by the CR supplier to the CE manufacturer is related to or obtained from products other than CR that are derived directly or indirectly from the pyrolysis of recycled waste or from recycled content of any downstream compound obtained from the pyrolysis of recycled waste.

31. The method, system, use or composition of claim 30, wherein: Such products, other than CR, contain r-ethylene, r-propylene, r-butadiene, r-aldehydes, r-alcohols or r-benzene.

32. The method, system, use or composition of any one of claims 1 to 15, wherein: The CR supplier transfers a recycling content quota to the CE manufacturer and supplies the CR to the CE manufacturer, the recycling content quota being associated with the CR manufactured by the supplier.

33. The method, system, use or composition according to any one of claims 1 to 15, wherein: The supplied CR is r-CR, and at least a portion of the recycled content quota being transferred is recycled content in the supplied r-CR.

34. The method, system, use or composition according to any one of claims 1 to 15, wherein: The quota is obtained by the CE manufacturer (or its family of entities) from any individual or entity without obtaining the supply of CR from the individual or entity.

35. The method, system, use or composition according to any one of claims 1 to 15, wherein: The person or entity transfers the products other than the CR to the CE manufacturer along with a recycling credit.

36. The method, system, use or composition of any one of claims 1 to 15, wherein: The CE manufacturer deposits the quota into recycling stock.

37. The method, system, use or composition of any one of claims 1 to 15, wherein: Any person or entity in the CE manufacturer or its family of entities: a. deposit the allowance 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 CE manufactured by the CE 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. Applying the recycled content value to the CE removed from the recycled stock.

38. The method, system, use or composition of any one of claims 1 to 15, wherein: The recycled content value applied to CE removed from recycled stock is derived directly or indirectly from the pyrolysis of recycled waste.

39. The method, system, use or composition of any one of claims 1 to 15, wherein: A recycling stock of allowances is created having multiple sources from which allowances are created, wherein the recycling stock traces back or accounts for the source or basis of the allowances stored in the recycling stock.

40. The method, system, use or composition of any one of claims 1-15, wherein: The CE manufacturer or a person or entity in its family of entities receives a supply and quota of CRs and at least part of said quota: a. Applied to CE prepared from the supplied CR; b. applied to CE not prepared from the supply of CR; or c. depositing into the recovery stock, deducting the recovery component value from the recovery stock, and applying at least a portion of the recovery component value to: i.CE, thereby obtaining r-CE, or ii. a compound or composition other than CE, or iii. Both; or d. Deposit into recovery stock and store.

41. The method, system, use or composition of any one of claims 1 to 15, wherein: r-CR is used to prepare the r-CE composition.

42. The method, system, use or composition of any one of claims 1-15, wherein: The recycled content value is obtained by subtracting it from the recycled stock.

43. The method, system, use or composition of any one of claims 1-15, wherein: A recovered component value subtracted from the recovered inventory is applied to the CE and products or compositions other than the CE.

44. The method, system, use or composition of any one of claims 1-15, wherein: The total amount of recycled content in the CE corresponds to the amount of recycled content value deducted from the recycled stock.

45. The method, system, use or composition of any one of claims 1-15, wherein: An individual owns an r-CE and increases the recycled content value in the r-CE by applying the recycled content value deducted from the recycled stock to the r-CE.

46. ​​The method, system, use or composition of any one of claims 1-15, wherein: The allowances in the recycling stock are assigned to different units of measurement, or are placed in unique modules, unique spreadsheets, unique columns or rows, unique databases, or have unique markers associated with the units of measurement, or a combination thereof, to distinguish a. The source of the technology used to create the quota, or b. The type of compound having a recycled component from which the allocated amount is obtained, or c. Supplier or site identification, or d. combinations thereof.

47. The method, system, use or composition of any one of claims 1-15, wherein: The allowances are deposited into the recycled stock and the recycled content value applied to the CE from the recycled stock is not obtained from allowances whose source is pyrolytic recycled waste.

48. The method, system, use or composition of any one of claims 1 to 15, comprising obtaining recycled content value derived directly or indirectly from pyrolysis recycled waste, such as derived from cracking of r-pyrolysis oil, or obtained from r-pyrolysis gas, or associated with r-composition, or associated with r-cellulose reactant, and: a. The portion without recovery component value is applied to the cellulose reactant composition to prepare CE, and applying at least a portion to CE to prepare r-CE; or b. Applying less than all of the portion to the cellulose reactant composition used to prepare CE, and storing the remainder in a recovery inventory or applying to future prepared CE or to existing CE in the recovery inventory.

49. The method, system, use or composition of any one of claims 1-15, wherein: Deducting the recycled content value from the recycled inventory includes adjusting the entry, removing, adding the entry as a loan item, an algorithm, or a combination thereof, which adjusts the input and output based on the amount of recycled content associated with the product and the cumulative amount of the allocated amount stored in the recycled inventory.

50. The method, system, use or composition of any one of claims 1-15, wherein: The application of the recycled content value includes the CE manufacturer shipping the CE to a customer and electronically delivering a recycled content credit or certification document to the customer, or by applying the recycled content value to a package or container containing the CE.

51. The method, system, use or composition according to any one of claims 1 to 15, wherein: a. Olefin Suppliers: i. cracking a cracker feed comprising a recycled pyrolysis oil to produce an olefin composition, at least a portion of which is obtained by cracking said recycled pyrolysis oil (r-olefins), or ii. preparing pyrolysis gas, at least part of which is obtained by pyrolysis of a recycled waste stream (r-pyrolysis gas), or iii. Both; and b. Cellulose ester manufacturers: i. obtaining quotas derived directly or indirectly from said r-olefins or said r-pyrolysis gas from a supplier or a third party that transfers said quotas, ii. preparing cellulose esters from a cellulose reactant, and iii. associating at least a portion of the quota with at least a portion of the cellulose ester, regardless of whether the cellulose reactant used to prepare the cellulose ester contained r-cellulose reactant.

52. The method, system, use or composition according to any one of claims 1 to 15, comprising: a. preparing r-olefins by cracking r-pyrolysis oil or separating olefins from r-pyrolysis gas; as well as b. converting at least a portion of the r-olefins in a synthesis process to produce a cellulose reactant, and c. converting at least a portion of any or said cellulose reactant into a cellulose ester; as well as d. applying the recycled content value to the cellulose ester to prepare r-CE; and e. Optionally, r-pyrolysis oil or r-pyrolysis gas or both are prepared by pyrolysis recovery of raw materials.

53. The method, system, use or composition of any one of claims 1-15, wherein: The kits include plastic or metal drums, railroad cars, tank containers, totes, plastic totes, IBC totes, bottles, jerry cans or plastic bags.

54. The method, system, use or composition according to any one of claims 1 to 15, wherein: The identifier includes a certification document, a product insert stating the recycled content; a label; a logo; or a certification mark from a certification body indicating that the article or packaging contains content or CE contains recycled content, or is made from a source or is associated with recycled content; or an electronic statement from a CE manufacturer accompanying a purchase order or product; or posted on a website as a statement, representation or logo indicating that CE contains a source associated with recycled content or is made from a source associated with recycled content or contains recycled content; or an advertisement transmitted electronically, through or in a website, by email, or through television, or through a trade show.

55. The method, system, use or composition according to any one of claims 1 to 15, comprising: a. cellulose esters ("CE"), and b. An identifier (eg, a credit, label, or certification) associated with the cellulose ester, the identifier being an indication that the cellulose ester has recycled content or is made from a source having recycled content.

56. The method, system, use or composition of any one of claims 1-15, wherein: The identifier is an electronic credit or certification that is electronically transferred to the consumer by the CE manufacturer in conjunction with the sale or transfer of the CE.

57. The method, system, use or composition of any one of claims 1-15, wherein: The identifier is an electronic recycled content credit derived directly or indirectly from pyrolytic recycled waste.

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