Recycled component cyclobutanediol polyester

Abstract

A method for preparing a recycled content polyester and a recycled content polyester composition comprising at least one polyester having at least one residue in the polyester derived from a recycled propylene composition are provided.

Description

Background Technology

[0001] There are well-known global problems with waste disposal, particularly for large quantities of consumer goods, such as plastics, textiles, and other polymers, which are considered non-biodegradable within acceptable timeframes. The public expects these types of waste to be incorporated into new products through recycling, reuse, or other means to reduce the amount of waste in circulation or landfills.

[0002] Consumer products in the market typically contain significant amounts of renewable, recyclable, reused, or other materials that will reduce carbon emissions, waste disposal, and other environmental sustainability issues.

[0003] Providing products with a significant content of renewable, recyclable, and reusable materials would be beneficial. Summary of the Invention

[0004] Polyesters are typically prepared by polycondensation or polyesterification of dicarboxylic acids and diols. Dicarboxylic acids and diols are typically derived from fossil fuel sources (e.g., petroleum, natural gas, coal). This invention provides a method for including recycled components in polyesters (e.g., polyesters containing cyclobutanediol residues) by providing polyesters made from organic compounds (e.g., acids and alcohols), said organic compounds being derived from recycled, reused, or other environmentally beneficial raw materials.

[0005] In one aspect, the present invention relates to a process for preparing a recycled polyester composition (r-polyester), comprising: (1) preparing a recycled propylene composition (r-propylene) from which a self-cracked recycled component pyrolysis oil composition (r-pyrolysis oil) is directly or indirectly derived; (2) using r-propylene as a raw material in a reaction scheme to produce at least one polyester reactant for preparing a polyester; and (3) reacting said at least one polyester reactant to prepare at least one polyester.

[0006] In another aspect, the present invention relates to the use of recycled propylene compositions (r-propylene) in the production of at least one polyester reactant. In embodiments, the present invention relates to the use of recycled propylene compositions (r-propylene) in the production of at least one polyester.

[0007] On the other hand, a polyester composition comprising at least one polyester having at least one monomer residue derived from a recycled propylene composition is provided.

[0008] In one aspect, articles comprising a polyester composition are provided. In embodiments, the articles are molded articles comprising polyester. In one embodiment, the molded articles are made of a thermoplastic composition comprising polyester. In one embodiment, the polyester is in the form of a moldable thermoplastic resin.

[0009] In another aspect, the present invention relates to an integrated method for preparing polyester, comprising the following processing steps: (1) preparing a recovered propylene composition (r-propylene) using a feedstock containing at least some amount of a recovered pyrolysis oil composition in a cracking operation; (2) preparing at least one chemical intermediate from said r-propylene; (3) reacting said chemical intermediate in a reaction scheme to prepare at least one polyester reactant for preparing polyester, and / or selecting said chemical intermediate as at least one polyester reactant for preparing polyester; and (4) reacting said at least one polyester reactant to prepare said polyester; wherein said polyester contains at least one monomer residue derived from r-propylene.

[0010] In the embodiments, processing steps (1) to (4), or (2) to (4), or (3) and (4) are performed in a fluid-connected system.

[0011] In an embodiment, a method for preparing a recycled polyester (r-polyester) is provided, the method comprising contacting a recycled component 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) (r-TMCD) with one or more dicarboxylic acids (or derivatives thereof) and (optionally) one or more other diols under conditions providing the r-polyester, wherein at least a portion of the r-TMCD is directly or indirectly derived from a cracked recycled component pyrolysis oil composition (r-pyrolysis oil).

[0012] In one embodiment, a method for obtaining recycled components of polyester is provided, comprising:

[0013] a. Obtain a TMCD composition designated as having a recycled component, and

[0014] b. Under conditions conducive to the efficient preparation of polyester, TMCD and one or more dicarboxylic acids (or their derivatives) and (optionally) one or more other diols are added to a reactor, and

[0015] Wherein, whether or not the designation indicates so, at least a portion of the TMCD composition is derived directly or indirectly from the cracked recovery pyrolysis oil composition (r-pyrolysis oil).

[0016] In the embodiments, a method for processing and recovering TMCD compositions is provided, at least a portion of which is directly or indirectly derived from cracked pyrolysis oil compositions (r-TMCD), the method comprising feeding r-TMCD and one or more dicarboxylic acids (or derivatives thereof) and (optionally) one or more other diols into a polycondensation and / or polyesterification reactor.

[0017] In this embodiment, an integrated process for preparing a polyester composition is provided, comprising:

[0018] a. Provide a TMCD manufacturing facility and prepare a recycled component TMCD composition (r-TMCD) from a feed composition, at least a portion of which is obtained through a reaction scheme starting with a recycled component propylene composition (r-propylene), wherein at least a portion of the r-propylene is generated by cracking and recovering pyrolysis oil, and

[0019] b. Provide a polyester manufacturing facility comprising a reactor containing one or more dicarboxylic acids (or derivatives thereof) and (optionally) one or more other diols that accept TMCD; and

[0020] c. Feeding r-TMCD from the TMCD manufacturing facility to the polyester manufacturing facility via a system in fluid communication between the facilities.

[0021] In one embodiment, an integrated system for the generation and consumption of recycled TMCD compositions is provided, comprising:

[0022] a. Provide a TMCD manufacturing facility adapted to prepare a recycled component TMCD composition (r-TMCD) from a feed composition, at least a portion of which is obtained through a reaction scheme starting with a recycled component propylene composition (r-propylene), wherein at least a portion of the r-propylene is generated by cracking and recovering pyrolysis oil, and

[0023] b. Provide a polyester manufacturing facility comprising a reactor containing one or more dicarboxylic acids (or derivatives thereof) and (optionally) one or more other diols that accept TMCD; and

[0024] c. A piping system connecting the two facilities, optionally with intermediate equipment or storage facilities, capable of removing TMCDs from the TMCD manufacturing facility and accepting TMCDs in the polyester facility.

[0025] In one embodiment, a method for introducing or establishing recycled components in a polyester is provided, comprising:

[0026] a. Obtain allocations or credits for recycled propylene compositions (r-propylene),

[0027] b. In the synthesis process, propylene is converted to prepare isobutyric acid and / or isobutyraldehyde, and isobutyraldehyde is converted to prepare isobutyric acid.

[0028] c. Optionally, isobutyric acid can be converted during the synthesis process to prepare isobutyric anhydride.

[0029] d. In the synthetic process, isobutyric anhydride and / or isobutyric acid are converted to prepare dimethyl ketone.

[0030] e. In the synthetic process, dimethyl ketene is converted to prepare TMCD.

[0031] f. Converting TMCD in the synthesis process to prepare polyester.

[0032] g. Specify that at least a portion of the polyester corresponds to at least a portion of the r-propylene allocation or credit amount, and optionally

[0033] h. To offer for sale or to sell polyester containing or obtained from the recycled components described below, wherein the recycled components correspond to the designation.

[0034] In one embodiment, a method for introducing or establishing recycled components in a polyester is provided, comprising:

[0035] a. A reaction scheme starting with propylene to obtain recovered TMCD (dr-TMCD), wherein at least a portion of the propylene is directly derived from cracked recovered pyrolysis oil (dr-propylene).

[0036] b. Prepare polyester using raw materials containing dr-TMCD.

[0037] c. Specify that at least a portion of the polyester is a recycled component containing at least a portion of the amount of dr-propylene contained in the feedstock corresponding to the reaction scheme, and optionally...

[0038] d. To offer for sale or to sell polyester containing or obtained from the recycled components described below, wherein the recycled components correspond to the designation.

[0039] In the embodiments, the use of recycled TMCD compositions that directly or indirectly derive self-cracked pyrolysis oil (r-TMCD) for the preparation of polyesters is provided.

[0040] In the embodiments, the use of recycled propylene composition (r-propylene) quotas is provided, including:

[0041] a. Converting propylene to prepare polyester in a synthetic process; and

[0042] b. Specify that at least a portion of the polyester corresponds to the r-propylene quota.

[0043] In one embodiment, a system is provided, comprising:

[0044] a. Polyester, and

[0045] b. A recycled component identifier associated with the polyester, the identifier indicating that the polyester contains or is derived from recycled components.

[0046] In one embodiment, a polyester composition is provided, comprising:

[0047] a. polyester; and

[0048] b. At least one impurity, including formaldehyde; chloromethane; nitrogen-containing compounds; acetone; methanol; acetaldehyde; oxygen-containing compounds other than acetone; methanol, CO and CO2; COS; or MAPD.

[0049] In an embodiment, a method for introducing impurities into a polyester composition is provided, comprising:

[0050] a. The reaction scheme involves preparing polyester starting from a first propylene feedstock; and

[0051] b. Providing a second propylene feedstock, at least a portion of which is obtained through cracking and recovery of pyrolysis oil and contains impurities not present in or present in greater quantities than those present in the first propylene feedstock, and which originate from the cracking of the recovered pyrolysis oil; and

[0052] c. The preparation of a polyester composition comprising polyester and impurities by step (b); and

[0053] d. Optionally, the polyester composition containing impurities can be recycled.

[0054] In one embodiment, a method for preparing polyester is provided, comprising:

[0055] a. Preparation of a recovered pyrolysis oil composition via pyrolysis recovery feed (r-pyrolysis oil); and

[0056] b. Cracking r-pyrolysis oil to prepare a first recovered propylene composition, at least a portion of which is obtained from cracked r-pyrolysis oil (r-propylene); and

[0057] c. In the synthesis process, at least a portion of γ-propylene is converted to prepare isobutyric acid and / or isobutyraldehyde, and isobutyraldehyde is converted to prepare isobutyric acid, and

[0058] d. Optionally, at least a portion of the isobutyric acid is converted during the synthesis process to prepare isobutyric anhydride, and

[0059] e. In the synthetic process, at least a portion of isobutyric acid and / or isobutyric anhydride is converted to prepare dimethyl ketene, and

[0060] f. In the synthetic process, dimethyl ketene is converted to prepare TMCD; and

[0061] g. React TMCD with a dicarboxylic acid (or a derivative thereof) and optionally another diol to prepare a polyester.

[0062] In an embodiment, a method for processing a recycled propylene composition is provided, at least a portion of which is directly or indirectly derived from a cracked recycled pyrolysis oil composition (r-propylene). The method includes a reaction scheme starting with the r-propylene to produce polyester, wherein the recycled pyrolysis oil is obtained by pyrolyzing a waste stream that contains no non-kosher material (or contains only post-industrial material).

[0063] In the embodiments, polyester compositions obtained by any of the methods described herein are provided.

[0064] In another aspect, the present invention relates to providing a recycled TMCD composition (r-TMCD). In embodiments, r-TMCD can be used as a polyester reactant.

[0065] A method for preparing TMCD (r-TMCD) is also provided, the method comprising carboxylating a recovered propylene composition (r-propylene) to produce a carboxylated effluent containing isobutyric acid, converting the isobutyric acid in a synthetic reaction scheme to prepare TMCD, wherein the r-propylene is derived directly or indirectly from cracked r-pyrolysis oil.

[0066] A method for preparing recycled TMCD (r-TMCD) is also provided, the method comprising hydroformylating a recycled propylene composition (r-propylene) to thereby produce a hydroformylated effluent containing isobutyraldehyde (r-isobutyraldehyde), and oxidizing r-isobutyraldehyde to thereby produce an oxidized effluent containing isobutyric acid (r-isobutyric acid), converting r-isobutyric acid in a synthetic reaction scheme to prepare TMCD, wherein the r-isobutyraldehyde and r-isobutyric acid are produced from the recycled propylene composition (r-propylene), and the r-propylene is directly or indirectly derived from a cracked recycled pyrolysis oil composition (r-pyrolysis oil).

[0067] A method for obtaining recycled components in a TMCD is also provided, the method comprising:

[0068] a. Obtaining a propylene composition designated as having recycled components, and

[0069] b. Under conditions conducive to the efficient preparation of isobutyric acid, the propylene is fed into the reactor, and

[0070] c. Under conditions conducive to the efficient preparation of TMCD, react the isobutyric acid in the reaction scheme.

[0071] Wherein, whether or not such designation is made, at least a portion of the propylene composition is derived directly or indirectly from the cracking recovery pyrolysis oil composition.

[0072] A method for obtaining recycled components in a TMCD is also provided, the method comprising:

[0073] a. Obtaining an isobutyric acid composition designated as having a recyclable component, and

[0074] b. Under conditions suitable for the efficient preparation of TMCD, the isobutyric acid is used as a starting material in the reaction scheme, and

[0075] Wherein, whether or not the designation is so specified, at least a portion of the isobutyric acid is generated from a recovered propylene composition derived directly or indirectly from a cracked recovered pyrolysis oil composition (r-pyrolysis oil).

[0076] In addition, a method for processing a recycled propylene composition, at least a portion of which is directly or indirectly derived from cracked recycled pyrolysis oil (r-propylene), is now provided. The method includes feeding r-propylene into a carboxylation reaction in which isobutyric acid is prepared, and converting isobutyric acid in a synthetic reaction scheme to prepare TMCD.

[0077] In addition, a method is now provided for processing recycled isobutyraldehyde (r-isobutyraldehyde) generated from a recycled propylene composition, at least a portion of which is directly or indirectly derived from a self-cracked recycled pyrolysis oil composition (r-propylene), the method comprising feeding r-isobutyraldehyde into an oxidation reactor, preparing isobutyric acid in the oxidation reactor, and converting r-isobutyric acid in a synthesis reaction scheme to prepare TMCD.

[0078] This process can also be an integrated process for fabricating TMCDs, including:

[0079] a. Providing a propylene manufacturing facility and preparing a propylene composition, at least a portion of which is derived from cracked pyrolysis oil (r-propylene), and

[0080] b. Provide isobutyric acid manufacturing facilities, including reactors that accept propylene; and

[0081] c. Feeding r-propylene from the propylene manufacturing facility to the isobutyric acid manufacturing facility via a system in fluid communication between the facilities.

[0082] d. Utilize at least a portion of isobutyric acid in the reaction scheme used to prepare TMCD.

[0083] An integrated system for generating and consuming recycled propylene compositions is also provided, comprising:

[0084] a. A propylene manufacturing facility suitable for preparing propylene compositions, at least a portion of which is derived from cracked recovery pyrolysis oil (r-propylene), and

[0085] b. Provide isobutyric acid manufacturing facilities, including reactors that accept propylene; and

[0086] c. A piping system connecting the two facilities, optionally including intermediate equipment or storage facilities, capable of removing propylene from the propylene production facility and receiving propylene in the isobutyric acid facility; and

[0087] d. Utilize at least a portion of isobutyric acid in the reaction scheme used to prepare TMCD.

[0088] A method for introducing or establishing a recyclable component in a TMCD includes:

[0089] a. Obtain allocations or credits for recycled propylene compositions (r-propylene),

[0090] b. In the synthetic process, propylene is converted to prepare isobutyric acid.

[0091] c. In the synthetic process, isobutyric acid is converted to prepare TMCD.

[0092] d. Specify that at least a portion of the TMCD corresponds to at least a portion of the r-propylene allocation or credit amount, and optionally...

[0093] e. Promising to sell or selling a TMCD containing or obtained from the following recycled ingredients, which correspond to the specified ingredient.

[0094] A method for introducing or establishing recycled components in a TMCD is also provided, including:

[0095] a. A propylene supplier whose cracking process includes recovering pyrolysis oil from a cracker feedstock to prepare a propylene composition, at least a portion of which is obtained by cracking the recovered pyrolysis oil (r-propylene).

[0096] b. Compound manufacturers:

[0097] i. Obtain the allocation or credit associated with the r-propylene from the supplier or a third party transferring the allocation or credit.

[0098] ii. Preparation of TMCD from propylene or reaction schemes starting from propylene, and

[0099] iii. Regardless of whether the propylene used to prepare the TMCD contains γ-propylene molecules, at least a portion of the allocation or credit amount shall be associated with at least a portion of the TMCD.

[0100] A method for introducing or establishing recycled components in a TMCD is also provided, including:

[0101] a. Obtaining a recovered propylene composition, at least a portion of which is directly derived from cracked recovered pyrolysis oil (dr-propylene),

[0102] b. In the reaction scheme, TMCD is prepared using a starting material containing dr-propylene.

[0103] c. Specify at least a portion of the TMCD as containing a recovered component corresponding to at least a portion of the amount of dr-propylene contained in the feedstock, and optionally...

[0104] d. To offer for sale or to sell a TMCD containing or obtained from the following recycled ingredients, which correspond to the designation.

[0105] It also provides the use of recovered propylene compositions that directly or indirectly derive from self-cracked pyrolysis oil (r-propylene), including the conversion of r-propylene in a synthetic process scheme to prepare TMCD.

[0106] It also provides the use of recovered isobutyric acid compositions (r-isobutyric acid) derived from recovered propylene compositions directly or indirectly derived from self-cracked recovered pyrolysis oil (r-propylene), including the conversion of r-isobutyric acid in a synthetic process scheme to prepare TMCD.

[0107] It also provides new uses for recycled propylene composition (r-propylene) quotas, including:

[0108] a. In the synthetic process, propylene or propylene-derived intermediates are converted to prepare TMCD, and

[0109] b. Specify that at least a portion of the TMCD corresponds to the r-propylene quota.

[0110] Additionally, a system is provided, comprising:

[0111] a.TMCD, and

[0112] b. A recycled ingredient identifier associated with the TMCD, the identifier indicating that the TMCD contains or is derived from a recycled ingredient.

[0113] The composition of a TMCD can also be different. One TMCD composition includes:

[0114] a.TMCD; and

[0115] b. At least one impurity comprising formaldehyde, dichloromethane, or a hydroxyl condensation product thereof.

[0116] A method for introducing impurities into a TMCD composition is also provided, comprising:

[0117] a. Preparation of TMCD using a first propylene feedstock; and

[0118] b. Providing a second propylene feedstock, at least a portion of which is obtained through cracking and recovery of pyrolysis oil and contains impurities not present in or present in greater quantities than those present in the first propylene feedstock, and which originate from the cracking of the recovered pyrolysis oil; and

[0119] c. Prepare a TMCD composition comprising the TMCD and the impurities from step (b); and

[0120] d. Optionally, the TMCD composition containing the impurities may be recovered.

[0121] A method for introducing impurities into a TMCD composition is also provided, comprising:

[0122] a. Preparation of isobutyric acid from a first propylene feedstock; and

[0123] b. Providing a second propylene feedstock, at least a portion of which is obtained through cracking and recovery of pyrolysis oil and contains impurities not present in or present in greater quantities than those present in the first propylene feedstock, and which originate from the cracking of the recovered pyrolysis oil; and

[0124] c. The isobutyric acid composition comprising isobutyric acid and the impurities prepared by step (b); and

[0125] d. Preparing a TMCD composition from the isobutyric acid composition, wherein the TMCD composition comprises TMCD and the impurity; and

[0126] e. Optionally, the TMCD composition containing the impurities may be recovered.

[0127] A method for preparing TMCD from raw materials (cradle) to a final product is also provided, comprising:

[0128] a. Preparation of a recovered pyrolysis oil composition via pyrolysis recovery feed (r-pyrolysis oil); and

[0129] b. Cracking r-pyrolysis oil to prepare a first recovered propylene composition, at least a portion of which is obtained from cracked r-pyrolysis oil (r-propylene); and

[0130] c. Converting at least a portion of the r-propylene in a synthetic process to prepare a recovered isobutyric acid composition (r-isobutyric acid); and

[0131] d. In a synthetic process, at least a portion of the isobutyric acid is converted to prepare TMCD.

[0132] TMCD compositions obtained by any of the methods described herein are also provided. Attached Figure Description

[0133] Figure 1This is a diagram illustrating a process for preparing an r-composition from one or more recycled component compositions using a recycled component pyrolysis oil composition (r-pyrolysis oil).

[0134] Figure 2 This is an illustration of an exemplary pyrolysis system that at least partially converts one or more recycled wastes, particularly recycled plastic waste, into a variety of useful r-products.

[0135] Figure 3 This is a schematic diagram of the pyrolysis process used to produce olefin-containing products.

[0136] Figure 4 This is a flow diagram showing the steps associated with the cracking furnace and separation zone of a system for producing r-compositions obtained from cracked r-pyrolysis oil and non-recovery cracker feed.

[0137] Figure 5 This is a schematic diagram of a cracking furnace suitable for receiving r-pyrolysis oil.

[0138] Figure 6 A furnace tray tube structure with multiple tubes is shown.

[0139] Figure 7 The various feed points for r-pyrolysis oil to enter the cracking furnace are shown.

[0140] Figure 8 A cracking furnace with a vapor-liquid separator is shown.

[0141] Figure 9 This is a block diagram illustrating the treatment of the effluent from the recovery component furnace.

[0142] Figure 10 A fractionation scheme for separating and isolating the main r-compositions is shown, including a demethanizer, a deethaner, a depropanizer, and a fractionation column. The main r-compositions include r-propylene, r-ethylene, r-butene, etc.

[0143] Figure 11 A laboratory-scale cracking unit design is shown.

[0144] Figure 12 The design features of a plant-based experimental feed of r-pyrolysis oil into a gas-feed cracker are described.

[0145] Figure 13 This is a boiling point curve of γ-pyrolysis oil obtained by gas chromatography, containing 74.86% C8+, 28.17% C15+, 5.91% aromatics, 59.72% alkanes, and 13.73% unidentified components.

[0146] Figure 14 This is a boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0147] Figure 15 This is a boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0148] Figure 16 This is a boiling point curve of the r-pyrolysis oil obtained by distillation and chromatographic analysis in the laboratory.

[0149] Figure 17 A boiling point curve for γ-pyrolysis oil distilled in the laboratory, wherein at least 90% of the boiling point is at 350°C, 50% of the boiling point is between 95°C and 200°C, and at least 10% of the boiling point is at 60°C.

[0150] Figure 18 A boiling point curve for γ-pyrolysis oil distilled in the laboratory, wherein at least 90% of the boiling point is at 150°C, 50% of the boiling point is between 80°C and 145°C, and at least 10% of the boiling point is at 60°C.

[0151] Figure 19 A boiling point curve for γ-pyrolysis oil distilled in the laboratory, wherein at least 90% boiling point is at 350°C, at least 10% boiling point is at 150°C, and 50% boiling point is between 220°C and 280°C.

[0152] Figure 20 This is a boiling point curve of γ-pyrolysis oil distilled in a laboratory at 250-300°C, where 90% of the boiling point is between 250-300°C.

[0153] Figure 21 This is a boiling point curve of γ-pyrolysis oil distilled in a laboratory with 50% boiling point between 60-80℃.

[0154] Figure 22 This is a boiling point curve of γ-pyrolysis oil distilled in a laboratory with an aromatic hydrocarbon content of 34.7%.

[0155] Figure 23 This is a boiling point curve of r-pyrolysis oil with an initial boiling point of about 40°C.

[0156] Figure 24 This is a graph showing the carbon distribution of the pyrolysis oil used in the factory test.

[0157] Figure 25 This is a graph showing the carbon distribution of the pyrolysis oil used in the factory test. Detailed Implementation

[0158] The terms “containing” and “including” are synonymous with “comprising.” When indicating a sequence of numbers, it should be understood that each number is modified to be the same as the first or last number in the sequence or sentence; for example, each number is “at least,” “up to,” or “no more than”, depending on the context; and each number is in an “or” relationship. For example, “at least 10, 20, 30, 40, 50, 75 wt.%…” means the same as “at least 10 wt.%, or at least 20 wt.%, or at least 30 wt.%, or at least 40 wt.%, or at least 50 wt.%, or at least 75 wt.%”; and “no more than 90 wt.%, 85, 70, 60…” means the same as “no more than 90 wt.%, or no more than 85 wt.%, or no more than 70 wt.%…”; and “at least 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% by weight…” This refers to the same as "at least 1 wt.%, or at least 2 wt.%, or at least 3 wt.%..." etc.; and "at least 5, 10, 15, 20 and / or not more than 99, 95, 90 weight percent" refers to the same as "at least 5 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, and / or not more than 99 wt.%, or not more than 95 wt.%, or not more than 90 weight percent..." etc.; or "at least 500, 600, 750°C..." refers to the same as "at least 500°C, or at least 600°C, or at least 750°C..." etc.

[0159] In several respects, methods for preparing recycled propionaldehyde are provided, which begin by feeding a recycled ethylene composition (“r-ethylene”) into a reactor for preparing propionaldehyde, wherein the r-ethylene is derived directly or indirectly from cracked r-pyrolysis oil.

[0160] Pyrolysis / cracking systems and processes

[0161] Unless otherwise stated, all concentrations or amounts are by weight. "Olefins-containing effluent" is furnace effluent obtained by cracking a cracker feed containing γ-pyrolysis oil. "Non-recovery olefins-containing effluent" is furnace effluent obtained by cracking a cracker feed not containing γ-pyrolysis oil. Hydrocarbon mass flow rates, MF1 and MF2 are in thousands of pounds per hour (klb / hr), unless otherwise stated, are molar flow rates.

[0162] Figure 1 This is an illustration of an example or a combination thereof of a process for preparing one or more recycled component compositions (e.g., ethylene, propylene, butadiene, hydrogen, and / or pyrolytic gasoline) (r-composition) from a recycled component pyrolysis oil composition (r-pyrolysis oil).

[0163] like Figure 1 As shown, recycled waste can be pyrolyzed in pyrolysis unit 10 to produce pyrolysis products / effluents containing a pyrolysis oil composition (r-pyrolysis oil) of recycled components. The r-pyrolysis oil can be fed into cracker 20 along with non-recycled cracker feed (e.g., propane, ethane, and / or natural gasoline). Recyclable cracked effluents (r-cracking effluents) can be generated from the cracker and then separated in 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-cracking effluents. The r-propylene stream may contain predominantly propylene, while the r-ethylene stream may contain predominantly ethylene.

[0164] As used herein, the furnace includes a convection zone and a radiation zone. The convection zone includes tubes and / or coils inside the convection chamber, which may also continue outside the convection chamber downstream of the coil inlet at the inlet of the convection chamber. For example, as Figure 5 As shown, convection zone 310 includes coils and pipes within convection box 312, and may optionally extend outside convection box 312 and return to or interconnect with pipes 314 within convection box 312. Radiation zone 320 includes radiant coils / pipes 324 and burner 326. Convection zone 310 and radiation zone 320 may be contained in a single integral box or in separate discrete boxes. Convection box 312 need not be a separate discrete box. Figure 5 As shown, the convection box 312 is integrated with the combustion chamber 322.

[0165] Unless otherwise stated, all component quantities provided herein (e.g., for feed, raw material, stream, composition and product) are expressed on a dry basis.

[0166] As used herein, “r-pyoil” or “r-pyrolysis oil” are interchangeable and refer to a composition of substances that is liquid when measured at 25°C and 1 atmosphere, and at least a portion thereof is derived from the cracking of recycled waste (e.g., waste plastics or waste streams).

[0167] As used herein, “r-ethylene” means a composition comprising: (a) ethylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) ethylene having a recovery component value attributable to at least a portion of the ethylene; and “r-propylene” means a composition comprising: (a) propylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) propylene having a recovery component value at least a portion of the propylene.

[0168] The reference to "r-ethylene molecule" refers to ethylene molecules directly derived from cracked feedstock containing r-pyrolysis oil. The reference to "r-propylene molecule" refers to propylene molecules directly derived from cracked feedstock containing r-pyrolysis oil.

[0169] As used herein, the term "major" means greater than 50% by weight, unless expressed as a mole percentage, in which case it means greater than 50 mol%. For example, a stream, composition, feedstock, or product that is majorly propane is a stream, composition, feedstock, or product containing greater than 50% by weight of propane, or, if expressed as mol%, a product containing greater than 50 mol% propane.

[0170] As used herein, the term “recycled component” is used as i) as a noun to refer to a physical component (e.g., a compound, molecule, or atom) derived from r-pyrolysis oil or ii) as an adjective to modify a particular composition (e.g., a feedstock or product) in which at least a portion is directly or indirectly derived from r-pyrolysis oil.

[0171] As used herein, compositions “directly derived from” cracked pyrolysis oil have at least one physical component traceable to the r-composition, at least a portion of which is obtained from or together with cracked r-pyrolysis oil, while compositions “indirectly derived from” cracked r-pyrolysis oil have an associated amount of recycled components and may or may not contain physical components traceable to the r-composition, at least a portion of which is obtained from or together with cracked r-pyrolysis oil.

[0172] "Recovery component value" is a unit of measurement representing the amount of material derived from γ-pyrolysis oil. The recovery component value can originate from any type of γ-pyrolysis oil and any type of cracking furnace used to crack the γ-pyrolysis oil.

[0173] Specific recovered component values ​​can be determined by mass balance methods, mass ratios, percentages, or any other units of measurement, and can be determined according to any system used for tracing, allocating, and / or storing recovered components in various compositions. The recovered component value can be deducted from the recovered component inventory and applied to the product or composition to attribute the recovered component to the product or composition. Unless otherwise stated, the recovered component value does not necessarily originate from the manufacture or cracking of r-pyrolysis oil. In one embodiment, or in combination with any of the mentioned embodiments, at least a portion of the r-pyrolysis oil from which the quota is obtained is also cracked in a cracking furnace as described throughout one or more embodiments herein.

[0174] In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the recovered component amount or value stored in the recovered component stock is obtained from the r-pyrolysis oil. Desiredly, at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at most 100% of the following:

[0175] a. quota, or

[0176] b. Stored in the inventory of recycled components, or

[0177] c. The value of recovered components in the inventory of recovered components, or

[0178] d. The value of the recovered component used in the composition to prepare the recovered component product, intermediate or article (recovered PIA) is obtained from the r-pyrolysis oil.

[0179] A recycled PIA can be a product, intermediate, or article that may include a compound or a composition containing a compound or polymer, and / or an article having an associated recycled component value. A PIA does not have an associated recycled component value. As used herein, the terms “recycled component quota” or “quota” refer to the recycled component value transferred from a starting composition to a receiving composition (the composition receiving the quota), at least a portion of which is obtained from or together with cracked r-pyrolysis oil, the receiving composition may or may not have traceable physical components to the composition, at least a portion of which is obtained from or together with cracked r-pyrolysis oil, wherein the recycled component value (whether by mass, percentage, or any other unit of measurement) is determined according to a standard system used to trace, allocate, and / or record recycled components in various compositions. A “composition” receiving a quota or recycled component value can include a composition of substances, compounds, products, polymers, or articles.

[0180] "Recycled component quota" or "quota" refers to the value of recycled components, which:

[0181] a. Transfer from r-pyrolysis oil or recycled waste used to prepare r-pyrolysis oil (collectively referred to herein as "r-pyrolysis oil") to a receiving composition or recycled PIA, said receiving composition or recycled PIA may or may not have a physical composition traceable to r-pyrolysis oil; or

[0182] b. Stored in the stock of recycled components, at least a portion of which is derived from r-pyrolysis oil.

[0183] Quotas can be allocations or credits. In one embodiment or in combination with any of the embodiments mentioned herein, the composition receiving a recovery component allocation can be a non-recovery composition, thereby converting the non-recovery composition into an r-composition. As used herein, "non-recovery" means a composition that is not directly or indirectly derived from the cracking of r-pyrolysis oil. As used herein, in the context of feed to a cracker or furnace, "non-recovery feed" means a feed that is not obtained from a waste stream or r-pyrolysis oil. Once a non-recovery feed or PIA receives a recovery component allocation (e.g., via credits or allocations), it becomes a recovered component feed, composition, or recovered PIA.

[0184] As used herein, the term "recycled ingredient allocation" refers to a type of recycled ingredient allocation in which an 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 an allocation, at least a portion of which may be associated with the composition sold or transferred by the supplying individual or entity to the receiving individual or entity. The supplying entity or individual may be controlled by the same person or entity or by various affiliates ultimately at least in part by a parent entity ("entity family"), or they may come from different entity families. Typically, the recycled ingredient allocation travels with the composition and its downstream derivatives. The allocation may be deposited into a recycled ingredient stock and withdrawn as an allocation from the recycled ingredient stock, and applied to the composition to prepare an r-composition or recycled PIA.

[0185] The term “recycled component credit” refers to a recycled component credit that is not limited to being associated with compositions made from cracked r-pyrolysis oil or its downstream derivatives, but has the flexibility to be obtained from r-pyrolysis oil and (i) be applied to compositions or PIAs made by processes other than cracking feedstocks in a furnace, or (ii) be applied to downstream derivatives of compositions made by processes other than cracking feedstocks in a furnace, or (iii) be sold or transferred to individuals or entities other than the quota owner, or (iv) be sold or transferred to individuals other than the composition supplier to the receiving entity or individual. For example, a quota may be a credit when it is obtained from r-pyrolysis oil and applied by the quota owner to a BTX composition or its fraction, which is manufactured by the owner or within its family of entities, obtained through refining and fractionation of petroleum rather than through cracker effluent products; or it may 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 compositions of the third party.

[0186] Credit lines can be sold, transferred, or used, or be sold, transferred, or used, or:

[0187] a. Do not sell the composition, or

[0188] b. Selling or transferring the composition, but the quota is not related to the sale or transfer of the composition, or

[0189] c. Storing into or removing from a recycled stock, wherein the recycled stock does not trace the molecules of the recycled raw materials to the molecules of the resulting composition prepared from the recycled raw materials, or the recycled stock has such traceability but does not trace the specific quota applied to the composition.

[0190] In one embodiment or in combination with any of the mentioned embodiments, quotas can be stored in a recovered component stock, and credits or allocations can be drawn from the stock and applied to the composition. This would be a situation where quotas are generated from r-pyrolysis oil and stored in a recovered component stock, and a recovered component value is deducted from the recovered component stock and applied to the composition to prepare an r-composition that does not contain a portion of products derived from a cracking furnace, or contains a portion of products derived from a cracking furnace, but such products constituting that portion of the composition are not obtained by cracking r-pyrolysis oil. In this system, it is not necessary to trace the source of the reactants to the olefin-containing effluent of the cracked r-pyrolysis oil or to any atoms contained in the olefin-containing effluent of the r-pyrolysis oil; instead, any reactants produced by any process can be used and associated with the recovered component allocation.

[0191] In one embodiment or in combination with any of the mentioned embodiments, a quota of the composition is received as a feedstock to prepare downstream derivatives of the composition, and such a composition is a product of cracking a cracker feedstock in a cracker furnace. In one embodiment or in combination with any of the mentioned embodiments, a process is provided in which:

[0192] a. Obtain r-pyrolysis oil,

[0193] b. Obtain the recovery component value (or quota) from r-pyrolysis oil and

[0194] i. Deposit into the recycled ingredient stock, withdraw quotas (or credits) from the recycled ingredient stock and apply them to any composition to obtain an r-composition, or

[0195] ii. Apply directly to any composition without storing it in the recycled component stock to obtain an r-composition; and

[0196] c. Optionally, at least a portion of the r-pyrolysis oil is cracked in a cracking furnace according to any of the designs or processes described herein; and

[0197] d. Optionally, at least a portion of the composition in step b is derived from cracker feedstock in a cracker furnace, and optionally, the composition has been obtained from any of the feedstocks comprising r-pyrolysis oil and the method described herein.

[0198] Steps b. and c. do not necessarily occur simultaneously. In one embodiment or in combination with any of the mentioned embodiments, 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. This process allows for the passage of time between the time when an entity or individual receives r-pyrolysis oil and generates quotas (which may occur upon receipt or possession of r-pyrolysis oil or its storage in stock) and the actual processing of the r-pyrolysis oil in the cracking furnace.

[0199] As used herein, “recycle content inventory” and “inventory” refer to a group or set of quotas (allocations or credits) from which the deposits and deductions of quotas under any unit can be traced. Inventory can be in any form (electronic or paper), using one or more software programs, or using various modules or applications (which together trace deposits and deductions as a whole). Desiredly, the total amount of recycled content removed (or applied to the composition) does not exceed the total amount of recycled content allocated to or deposited in the recycled content inventory (from any source, not just 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 a 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 effluent manufacturer or a member of its entity family, or alternatively, rebalancing can be performed within one (1) year, six (6) months, three (3) months, or one (1) month of achieving a deficit. The timing of depositing quotas into the recycled component stock, applying quotas (or credits) 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 recycled component value or quota from that volume of r-pyrolysis oil is deposited into the recycled component stock. Furthermore, the quota or recycled component value removed from the recycled component stock does not need to be traceable to the r-pyrolysis oil or cracked r-pyrolysis oil, but can be obtained from any waste recovery stream and any method from processing recycled waste streams. Desiredly, at least a portion of the recycled component value in the recycled component stock is obtained from the 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 recycled component value is deposited into the recycled component stock) is also processed by any or more of the cracking processes described herein.

[0200] The determination of whether an r-composition is directly or indirectly derived from cracked r-pyrolysis oil is not based on the presence of intermediate steps or entities in the supply chain, but on whether at least a portion of the r-composition fed into the reactor used to prepare the final product is traceable to the r-composition prepared by cracking r-pyrolysis oil.

[0201] As described above, the final product is considered directly derived from the cracked r-pyrolysis oil if at least a portion of the atoms or molecules in the reactant feedstock used to prepare the product can be traced via one or more intermediate steps or entities back to at least a portion of the atoms or molecules constituting the r-composition generated during the feeding of the r-pyrolysis oil into the cracker. Any number of intermediates and intermediate derivatives can be prepared prior to the preparation of the r-composition. R-composition manufacturers typically sell such r-compositions to intermediate entities after refining and / or purifying and compressing them to produce a specific grade of the desired r-composition. These intermediate entities then sell the r-composition or one or more derivatives thereof to another intermediate entity for the preparation of intermediate products, or directly to the product manufacturer. Any number of intermediates and intermediate derivatives can be prepared prior to the preparation of the final product. The actual volume of the r-composition, whether condensed as a liquid, supercritical, or stored as a gas, can remain in the equipment in which it was prepared, or can be transported to different locations, or maintained in off-site storage facilities before use by intermediate or product manufacturers. For traceability purposes, once an r-composition obtained from cracked r-pyrolysis oil is mixed with another volume of composition (e.g., r-ethylene mixed with non-recovered ethylene) in, for example, a storage tank, salt dome, or cave, the entire tank, dome, or cave becomes a source of the r-composition, and for traceability purposes, the extract from such storage facility is removed from the source of the r-composition until, after the feeding of the r-composition into the tank is stopped, the entire volume or stock of the storage facility is flipped or removed and / or replaced with the non-recovered composition.

[0202] If an r-composition is associated with a recoverable component quota and may or may not contain physical components traceable to the r-composition, then the r-composition is considered to be indirectly derived from r-pyrolysis oil, at least a portion of which is obtained through or accompanied by the cracking of the r-pyrolysis oil. For example, (i) a product manufacturer may operate within a legal framework, or an association framework, or an industry-recognized framework, to claim recoverable components through a system of credits, for example, transferred to the product manufacturer, regardless of where or from whom the r-composition, or its derivatives, or reactant feedstocks used to manufacture the product, is purchased or acquired; or (ii) a supplier of the r-composition or its derivatives (“Supplier”) operates within a quota framework that allows the association of recoverable component values ​​with a portion or all of the compounds within the olefin-containing effluent or its derivatives, and the transfer of that quota to the product manufacturer or any intermediary from which the supplier obtains a supply of one or more compounds from the olefin-containing effluent or its derivatives. The transfer may be made by the supplier transferring the r-compound to the product or the intermediary manufacturer, or by transferring a quota (e.g., a credit) without associating such quota with the transferred compound. In this system, there is no need to trace the source of the olefin volume from the cracked r-pyrolysis oil; instead, any olefin volume produced by any process can be used, and a recovery allocation can be associated with that olefin volume.

[0203] Examples of r-compositions being r-olefins (e.g., r-ethylene or r-propylene) and products being olefin-derived petrochemical products (e.g., reaction products of r-olefins or blends of r-olefins) directly or indirectly derived from r-pyrolysis oils include:

[0204] A cracker facility, wherein the r-olefins produced in the facility are in continuous or intermittent fluid communication via interconnected pipes, optionally via one or more storage containers and valves or interlocks, to an olefin-derived petrochemical forming facility (which may be a storage container to the olefin-derived petrochemical forming facility or directly to an olefin-derived petrochemical forming reactor), and the r-olefin feedstock is connected via interconnected pipes:

[0205] During or after the preparation of r-olefins, while r-olefins are being transported via pipeline to olefin-derived petrochemical product forming facilities, they are being removed from the cracking facility.

[0206] Withdrawal from one or more storage tanks at any time, provided that at least one storage tank is fed with r-olefins, provided that the entire volume of one or more storage tanks is replaced by a feed without r-olefins; or

[0207] Olefins containing or fed with r-olefins are transported from storage containers, domes, or facilities, or in isotainers, by truck, rail, ship, or other means other than pipelines, until the entire volume of the container, dome, or facility is replaced by olefin feedstock free of r-olefins; or

[0208] Manufacturers of olefin-derived petrochemical products wholly or partially certify or advertise to their consumers or the public that their olefin-derived petrochemical products contain recycled ingredients or are derived from recycled ingredients, wherein such recycled ingredients are claimed to be based on the production of γ-olefins; or

[0209] Manufacturers of olefin-derived petrochemical products have obtained: the amount of olefins produced from r-pyrolysis oil as certified, indicated, or advertised, or have transferred credit lines for olefin supply to manufacturers of olefin-derived petrochemical products sufficient to allow manufacturers of olefin-derived petrochemical products to meet certification requirements or make their indicated or advertised amounts, or have olefins with relevant recoverable component values ​​obtained from r-pyrolysis oil through one or more intermediate independent entities.

[0210] In one embodiment or in combination with any of the embodiments mentioned herein, the recycled components may be derived directly or indirectly from cracked r-pyrolysis oil, wherein at least a portion of the r-pyrolysis oil is obtained from the pyrolysis of recycled waste (e.g., waste plastics or waste streams).

[0211] In one embodiment or in combination with any of the mentioned embodiments, various methods are provided for distributing recovered components among various volumes of olefin-containing effluents or their compounds made from any of the entities or combinations of entities in the entity family. For example, a cracker owner or operator, or any of the entities in the entity family, or a site, may:

[0212] a. A symmetrical distribution of recoverable component values ​​is adopted among at least two compounds in the olefin-containing effluent or among RIAs, based on the same percentage fraction of recovered components in one or more feedstocks or based on the received quota amount. For example, if 5 wt% of the total cracker feedstock added to the furnace is r-pyrolysis oil, then one or more compounds in the olefin-containing effluent may contain a 5 wt% recoverable component value, or one or more compounds may contain a 5 wt% recoverable component value minus any yield loss, or one or more PIAs may contain a 5% recoverable component value. In this case, the amount of recovered component in the compound is proportional to all other products receiving the recovered component value; or

[0213] b. An asymmetric distribution of recoverable component values ​​among compounds in the olefin-containing effluent or among its PIAs. In this case, the recoverable component value associated with a compound or RIA may exceed the recoverable component value associated with other compounds or RIAs. For example, a volume or batch of olefin-containing effluent may receive a higher recoverable component value than other batches or volumes of olefin-containing effluent, or one or a combination of compounds in the olefin-containing effluent may receive a disproportionately higher recoverable component value relative to other compounds in the olefin-containing effluent or other PIAs, some of which may not receive recoverable component values. One volume of olefin-containing effluent or PIA may contain 20% by mass of recovered components, and another volume or RIA may contain 0% recovered components, even if the two volumes are compositionally identical and produced continuously, provided that the value of recovered components taken from the recovered component stock and applied to the olefin-containing effluent does not exceed the value of recovered components stored in the recovered component value stock, or if a shortfall occurs, the overdraft will be rebalanced to zero or a positive credit level as described above, or if there is no recovered component value stock, the condition is that the total value of recovered components associated with any one or more compounds in the olefin-containing effluent does not exceed the quota obtained from the r-pyrolysis oil, or if the quota is exceeded, then rebalancing will occur. In an asymmetric distribution of recovered components, the manufacturer may adapt the recovered components to the volume of the olefin-containing effluent or PIA or to the compounds of interest in the olefin-containing effluent or PIA, which are sold according to customer needs, thereby providing flexibility among customers, some of whom may require more recovered components than other customers in the r-compounds or recycled PIA.

[0214] In one embodiment or in combination with any of the embodiments mentioned herein, the symmetrical and asymmetrical distribution of recovered components may be proportional on a site-wide or multi-site basis. In one embodiment or in combination with any of the mentioned embodiments, recovered components obtained from r-pyrolysis oil may be within a site, and the recovered component values ​​from r-pyrolysis oil may be applied to one or more compounds in one or more olefin-containing effluent volumes or olefin-containing effluent volumes, or to one or more PIAs prepared at the same site from compounds in the olefin-containing effluent. The recovered component values ​​may be applied symmetrically or asymmetrically to one or more different olefin-containing effluent volumes or one or more compounds in the olefin-containing effluent, or to PIAs prepared at that site.

[0215] In one embodiment or in combination with any of the mentioned embodiments, the input or generation of recovered components (recovered component feedstock or quota) may be to or from a first site, and the recovered component value from said input is transferred to a second site and applied to one or more compositions prepared at the second site. The recovered component value may be applied to the composition symmetrically or asymmetrically at the second site. The presence or absence of recovered component values ​​directly or indirectly “derived from cracked r-pyrolysis oil” or “obtained from cracked r-pyrolysis oil” or derived from cracked r-pyrolysis oil does not imply the time when the recovered component value or quota is retrieved, captured, stored in the recovered component stock, or transferred. The timing of storing quotas or recovered component values ​​in the recovered component stock or realizing, identifying, capturing, or transferring them is flexible and may occur as early as when the r-pyrolysis oil is received at a site within the family of entities that own it, or when the r-pyrolysis oil is brought into the stock by an entity or individual that owns or operates the cracking facility, or within the family of entities. Therefore, a quota or recovery component value for the volume of r-pyrolysis oil that can be obtained, captured, stored in the recovery component stock, or transferred to the product, before that volume has been fed into the cracker and cracked. This quota can also be obtained during the feeding of r-pyrolysis oil into the cracker, during cracking, or when preparing the r-composition. The quota used when r-pyrolysis oil is owned, possessed, or received and stored in the recovery component stock 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 at the time of its use or storage, provided that the r-pyrolysis oil is cracked at some future point in time.

[0216] In one embodiment, the r-composition, or its downstream reaction product, or the recycled PIA, has an associated, contained, or labeled, advertised, or certified as containing a recycled component in an amount of at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, or at least 0.5 wt.%, or at least 0.75 wt.%, or at least 1 wt.%, or at least 1.25 wt.%, or at least 1.5 wt.%, or at least 1.75 wt.%, or at least 2 wt.%, or at least 2.25 wt.%, or at least 2.5 wt.%, or at least 2.75 wt.%, or at least 3 wt.%, or at least 3.5 wt.%, or at least 4 wt.%, or at least 4.5 wt.%, or at least 5 wt.%, or at least 6 wt.%, or at least 7 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%. Or at least 45 wt.%, or at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.%, or at least 65 wt.% and / or the amount may be up to 100 wt.%, or up to 95 wt.%, or up to 90 wt.%, or up to 80 wt.%, or up to 70 wt.%, or up to 60 wt.%, or up to 50 wt.%, or up to 40 wt.%, or up to 30 wt.%, or up to 25 wt.%, or up to 22 wt.%, or up to 2 0 wt.%, or up to 18 wt.%, or up to 16 wt.%, or up to 15 wt.%, or up to 14 wt.%, or up to 13 wt.%, or up to 11 wt.%, or up to 10 wt.%, or up to 8 wt.%, or up to 6 wt.%, or up to 5 wt.%, or up to 4 wt.%, or up to 3 wt.%, or up to 2 wt.%, or up to 1 wt.%, or up to 0.9 wt.%, or up to 0.8 wt.%, or up to 0.7 wt.%. The recovered component value associated with the r-composition, r-compound, or its downstream reaction product can be associated with a quota (credit or allocation) applied to any manufactured or sold composition, compound, or PIA. This quota can be included in a quota stock created, maintained, or operated by or for the manufacturer of the recovered PIA or r-composition. This quota can be obtained from any source along any manufacturing chain of the product, provided it originates from a feedstock containing r-pyrolysis oil obtained through cracking.

[0217] In one embodiment or in combination with any of the mentioned embodiments, a recycled PIA manufacturer may produce recycled PIA, or produce recycled PIA by processing reactants (e.g., any compound of olefin-containing cracker effluent) obtained from any source from a supplier (e.g., a cracker manufacturer or one of its entity families) and whether or not such reactants contain any recycled components, and:

[0218] i. Obtaining a share of the recovered components used for the same reactant from the same reactant supplier, or

[0219] ii. Obtain the recycling contribution from any individual or entity without providing reactants from the individual or entity transferring the recycling contribution.

[0220] The quota in (i) is obtained from the reactant supplier, who also supplies reactants to the recycled PIA manufacturer or within its entity family. The situation described in (i) allows the recycled PIA manufacturer to obtain a supply of reactants as non-recoverable components, and also a recycling component quota from the supplier. In one embodiment or in combination with any of the mentioned embodiments, the reactant (e.g., propylene, ethylene, butene, etc.) supplier assigns a recycling component quota to the recycled PIA manufacturer and transfers the supply of reactants to the recycled PIA manufacturer, wherein the recycling component quota is not associated with the supplied reactants, or even with any reactants prepared by the reactant supplier. The recycling component quota need not be linked to the amount of recovered components in the supplied reactants or the reactants used to prepare the recycled PIA, or to olefin-containing effluents, which allows flexibility between the reactant supplier and the recycled PIA manufacturer in allocating recovered components among the various products they each prepare. However, in each of these cases, the recycling component quota is associated with the cracked r-pyrolysis oil.

[0221] In one embodiment, or in combination with any of the embodiments mentioned, the reactant supplier assigns a recovery component quota to the recycled PIA manufacturer and transfers the supply of reactants to the recycled PIA manufacturer, wherein the recovery component quota is associated with the reactants. This quota transfer may be made solely by supplying reactants having associated recovery components. Optionally, the supplied reactants are r-compounds separated from olefin-containing effluents obtained through cracking r-pyrolysis oil, and at least a portion of the recovery component quota is associated with the r-compound (or r-reactant). The recovery component quota transferred to the recycled PIA manufacturer may be provided in advance with the reactants, optionally in batches, or with each batch of reactants, or allocated among the parties as needed.

[0222] The quota in (ii) is obtained by the recycled PIA manufacturer (or its family of entities) from any individual or entity without obtaining a supply of reactants from that individual or entity. This individual or entity may be a reactant manufacturer that does not supply reactants to the recycled PIA manufacturer or its family of entities, or it may be a manufacturer that does not manufacture reactants. In either case, the situation in (ii) allows the recycled PIA manufacturer to obtain the recycled component quota without having to purchase any reactants from the entity or individual supplying the recycled component quota. For example, the individual or entity may transfer the recycled component quota to the recycled PIA manufacturer or its family of entities through a buy / sell model or contract without needing to purchase or sell the quota (e.g., as a product exchange for a product that is not a reactant), or the individual or entity may sell the quota directly to one of the recycled PIA manufacturers or its family of entities. Alternatively, the individual or entity may transfer products other than reactants along with their associated recycled component quota to the recycled PIA manufacturer. This is attractive to recycled PIA manufacturers with diversified businesses that prepare various PIAs rather than requiring PIAs manufactured from supplied reactants.

[0223] Quotas can be stored in a recycled component stock (e.g., a quota stock). In one embodiment or in combination with any of the mentioned embodiments, the quota is generated by the manufacturer of the olefin-containing effluent. The manufacturer may also manufacture the PIA, whether or not the recycled component is applied to the PIA, and whether or not the recycled component (if applied to the PIA) is taken from the recycled component stock. For example, the olefin-containing effluent manufacturer may:

[0224] a. Store the quota in the stock and only store it; or

[0225] b. Olefin-containing effluents: Quotas for olefin-containing effluents are deposited into the stock, and quotas from the stock are applied to one or more compounds within the olefin-containing effluent or to any PIA manufactured by the manufacturer, or

[0226] c. Sell or transfer the quota from the stock of recycled ingredients to a third party, wherein at least one quota obtained as described above is deposited into the stock of recycled ingredients.

[0227] If necessary, any amount of any recovered component credit can be deducted and applied to PIA to prepare recovered PIA, or applied to effluent containing non-recovered olefins to prepare olefin-containing effluent. For example, credits can be generated from various sources used to create credits. Some recovered component credits (credits) may originate from methanol decomposition of recycled waste, or from gasification of other types of recycled waste, or from mechanical recycling of waste plastics or metals, or from any other chemical or mechanical recycling technology. The recovered component stock may or may not trace the source or basis from which the recovered component value is obtained, or the stock may not allow the source or basis of the credit to be associated with the credit applied to the r-composition. The quota is sufficient to be deducted from the stock of recovered components and applied to PIA or effluent containing non-recovered olefins, regardless of the source of the quota, as long as the recovered component quota obtained from the r-pyrolysis oil is present in the stock of recovered components at the time of withdrawal, or the recovered component quota is obtained by the recovered PIA manufacturer as specified in step (i) or step (ii), regardless of whether the recovered component quota is actually stored in the stock of recovered components.

[0228] In one embodiment or in combination with any of the mentioned embodiments, the recovery component allocation obtained in step (i) or (ii) is deposited into the quota stock. In one embodiment or in combination with any of the mentioned embodiments, the recovery component allocation deducted from the recovery component stock and applied to PIA or effluent containing non-recovered olefins (or any compound thereof) is derived from r-pyrolysis oil.

[0229] As used throughout, the stock of recovered components may be owned by the owner of the cracker processing the pyrolysis oil or one of its entity families, the olefin-containing effluent, or the recycled PIA manufacturer, or operated by any of them, or owned or operated by any of them but at least partially benefiting from any of them, or licensed by any of them or licensed to any of them. Similarly, the cracker olefin-containing effluent manufacturer or the recycled PIA manufacturer may also include any of their entity families. For example, while any of them may not own or operate the stock, one of their entity families may own such a platform, license it from an independent supplier, or operate it for any of them. Alternatively, an independent entity may own and / or operate the stock and, for a service fee, operate and / or manage at least a portion of the stock for any of them.

[0230] In one embodiment or in combination with any of the mentioned embodiments, the recycled PIA manufacturer obtains a supply of reactants from a supplier, and also obtains a quota from the supplier, wherein such quota is derived from r-pyrolysis oil, and optionally, the quota is associated with the reactants supplied by the supplier. In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the quota obtained by the recycled PIA manufacturer is:

[0231] a. Applied to PIA prepared by supplying reactants;

[0232] b. Applicable to PIAs made from the same type of reactants, but not from the volume of the supplied reactants, for example, PIAs made from the same type of reactants that have already been made and stored in stock or in future-manufactured PIAs; or

[0233] c. Add to the stock, deduct from the stock the quota applicable to PIA, which is made from a different type of reactant than that supplied, or

[0234] d. Store in the stock and save.

[0235] It is not necessary to use the r-reactant in all embodiments to prepare the recovered PIA, or to obtain the recovered PIA from the recovery component quota associated with the reactant. Furthermore, it is not necessary to apply the quota to the feedstock to prepare the recovered PIA to which the recovered component is applied. Instead, as described above, the quota may be stored in the electronic inventory even when associated with the reactant at the time of its acquisition. However, in one embodiment or in combination with any mentioned embodiments, the reactant associated with this quota is used to prepare the recovered PIA. In one embodiment or in combination with any mentioned embodiments, the recovered PIA is obtained from the recovery component quota associated with the r-reactant or r-pyrolysis oil or cracked r-pyrolysis oil.

[0236] In one embodiment or in combination with any of the mentioned embodiments, the olefin-containing effluent manufacturer generates a quota from r-pyrolysis oil, and:

[0237] a. Applying quotas to any PIA produced directly or indirectly (e.g., via a reaction scheme involving several intermediates) from cracked r-pyrolysis oil olefin-containing effluents; or

[0238] b. Apply the quota to any PIA not directly or indirectly prepared from olefin-containing effluents of cracked r-pyrolysis oil, such as PIA that has already been prepared and is stored in stock or PIA to be prepared in the future; or

[0239] c. Deposit into the stock, deduct any quotas applied to PIA from the stock; and the deposited quotas may or may not be associated with a specific quota applied to PIA; or

[0240] d. It is stored in the inventory and stored for later use.

[0241] In embodiments, packaging or a combination of recycled PIA and a recycled component identifier associated with the recycled PIA is also provided, wherein the identifier is or contains a representation that the recycled PIA contains, originates from, or is associated with a recycled component. The packaging can be any suitable packaging for containing the polymer and / or articles, such as plastic or metal drums, railway cars, isotainers, tote bags, polytote bags, bales, IBC tote bags, bottles, compression bales, drums, plastic bags, spools, roving, wrapping, or cardboard packaging. Identifiers can be certificate documents, product instructions stating the recycled ingredient, labels, marks or certification marks from certification bodies indicating that the article or packaging contains or is made from or associated with the recycled ingredient, or can be an electronic statement from the recycled PIA manufacturer accompanying a purchase order or product, or posted as a statement, display, or mark indicating that the recycled PIA contains or is made from or associated with the recycled ingredient, or can be electronically transmitted, on or in connection with an advertisement for the recycled PIA via a website, email, television, or trade show, in each case, an advertisement associated with the recycled PIA. Identifiers do not need to state or indicate that the recycled ingredient is derived from r-pyrolysis oil. Rather, identifiers may simply convey or communicate that the recycled PIA has or is derived from the recycled ingredient, regardless of the source. However, the recycled PIA has a recycled ingredient allocation that is at least partially associated with r-pyrolysis oil.

[0242] In one embodiment or in combination with any of the mentioned embodiments, information regarding the recycled components of recycled PIA may 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 may be a customer of the olefin-containing effluent manufacturer or the recycled PIA manufacturer, or may be any other individual or entity or government organization other than an entity that owns either of them. Transmission may be electronic, by document, by advertisement, or by any other means of communication.

[0243] In one embodiment or in combination with any of the mentioned embodiments, a system or package is provided comprising:

[0244] a. Recycling PIA, and

[0245] b. Identifiers, such as credits, labels, or certificates associated with the PIA, wherein the identifier is an indication that the PIA has or originates from recycled components (which need not identify the source of the recycled components or quotas), provided that the recycled PIA thus prepared has a quota, or is prepared from reactants, and is at least partially associated with r-pyrolysis oil.

[0246] The system can be a physical combination, such as packaging containing at least some recycled PIAs as its contents, and a label, such as an identifier, that identifies, for example, that the contents of the recycled PIA have or originate from recycled ingredients. Alternatively, whenever it transfers or sells recycled PIAs having or originating from recycled ingredients, the label or certificate can be issued to third parties or customers as part of the entity’s standard operating procedures. The identifier does not need to be physically on the recycled PIA or packaging, and does not need to be on any physical document accompanying the recycled PIA or associated with the recycled PIA or packaging. For example, the identifier can be an electronic document, certificate, or identification mark associated with the sale of the recycled PIA to a customer. The identifier itself only needs to convey or communicate that the recycled PIA has or originates from recycled ingredients, regardless of the source. In one embodiment or in combination with any of the mentioned embodiments, articles made from recycled PIAs may have an identifier, such as a stamp or mark embedded or affixed to the article or packaging. In one embodiment or in combination with any of the mentioned embodiments, the identifier is an electronic recycled ingredient credit from any source. In one embodiment or in combination with any of the mentioned embodiments, the identifier is an electronic recycled ingredient credit originating from r-pyrolysis oil.

[0247] The recovery of PIA is supported by reactants, regardless of whether those reactants are recoverable component reactants. Once a PIA is prepared, it can be designated as having a recoverable component based on and derived from at least a portion of the quota. The quota can be withdrawn or deducted from the recoverable component stock. The amount deducted and / or applied to the PIA can correspond to any method, such as the mass balance method.

[0248] In one embodiment, recycled PIA can be prepared by having a stock of recycled components, reacting reactants in a synthesis process to produce PIA, extracting quotas from the stock of recycled components with recycled component values, and applying the recycled component values ​​to the PIA to obtain recycled PIA. The amount of quotas deducted from the stock is flexible and will depend on the amount of recycled components applied to the PIA. If not the full amount, it is sufficient to correspond to at least a portion of the recycled components applied to the PIA. The recycled component quotas applied to the PIA do not necessarily have to originate from r-pyrolysis oil, but can originate from any other method of generating quotas from recycled waste, such as by methanol hydrolysis or gasification of recycled waste, as long as the stock of recycled components still contains quotas or has quota deposits originating from r-pyrolysis oil. However, in one embodiment or in combination with any of the mentioned embodiments, the recycled component quotas applied to the PIA are quotas obtained from r-pyrolysis oil.

[0249] The following are examples of applying recovered components to PLA or effluents containing non-recovered olefins or compounds:

[0250] 1. A PIA manufacturer applies at least a portion of the quota to PIA to obtain recycled PIA, wherein the quota is associated with r-pyrolysis oil and the reactants used to prepare PIA do not contain any recycled components; or

[0251] 2. The PIA manufacturer applies at least a portion of the quota to PIA to obtain recycled PIA, wherein the quota is obtained from the recycled component reactant, regardless of whether the volume of the reactant is used to prepare the recycled PIA; or

[0252] 3. The PIA manufacturer applies at least a portion of the quota to PIA to produce recycled PIA, wherein the quota is derived from r-pyrolysis oil, and:

[0253] a. Apply all recovered components in the r-pyrolysis oil to determine the amount of recovered components in the recovered PIA, or

[0254] b. Only a portion of the recovered components from the r-pyrolysis oil feedstock is applied to determine the amount of recovered components in the recovered PIA, with the remainder stored in the recovered component stock for future use or application to other PIAs, or to increase the recovered components on existing recovered PIAs, or combinations thereof, or

[0255] The recovered components in the Cr-pyrolysis oil feedstock are not used in PIA, but are stored in stock. The recovered components from any source are deducted from the stock and then used in PIA to prepare recycled PIA; or

[0256] 4. A manufacturer of recycled PIA applies at least a portion of its quota to reactants used to manufacture recycled PIA, thereby obtaining PIA, wherein the quota is obtained by transferring or purchasing the same reactants used to manufacture PIA, and the quota is associated with the recycled component in the reactants; or

[0257] 5. A manufacturer of recycled PIA applies at least a portion of its quota to reactants used to manufacture recycled PIA, thereby obtaining PIA, wherein the quota is obtained by transferring or purchasing the same reactants used to manufacture PIA, and the quota is not associated with the recycled components in the reactants but with the recycled components of the monomers used to prepare the reactants; or

[0258] 6. A PIA recycling manufacturer applies at least a portion of its quota to reactants used to manufacture recycled PIA, thereby obtaining PIA, wherein the quota is not obtained by transferring or purchasing reactants, and the quota is associated with the recycled component in the reactants; or

[0259] 7. A manufacturer of recycled PIA obtains recycled PIA by applying at least a portion of the quota to reactants used to manufacture PIA, wherein the allocation is not obtained by transferring or purchasing reactants, and the quota is not associated with the recycled components in the reactants but with the recycled components of any monomers used to manufacture the reactants; or

[0260] 8. Recycling PIA manufacturers obtain quotas derived from r-pyrolysis oil, and:

[0261] a. Instead of applying a portion of this allowance to the reactants to prepare PIA, at least a portion of this allowance is applied to the PIA to prepare recycled PIA; or

[0262] b. Less than all of the fraction is used in the reactants for the preparation of recovered PIA, while the remainder is stored in stock or used in future PIA preparations or in existing recovered PIA in stock to increase its recovery value.

[0263] In one embodiment or in combination with any of the mentioned embodiments, recycled PIA or articles thereof may be offered for sale or sold as recycled PIA containing or obtained from recycled ingredients. The sale or offer for sale may be accompanied by certification or representation of a claim regarding the recycled ingredients associated with the recycled PIA.

[0264] Designating at least a portion of the recycled PIA or olefin-containing effluent to correspond to at least a portion of the quota (e.g., allocation amount or credit) can be done in various ways and depending on the system used by the recycled PIA manufacturer or olefin-containing effluent manufacturer, and can vary from manufacturer to manufacturer. For example, this designation can occur solely internally, through log entries in the manufacturer's or other stock software programs' books or files, or through instructions, packaging, advertisements or statements on the product, through markings associated with the product, through certification declarations associated with the products sold, or through a formula that calculates the amount to be deducted from the stock relative to the amount of recycled component applied to the product.

[0265] Optionally, recycled PIA can be sold. In one embodiment or in combination with any of the mentioned embodiments, a method is provided for offering to sell or selling the polymer and / or articles thereof by:

[0266] a. Any manufacturer of recycled PIA or olefin-containing effluent, or any of its entity families (collectively, the Manufacturers), obtains or generates a recycled component quota, which is available through any of the methods described herein and can be deposited into the recycled component stock, the source of which is r-pyrolysis oil.

[0267] b. In the synthetic process, the reactants are converted to prepare PIA, and the reactants can be any reactant or a γ-reactant.

[0268] c. The recycled components are designated (e.g., assigned or associated) to at least a portion of the PIA from a stock of recycled components to prepare the recycled PIA, wherein the stock contains at least one entry as a quota associated with the r-pyrolysis oil. This designation may be a quota amount deducted from the stock, or an amount of recycled components declared or determined by the recycled PIA manufacturer in its accounts. Therefore, the amount of recycled components does not necessarily have to be physically applied to the recycled PIA product. This designation may be made to or internally by: the manufacturer, or a service provider with a contractual relationship with the manufacturer, and

[0269] d. Offer to sell or sell a recycled PIA containing or obtained from the following recycled components, wherein the recycled components at least partially correspond to the designation. This is indicated by the amount of recycled components contained in the recycled PIA being sold or offered to sell relating to or related to the designation. The amount of recycled components may be a 1:1 relationship between the amount of recycled components declared on the recycled PIA being offered to sell or sold and the amount of recycled components allocated or designated to the recycled PIA by the recycled PIA manufacturer.

[0270] The steps do not have to be sequential and can be independent of each other. For example, step a) of obtaining the quota and step of preparing recycled PIA can be performed simultaneously.

[0271] As used throughout, the step of deducting quotas from the inventory of recycled ingredients does not need to be applied to recycled PIA products. Deduction does not mean the quantity disappears or is removed from the inventory log. Deduction can be adjusting entries, removing, adding entries as debits, or any other algorithm that adjusts inputs and outputs based on the amount of recycled ingredients associated with the product and one or more accumulated deposited quotas in the inventory. For example, deduction can be a simple step within the same procedure or book to deduct / debit an entry from one column and add / credit to another, or an algorithm that automates deduction and entry / addition and / or application or assignment to the product dashboard. The step of applying quotas to PIAs (where such quotas are deducted from the inventory) also does not need to physically apply the quotas to recycled PIA products or to any documents published in connection with the sold recycled PIA products. For example, a recycled PIA manufacturer can ship recycled PIA products to customers and fulfill the "application" of quotas for recycled PIA products by electronically transmitting recycled ingredient credits to customers.

[0272] Uses of r-pyrolysis oil are also provided, including converting the r-pyrolysis oil in a gas cracker to produce olefin-containing effluents. Uses of the r-pyrolysis oil are also provided, including 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 entry into the stock is associated with the r-pyrolysis oil.

[0273] In one embodiment or in combination with any of the mentioned embodiments, a reclaimed PIA obtained by any of the methods described above is provided.

[0274] Reactants can be stored in storage containers and transported by truck, pipeline, or ship to a PIA recycling manufacturing facility, or, as further described below, an olefin-containing effluent manufacturing facility can be integrated with a PIA facility. Reactants can be transported or transferred to operators or facilities that produce polymers and / or articles.

[0275] In one embodiment, the method for preparing recycled PIA can be an integrated method. One such example is a method for preparing recycled PIA through the following steps:

[0276] a. Cracking r-pyrolysis oil to prepare olefin-containing effluent; and

[0277] b. Separating the compounds from the olefin-containing effluent to obtain the separated compounds; and

[0278] c. React any reactants in the synthesis process to prepare PIA;

[0279] d. Deposit the quota into the quota stock, wherein the quota is derived from r-pyrolysis oil; and

[0280] e. Apply any quota from the existing stock to PIA to obtain recycled PIA.

[0281] In one embodiment or in combination with any of the mentioned embodiments, two or more facilities can be integrated to produce recycled PIA. The facility for producing recycled PIA or olefin-containing effluent can be a separate facility or a facility integrated with each other. For example, a system for producing and consuming reactants can be established as follows:

[0282] a. Provide facilities for manufacturing olefin-containing effluents configured to produce reactants;

[0283] b. Providing a PIA manufacturing facility having a reactor configured to receive reactants from the olefin-containing effluent manufacturing facility; and

[0284] c. A supply system that provides fluid communication between the two facilities and enables the supply of reactants from the olefin-containing effluent manufacturing facility to the PIA manufacturing facility.

[0285] The method for generating or participating in the generation of quota and cracked γ-pyrolysis oil in olefin-containing effluent manufacturing facilities, and:

[0286] (i) Apply the quota to the reactants or to the PIA, or

[0287] (ii) The quota is deposited into the quota stock and optionally a share is drawn from the stock and applied to the reactants or to the PIA.

[0288] Recycled PIA manufacturing facilities can produce recycled PIA by accepting any reactants from olefin-containing effluent manufacturing facilities and applying the recycled components to recycled PIA made from the reactants by deducting quotas from their stock and applying them to PIA.

[0289] In one embodiment or in combination with any of the mentioned embodiments, a system for producing recycled PIA is also provided as follows:

[0290] a. Provide an olefin-containing effluent manufacturing facility configured to produce an output composition comprising an olefin-containing effluent;

[0291] b. Provide a reactant manufacturing facility configured to accept compounds isolated from olefin-containing effluents and prepare one or more downstream products of said compounds by a reaction protocol to prepare an output composition comprising the reactants;

[0292] c. Provide a PIA manufacturing facility with a reactor configured to receive reactants and prepare an output composition containing PIA;

[0293] d. A supply system that provides fluid communication between at least two of these facilities and is capable of supplying an output composition from one manufacturing facility to one or more other manufacturing facilities.

[0294] PIA production facilities can produce recycled PIA. In this system, an olefin-containing effluent manufacturing facility can have its output fluidly connected to a reactant composition manufacturing facility, and conversely, a reactant compound or composition manufacturing facility can have its output fluidly connected to a PIA manufacturing facility. Alternatively, manufacturing facilities a) and b) can be fluidly connected individually, or only b) and c) can be fluidly connected. In the latter case, the PIA manufacturing facility can produce recycled PIA by deducting quotas from the recycled component stock and applying them to PIA. The quotas obtained and stored in the stock can be obtained by any of the methods described above.

[0295] Fluid communication can be gaseous, 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 via an interconnected network of pipes without the use of trucks, trains, ships, or airplanes. Furthermore, facilities can share the same site, or in other words, a site can contain two or more facilities. Additionally, facilities may share storage tank sites or storage tanks for auxiliary chemicals, or they may share utilities, steam, or other heat sources, but because their unit operations are separate, they are also considered separate facilities. Facilities are typically defined by plant boundaries.

[0296] In one embodiment or in combination with any of the mentioned embodiments, the integrated process includes at least two facilities located within 5 miles, 3 miles, 2 miles, or 1 mile (as measured in a straight line) of each other. In one embodiment or in combination with any of the mentioned embodiments, at least two facilities are owned by the same entity family.

[0297] In one embodiment, an integrated system for recycling PIA production and consumption is also provided. This system includes:

[0298] a. Provide an olefin-containing effluent manufacturing facility configured to produce an output composition comprising an olefin-containing effluent;

[0299] b. Provide a reactant manufacturing facility configured to accept compounds isolated from olefin-containing effluents and prepare one or more downstream products of said compounds by a reaction protocol to prepare an output composition comprising the reactants;

[0300] c. Provide a PIA manufacturing facility with a reactor configured to receive reactants and prepare an output composition containing PIA;

[0301] d. A piping system that interconnects at least two of the facilities, optionally with intermediate processing equipment or storage facilities, the piping system being capable of retrieving an output composition from one facility and receiving the output at any one or more other facilities.

[0302] This system does not necessarily require fluid connectivity between the two facilities, although such connectivity is desirable. For example, compounds separated from olefin-containing effluents can be transported to the reactant facility via an interconnected piping network that can be interrupted by other processing equipment, such as treatment, purification, pumping, compression, or equipment or storage facilities suitable for combining streams, all of which include optional metering, valves, or interlocking devices. This equipment can be fixed to the ground or to a ground-mounted structure. The interconnected piping does not need to connect to the reactant reactor or cracker, but rather to the delivery and receiving points at their respective facilities. The interconnected piping system does not need to connect all three facilities to each other; rather, the interconnected piping system can exist between facilities a)-b), or b)-c), or a)-b)-c).

[0303] A method for manufacturing a ring is also provided, the method comprising:

[0304] a. Provide r-pyrolysis oil, and

[0305] b. Cracking r-pyrolysis oil to produce olefin-containing effluent, and

[0306] (i) Reacting the compounds separated from the olefin-containing effluent to prepare recovered PIA, or

[0307] (ii) Combining a recovered component fraction obtained from the r-pyrolysis oil with a PIA prepared from a compound separated from an effluent containing non-recovered olefins to produce a recovered PIA; and

[0308] c. Taking at least a portion of the recovered PIA or any other article, compound or polymer prepared from the recovered PIA as a raw material to prepare the r-pyrolysis oil.

[0309] The above process provides fully circular or closed-loop processes in which PIA can be recycled multiple times.

[0310] Examples of articles included in PIA include fibers, yarns, tows, continuous filaments, staple fibers, rovings, fabrics, textiles, sheets, films (e.g., polyolefin films), sheets, composite sheets, plastic containers, and consumer articles. In one embodiment or in combination with any of the mentioned embodiments, the recycled PIA is a polymer or article of the same family or class as the polymer or article used to prepare γ-pyrolysis oil.

[0311] As used herein, the terms “recycled waste,” “waste stream,” and “recycled waste stream” are used interchangeably to refer to any type of waste or waste-containing stream that is reused in a production process rather than permanently disposed of (e.g., in a landfill or incinerator). A recycled waste stream is a flow or accumulation of waste from industrial and consumer sources that is at least partially recycled. Recycled waste streams include materials, products, and articles of manufacture (collectively referred to as “materials” when used individually). Waste can be solid or liquid. Examples of solid waste streams include plastics, rubber (including tires), textiles, wood, biological waste, modified cellulose, wet-laid products, and any other materials capable of pyrolysis. Examples of liquid waste streams include industrial sludge, oils (including those derived from plants and petroleum), recycled lubricants, or vegetable or animal oils, and any other chemical streams from industrial plants.

[0312] In one embodiment or in combination with any of the embodiments mentioned herein, the recycled waste stream that is pyrolyzed includes at least a portion of a stream containing post-industrial materials, or post-consumer materials, or both post-industrial and post-consumer materials. In one embodiment or in combination with any of the embodiments mentioned herein, post-consumer materials are materials that have been used at least once for their intended application over any period of time, regardless of wear, or have been sold to end-user consumers, or have been discarded into recycling bins by any individual or entity other than the manufacturer or enterprise engaged in the manufacture or sale of the materials. In one embodiment or in combination with any of the embodiments mentioned herein, post-industrial materials are materials that have been generated but not yet used for their intended application, or have not yet been sold to end-user customers, or have not been discarded by the manufacturer or any other entity involved in the sale of the materials. Examples of post-industrial materials include reprocessed, re-grinded, scrap, trimmed, non-conforming materials, and finished materials transferred from the manufacturer to any downstream customer (e.g., manufacturer to wholesaler to distributor) but not yet used or sold to end-user customers.

[0313] The form of the recycled waste stream fed to the pyrolysis unit is unrestricted and can include any form of article, product, material, or portion thereof. A portion of an article may take the form of sheet, extruded profile, molded article, film, laminate, foam sheet, fragment, flake, granule, agglomerate, briquette, powder, scrap, strip, or sheet of any shape of various forms, or any other form besides the original form of the article, and is suitable for feeding into the pyrolysis unit. In one embodiment or in combination with any embodiment mentioned herein, the waste is reduced in diameter. Diameter reduction can be performed in any manner, including shredding, shredding, harrowing, confricing, crushing, cutting raw materials, molding, compressing, or dissolving in a solvent.

[0314] Recycled waste plastics can be separated as a type of polymer stream or can be a mixed waste plastic stream. Plastics can be any organic synthetic polymer that is solid at 25°C and 1 atm. Plastics can be thermosetting, thermoplastic, or elastomer 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, epoxy resins, polyamides, phenolic resins, polyacetals, polycarbonates, polyphenylene alloys, polypropylene and its copolymers, polystyrene, styrene compounds, vinyl compounds, styrene-acrylonitrile, thermoplastic elastomers, urea-based polymers, and melamine-containing polymers.

[0315] Suitable recycled waste plastics also include any of those with resin ID codes 1-7 within the chasing arrow triangle established by the SPI. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil is made from a recycled waste stream, at least a portion of which contains plastics that are not normally recycled. These include plastics with the numbers 3 (polyvinyl chloride), 5 (polypropylene), 6 (polystyrene), and 7 (others). In one embodiment or in combination with any embodiment mentioned herein, the pyrolyzed waste stream contains less than 10% by weight, or no more than 5% by weight, or no more than 3% by weight, or no more than 2% by weight, or no more than 1% by weight, or no more than 0.5% by weight, or no more than 0.2% by weight, or no more than 0.1% by weight, or no more than 0.05% by weight of plastic number 3 (polyvinyl chloride), or optionally plastic numbers 3 and 6, or optionally plastic numbers 3, 6, and 7.

[0316] Examples of recycled rubber include both natural and synthetic rubber. The form of rubber is not limited, including tires. Examples of recycled waste wood include softwood and hardwood, wood chips, pulp, or finished products. Large quantities of waste wood originate from industrial, construction, or demolition sources. Examples of recycled biological waste include household biological waste (e.g., food), green or garden biological waste, and biological waste from industrial food processing industries.

[0317] Examples of recycled textiles include natural and / or synthetic fibers, rovings, yarns, nonwoven fiber webs, fabrics, textiles, and products made from or containing any of the aforementioned items. Textiles can be woven, knitted, knotted, sewn, tufted, or made by pressing fibers together, such as in felting operations, embroidered, lace-like, crocheted, braided, or nonwoven fiber webs and materials. Textiles include fabrics and fibers, waste, or non-standard fibers or yarns separated from textiles or other products containing fibers, or any other loose fiber and yarn sources. Textiles also include staple fibers, continuous fibers, threads, tows, twisted and / or staple yarns, greige fabrics made from yarns, finished textiles made from wet-processed greige fabrics, and garments made from finished textiles or any other textiles. Textiles include clothing, interior furnishings, and industrial textiles.

[0318] Examples of recycled textiles in the clothing category (things worn by humans or made for the body) include sports jackets, suits, trousers and casual or work pants, shirts, socks, sportswear, dresses, close-fitting garments, outerwear such as raincoats, low-temperature jackets and coats, sweaters, protective clothing, uniforms, and accessories such as scarves, hats, and gloves. Examples of textiles in the interior furnishings category include furniture upholstery and covers, carpets and mats, curtains, bedding such as sheets, pillowcases, comforters, quilts, and mattress covers; linen products, tablecloths, towels, and blankets. Examples of industrial textiles include transportation (car, airplane, train, bus) seats, floor mats, trunk liners, and roof linings; outdoor furniture and mats, tents, backpacks, luggage, ropes, conveyor belts, calender roll felt, polishing cloths, rags, soil-eroded textiles and geotextiles, agricultural mats and screens, personal protective equipment, bulletproof vests, medical bandages, stitching, tape, etc.

[0319] Recycled nonwoven fiber webs can also be dry-laid nonwoven fiber webs. Examples of suitable articles that can be formed from dry-laid nonwoven fiber webs as described herein include those for personal, consumer, industrial, food service, medical, and other types of end uses. Specific examples may include, but are not limited to, baby wipes, flushable wipes, disposable diapers, training pants, feminine hygiene products such as sanitary napkins and tampons, adult incontinence pads, underwear, and pet training pads. Other examples include a variety of different dry or wet wipes, including those for consumer (such as personal care or home) and industrial (such as food service, healthcare, or professional) use. Nonwoven fiber webs can also be used as pillows, mattresses, and furniture upholstery, and as wadding for bedding and duvet covers. In the medical and industrial fields, the nonwoven fiber webs of the present invention can be used in medical and industrial face shields, protective clothing, caps and shoe covers, disposable sheets, surgical gowns, curtains, bandages, and medical dressings. In addition, nonwoven fiber webs can be used in environmental textiles, such as geotextiles and tarpaulins, oil pads and chemical absorbent pads, as well as building materials, such as sound or heat insulation, tents, timber and soil mulch and sheets. Nonwoven fiber webs can also be used for other consumer end-uses, such as for carpet backing, packaging for consumer, industrial and agricultural products, heat or sound insulation, and various types of clothing. Dry-laid nonwoven fiber webs can also be used in a variety of filtration applications, including transportation (e.g., automotive or aerospace), commercial, residential, industrial or other professional applications. Examples may include filter elements for consumer or industrial air or liquid filters (e.g., gasoline, oil, water), including nanofiber webs for microfiltration and end-uses such as tea bags, coffee filters and dryer sheets. Furthermore, nonwoven fiber webs can be used to form a variety of automotive components, including but not limited to brake pads, trunk liners, carpet tufting and underfill.

[0320] Recycled textiles may include one or more types of natural fibers and / or one or more types of synthetic fibers. Examples of textile fiber combinations include all-natural, all-synthetic, two or more types of natural fibers, two or more types of synthetic fibers, one type of natural fiber and one type of synthetic fiber, one type of natural fiber and two or more types of synthetic fibers, two or more types of natural fibers and one type of synthetic fiber, and two or more types of natural fibers and two or more types of synthetic fibers.

[0321] Examples of recycled wet-laid products include cardboard, office paper, newsprint and magazines, printing and writing paper, toilet paper, tissue / towel paper, packaging / container board, specialty paper, clothing, bleached cardboard, corrugated base paper, wet-laid molded products, unbleached kraft paper, decorative laminates, security paper and currency, extra-large graphics, specialty products, and food and beverage products.

[0322] Examples of modified cellulose include cellulose acetate, cellulose diacetate, cellulose triacetate, and regenerated cellulose such as viscose, rayon, and Lyocel. TM Products, which are in any form such as tows, short fibers, continuous fibers, films, sheets, molded or stamped products, and contained in or on any article such as cigarette filter rods, ophthalmic products, screwdriver handles, optical films, and coatings. Examples of recycled vegetable or animal oils include oils recovered from animal processing facilities and waste from restaurants.

[0323] The sources of recyclable post-consumer or post-industrial waste are unrestricted and may include waste present in and / or separated from municipal solid waste streams (“MSW”). For example, MSW streams may be processed and sorted into several discrete components, including textiles, fibers, paper, wood, glass, metals, etc. Other textile sources include those obtained by collection agencies, or those obtained by textile brand owners or alliances or organizations, or those obtained on behalf of such organizations, or those obtained by brokers, or those obtained from post-industrial sources such as waste from mills or commercial production facilities, unsold textiles from wholesalers or distributors, from mechanical and / or chemical sorting or separation facilities, from landfills, or stranded on docks or ships.

[0324] In one embodiment or in combination with any embodiment mentioned herein, the feed to the pyrolysis unit may contain at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99 different kinds of recycled waste in each case. The reference to "kind" is determined by resin ID codes 1-7. In one embodiment or in combination with any embodiment mentioned herein, the feed to the pyrolysis unit contains less than 25, or more than 20, or more than 15, or more than 10, or more than 5, or more than 1% by weight of polyvinyl chloride and / or polyethylene terephthalate in each case. In one embodiment or in combination with any embodiment mentioned herein, the recycled waste stream contains at least one, two, or three plasticized plastics.

[0325] Figure 2 An exemplary pyrolysis system 110 is described, which can be used to at least partially convert one or more recycled wastes, particularly recycled plastic waste, into a variety of useful pyrolysis derivatives. It should be understood that... Figure 2The pyrolysis system shown is merely one example of a system in which this disclosure can be implemented. The invention can be applied to a variety of other systems where it is desirable to efficiently and effectively pyrolyze recycled waste, particularly recycled plastic waste, into various desired end products. A more detailed description will now follow. Figure 2 The exemplary pyrolysis system shown is illustrated.

[0326] like Figure 2 As shown, the pyrolysis system 110 may include a waste plastic source 112 for supplying one or more waste plastics to the system 110. The plastic source 112 may be, for example, a hopper, storage bin, railcar, long-haul trailer, or any other device capable of containing or storing waste plastics. In one embodiment or in combination with any of the embodiments mentioned herein, the waste plastic supplied by the plastic source 112 may be in the form of solid particles, such as fragments, flakes, or powder. Although in Figure 2 As not described herein, the pyrolysis system 110 may also include additional sources of other types of recycled waste, which may be used to provide other types of feed to the system 110.

[0327] In one embodiment or in combination with any of the embodiments mentioned herein, 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 combinations thereof. In one embodiment or in combination with any of the embodiments mentioned herein, waste plastics may include high-density polyethylene, low-density polyethylene, polypropylene, or combinations thereof. As used herein, “post-consumer” refers to non-virgin plastics that have previously been introduced into the consumer market.

[0328] In one embodiment or in combination with any of the embodiments mentioned herein, a feed containing waste plastics may be supplied from plastic source 112. In one embodiment or in combination with any of the embodiments mentioned herein, the feed containing waste plastics may comprise, substantially comprise, 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.

[0329] In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastics 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% of at least one, two, three, or four different kinds of waste plastics. 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% of polyvinyl chloride and / or polyethylene terephthalate by weight in each case. In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastics may contain at least one, two, or three plasticized plastics. The reference to "kind" is determined by resin ID codes 1-7.

[0330] like Figure 2 As shown, solid waste plastic feed from plastic source 112 can be supplied to raw material pretreatment unit 114. In raw material pretreatment unit 114, the introduced waste plastic can undergo various pretreatments to facilitate subsequent pyrolysis reactions. Such pretreatments may include, for example, washing, mechanical agitation, flotation, diameter reduction, or any combination thereof. In one embodiment or in combination with any of the embodiments mentioned herein, the introduced plastic waste may be subjected to mechanical agitation or diameter reduction operations to reduce the particle size of the plastic waste. Such mechanical agitation can be provided by any mixing, shearing, or grinding apparatus 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%.

[0331] Next, the pretreated plastic raw material can be introduced into the plastic feeding system 116. The plastic feeding system 116 can be configured to introduce the plastic feed into the pyrolysis reactor 118. The plastic feeding 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 feeding system 116 can include a screw feeder, a hopper, a pneumatic conveying system, a mechanical metal bar or chain, or a combination thereof.

[0332] When in pyrolysis reactor 118, at least a portion of the plastic feed can undergo a pyrolysis reaction, producing a pyrolysis effluent containing pyrolysis oil (e.g., γ-pyrolysis oil) and pyrolysis gas (e.g., γ-pyrolysis gas). Pyrolysis reactor 118 can be, for example, an extruder, a tubular reactor, a tank, a stirred tank reactor, a riser reactor, a fixed bed reactor, a fluidized bed reactor, a rotary kiln, a vacuum reactor, a microwave reactor, an ultrasonic or supersonic reactor, or an autoclave, or a combination of these reactors.

[0333] Typically, pyrolysis is a process involving the chemical and thermal decomposition of an introduced feedstock. While all pyrolysis processes can generally be characterized by a substantially oxygen-free reaction environment, a pyrolysis process can be further defined by factors such as the pyrolysis reaction temperature within the reactor, the residence time within the pyrolysis reactor, the reactor type, the pressure within the pyrolysis reactor, and the presence or absence of a pyrolysis catalyst.

[0334] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction may include heating and converting the plastic raw material in a substantially oxygen-free atmosphere or in an atmosphere containing 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 may contain, in each case, no more than 5%, or no more than 4%, or no more than 3%, or no more than 2%, or no more than 1%, or no more than 0.5% of oxygen in total percentage.

[0335] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis process may be carried out in the presence of an inert gas such as nitrogen, carbon dioxide, and / or vapor. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis process may be carried out in the presence of a reducing gas such as hydrogen and / or carbon monoxide.

[0336] In one embodiment or in combination with any of the embodiments mentioned herein, the temperature in the pyrolysis reactor 118 may be adjusted to facilitate the production of certain end products. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 may be at least 325°C, or at least 350°C, or at least 375°C, or at least 400°C, or at least 425°C, or at least 450°C, or at least 475°C, or at least 500°C, or at least 525°C, or at least 550°C, or at least 575°C, or at least 600°C, or at least 625°C, or at least 650°C, or at least 675°C, or at least 700°C, or at least 725°C, or at least 750°C, or at least 775°C, or at least 800°C. Additionally, or alternatively... In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 may be no more than 1,100°C, or no more than 1,050°C, or no more than 1,000°C, or no more than 950°C, or no more than 900°C, or no more than 850°C, or no more than 800°C, or no more than 750°C, or no more than 700°C, or no more than 650°C, or no more than 600°C, or no more than 550°C, or no more than 525°C, or no more than 500°C, or no more than 475°C, or no more than 450°C, or no more than 425°C, or no more than 400°C. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 may be in the range of 325 to 1,100°C, 350 to 900°C, 350 to 700°C, 350 to 550°C, 350 to 475°C, 500 to 1,100°C, 600 to 1,100°C, or 650 to 1,000°C.

[0337] In one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction may be at least 1 second, or at least 2 seconds, 3 seconds, or at least, or at least 4 seconds, or at least 10, or at least 20 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes, or at least 75 minutes, or at least 90 minutes. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction may not exceed 6 hours, or not exceed 5 hours, or not exceed 4 hours, or not exceed 3 hours, 2 hours, or not exceed 1 hour, or not exceed 0.5 hours, 1 hour, or not exceed 0.5 hours. In one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction may range from 30 minutes to 4 hours, or 30 minutes to 3 hours, or 1 hour to 3 hours, or 1 hour to 2 hours.

[0338] In one embodiment or in combination with any embodiment mentioned herein, the pressure within the pyrolysis reactor 118 may 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 not exceeding 60 bar, or not exceeding 50 bar, or not exceeding 40 bar, or not exceeding 30 bar, or not exceeding 20 bar, or not exceeding 10 bar, or not exceeding 8 bar, or not exceeding 5 bar, or not exceeding 2 bar, or not exceeding 1.5 bar, or not exceeding 1.1 bar. In one embodiment or in combination with any embodiment mentioned herein, the pressure within the pyrolysis reactor 18 may be maintained at approximately atmospheric pressure or within the range of 0.1 to 100 bar, or 0.1 to 60 bar, or 0.1 to 30 bar, or 0.1 to 10 bar, or 1.5 bar, 0.2 to 1.5 bar, or 0.3 to 1.1 bar.

[0339] In one embodiment or in combination with any of the embodiments mentioned herein, a pyrolysis catalyst may be introduced into the plastic feed and / or directly into the pyrolysis reactor 118 prior to its introduction into the pyrolysis reactor 118 to produce r-catalytic pyrolysis oil or r-pyrolysis oil prepared by a catalytic pyrolysis process. In one embodiment or in combination with any of the embodiments mentioned herein, the catalyst may comprise: (i) a solid acid, such as a zeolite (e.g., ZSM-5, mordenite, β, magnesium alkali zeolite and / or zeolite-Y); (ii) a superacid, such as zirconium oxide, titanium dioxide, alumina, sulfonated, phosphorylated or fluorinated forms of silica-alumina, and / or clay; (iii) a solid base, such as metal oxides, mixed metal oxides, metal hydroxides and / or metal carbonates, particularly those of alkali metals, alkaline earth metals, transition metals and / or rare earth metals; (iv) hydrotalcite 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.

[0340] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 occurs in the substantially absence of a catalyst, particularly the catalyst described above. In such embodiments, 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.

[0341] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 can occur in the absence of a pyrolysis catalyst, at a temperature in the range of 350 to 550°C, at a pressure in the range of 0.1 to 60 bar, and at a residence time of 0.2 seconds to 4 hours or 0.5 hours to 3 hours.

[0342] Refer again Figure 2 The pyrolysis effluent 120 exiting the pyrolysis reactor 118 typically comprises pyrolysis gases, pyrolysis vapors, and residual solids. As used herein, the vapors generated during the pyrolysis reaction can 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 comprise carbon, ash, unconverted plastic solids, other unconverted solids from the feedstock, and / or particles of spent catalyst (if a catalyst is used).

[0343] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain, in each case, 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% by weight of pyrolysis vapor, which may subsequently condense into the 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, in each case, at a weight percentage not exceeding 99, or not exceeding 95, or not exceeding 90, or not exceeding 85, or not exceeding 80, or not exceeding 75, or not exceeding 70, or not exceeding 65, or not exceeding 60, or not exceeding 55, or not exceeding 50, or not exceeding 45, or not exceeding 40, or not exceeding 35, or not exceeding 30%. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis effluent 120 may contain 20 to 99% by weight, 40 to 90% by weight, or 55 to 90% by weight of pyrolysis vapor.

[0344] In one embodiment or in combination with any embodiment mentioned herein, pyrolysis effluent 120 may contain, in each case, at least 1, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12% by weight of pyrolysis gas (e.g., r-pyrolysis gas). As used herein, “pyrolysis gas” means 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, pyrolysis effluent 20 may contain, in each case, at a weight percentage not exceeding 90, or not exceeding 85, or not exceeding 80, or not exceeding 75, or not exceeding 70, or not exceeding 65, or not exceeding 60, or not exceeding 55, or not exceeding 50, or not exceeding 45, or not exceeding 40, or not exceeding 35, or not exceeding 30, or not exceeding 25, or not exceeding 20, or not exceeding 15% of pyrolysis vapor. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis effluent 120 may 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 of pyrolysis gas.

[0345] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain residual solids in each case in a weight percentage not exceeding 15, or not exceeding 10, or not exceeding 9, or not exceeding 8, or not exceeding 7, or not exceeding 6, or not exceeding 5, or not exceeding 4, or not exceeding 3.

[0346] In one embodiment or in any combination of the mentioned embodiments, a cracker feedstock composition comprising pyrolysis oil (r-pyrolysis oil) is provided, wherein the r-pyrolysis oil composition comprises a recoverable component catalytic pyrolysis oil (r-catalytic pyrolysis oil) and a recoverable component pyrolysis oil (r-pyrolysis oil). The r-pyrolysis oil is a pyrolysis oil prepared without the addition of a pyrolysis catalyst. The cracker feedstock may include at least 5, 10, 15, or 20 weight percent of r-catalytic pyrolysis oil, which may optionally be 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. Optionally, the blended stream may contain no more than 10, 5, 3, 2, or 1 weight percent of unhydrotreated r-catalytic pyrolysis oil. In one embodiment or in any combination of the mentioned embodiments, the r-pyrolysis oil is free of r-catalytic pyrolysis oil.

[0347] like Figure 2As shown, the conversion effluent 120 from the pyrolysis reactor 118 can be introduced into a solids separator 122. The solids 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 of the embodiments mentioned herein, the solids separator 122 removes a majority of the solids from the conversion effluent 120. In one embodiment or in combination with any of the embodiments mentioned herein, at least a portion of the solid particles 24 recovered in the solids separator 122 can be introduced into an optional regenerator 126 for regeneration, typically by combustion. After regeneration, at least a portion of the thermally regenerated solids 128 can be directly introduced into the pyrolysis reactor 118. In one embodiment or in combination with any of the embodiments mentioned herein, at least a portion of the solid particles 124 recovered in the solids separator 122 can be directly introduced back into the pyrolysis reactor 118, particularly if the solid particles 124 contain a significant amount of unconverted plastic waste. Solids can be removed from the regenerator 126 via line 145 and discharged from the system.

[0348] Back Figure 2 The residual gas and vapor reforming products 130 from the solids separator 122 can be introduced into the fractionation column 132. In the fractionation column 132, at least a portion of the pyrolysis oil vapor can be separated from the cracked gas, thereby forming a cracked gas product stream 134 and a pyrolysis oil vapor stream 136. Suitable systems used as the fractionation column 132 may include, for example, distillation columns, membrane separation units, quench columns, condensers, or any other known separation units in the art. In one embodiment or in combination with any of the embodiments mentioned herein, any residual solids 146 accumulated in the fractionation column 132 can be introduced into an optional regenerator 126 for further processing.

[0349] In one embodiment or in combination with any of the embodiments mentioned herein, at least a portion of the pyrolysis oil vapor stream 136 may be introduced into the quenching unit 138 to quench the pyrolysis vapors at least partially into their liquid form (i.e., pyrolysis oil). The quenching unit 138 may include any suitable quenching system known in the art, such as a quenching tower. The resulting liquid pyrolysis oil stream 140 may be removed from system 110 and used for other downstream applications described herein. In one embodiment or in combination with any of the embodiments mentioned herein, the liquid pyrolysis oil stream 140 may not undergo any additional treatment, such as hydrotreating and / or hydrogenation, prior to use in any of the downstream applications described herein.

[0350] In one embodiment or in combination with any of the embodiments mentioned herein, at least a portion of the pyrolysis oil vapor stream 136 may be introduced into a hydrotreating unit 142 for further refining. The hydrotreating unit 142 may include a hydrocracker, a catalytic cracker operating with a hydrogen feed stream, a hydrotreating unit, and / or a hydrogenation unit. In the hydrotreating unit 142, the pyrolysis oil vapor stream 136 may be treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil and remove unwanted byproducts from the pyrolysis oil. The resulting hydrotreated pyrolysis oil vapor stream 144 may be removed and introduced into a quenching unit 138. Alternatively, the pyrolysis oil vapor may be cooled, liquefied, and then treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil. In this case, hydrogenation or hydrotreating is performed in the liquid phase of the pyrolysis oil. In this embodiment, post-hydrogenation or post-hydrotreating does not require a quenching step.

[0351] 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 for various downstream applications based on their desired formulation. Various characteristics and properties of the pyrolysis oil and pyrolysis gas are described below. It should be noted that although all the following characteristics and properties may be listed individually, it is conceivable that each of the following characteristics and / or properties of the pyrolysis oil or pyrolysis gas is not mutually exclusive and may exist in any combination.

[0352] Pyrolysis oil can primarily consist of hydrocarbons with 4 to 30 carbon atoms per molecule (e.g., C4 to C5). 30 Hydrocarbons). As used herein, the term “Cx” or “Cx hydrocarbon” refers to a hydrocarbon compound comprising x total carbon atoms per molecule, and includes all alkenes, alkanes, aromatics, and isomers having that number of carbon atoms. For example, each of the n-, iso-, and tert-butane molecules and butene and butadiene molecules will fall under the general description “C4”.

[0353] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the cracker may have a C4-C content of at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95% by weight in each case. 30 Hydrocarbon content, based on the weight of pyrolysis oil.

[0354] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed into the furnace may primarily consist of C5-C. 25 C5-C22 or C5-C20 hydrocarbons, or may contain, in each case, 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% C5-C20 hydrocarbons by weight. 25C5-C 22 Or C5-C 20 Hydrocarbons, based on the weight of pyrolysis oil.

[0355] A gas furnace can accommodate a variety of hydrocarbon numbers in the pyrolysis oil feedstock, thus avoiding the need for separation techniques to deliver smaller or lighter hydrocarbon fractions to the cracker. In one embodiment or any of the mentioned embodiments, the pyrolysis oil does not undergo separation processes to separate the heavy hydrocarbon fractions from the lighter hydrocarbon fractions relative to each other after being delivered from the pyrolysis manufacturer and before being fed into the cracker furnace. Feeding the pyrolysis oil into the gas furnace allows the use of pyrolysis oil containing a heavy tail or a carbon number of 12 or higher. In one embodiment or any of the mentioned embodiments, the pyrolysis oil fed into the cracker is C5-C. 25 Hydrocarbon stream containing at least 3 wt.%, or at least 5 wt.%, or at least 8 wt.%, or at least 10 wt.%, or at least 12 wt.%, or at least 15 wt.%, or at least 18 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%, or at least 45 wt.%, or at least 50 wt.%, or less than 55 wt.%, or at least 60 wt.% of C 12 To C 25 Within the range of (including endpoints), or in C 14 To C 25 Within the range of (including endpoints), or in C 16 To C 25 Hydrocarbons within the range of (including end values).

[0356] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a C6-C content of at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55% by weight in each case. 12 Hydrocarbon content, based on the weight of the pyrolysis oil. Additionally or alternatively, in one embodiment or in combination with any embodiments mentioned herein, the pyrolysis oil may have a C6-C content of no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60% by weight in each case. 12 Hydrocarbon content. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have 10 to 95% by weight, 20 to 80% by weight, or 35 to 80% by weight of C6-C4 hydrocarbons. 12 Hydrocarbon content.

[0357] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a C content of at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30% by weight in each case. 13 -C 23 Hydrocarbon content. Additionally or alternatively, in one embodiment or in combination with any 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% by weight in each case. 13 To C 23 Hydrocarbon content. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have 1 to 80 wt%, 5 to 65 wt%, or 10 to 60 wt% C. 13 To C 23 Hydrocarbon content.

[0358] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil fed to the cracker, or the r-pyrolysis oil fed to the cracker that has received predominantly C2-C4 feedstock prior to the feed pyrolysis oil (and any mention of r-pyrolysis oil or pyrolysis oil herein refers to any of these embodiments), may have a C content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5% by weight in each case. 24+ Hydrocarbon content. Additionally or alternatively, in one embodiment or in combination with any embodiments mentioned herein, the pyrolysis oil may have a C content of no more than 15, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6. 24+ Hydrocarbon content, in each case, is a weight percentage. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have 1 to 15 weight percentage, 3 to 15 weight percentage, 2 to 5 weight percentage, or 5 to 10 weight percentage of C. 24+ Hydrocarbon content.

[0359] The pyrolysis oil may also include various amounts of olefins, aromatic hydrocarbons, and other compounds. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil contains, in each case, at least 1, or at least 2, or at least 5, or at least 10, or at least 15, or at least 20% by weight of olefins and / or aromatic hydrocarbons. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may contain, in each case, at a weight percentage not exceeding 50, or not exceeding 45, or not exceeding 40, or not exceeding 35, or not exceeding 30, or not exceeding 25, or not exceeding 20, or not exceeding 15, or not exceeding 10, or not exceeding 5, or not exceeding 2, or not exceeding 1.

[0360] 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 as a weight percentage. In one embodiment or in combination with any of the mentioned embodiments, 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 as a weight percentage.

[0361] 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% by weight 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 an undetectable amount by weight 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 an undetectable amount by weight. Alternatively, the pyrolysis oil may contain 1 to 50 percent, 5 to 50 percent, or 10 to 45 percent of cycloalkanes, especially if the r-pyrolysis oil has undergone a hydrotreating process.

[0362] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane content of at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50% by weight in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane content of 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% by weight in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane content of 25 to 90%, 35 to 90%, or 40 to 80%, or 40 to 70%, or 40 to 65% by weight.

[0363] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a n-alkane content of at least 5, or at least 10, or at least 15, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50% by weight in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a n-alkane content of no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55% by weight in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a n-alkane content of 25 to 90%, 35 to 90%, or 40 to 70%, or 40 to 65%, or 50 to 80% by weight.

[0364] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane to olefin weight ratio of at least 0.2:1, or at least 0.3:1, or at least 0.4:1, or at least 0.5:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1:1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have an alkane to olefin weight ratio of 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 pyrolysis oil may have an alkane to olefin weight ratio of 0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1 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.

[0365] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a n-chain alkane to isochain alkane weight ratio of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a n-chain alkane to isochain alkane 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 of the embodiments mentioned herein, the pyrolysis oil may have a weight ratio of n-alkanes to isoalkanes in the range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0366] It should be noted that all the above-mentioned hydrocarbon weight percentages can be determined using gas chromatography-mass spectrometry (GC-MS).

[0367] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can exhibit at least 0.6 g / cm³ at 15°C. 3 or at least 0.65 g / cm³ 3 or at least 0.7 g / cm 3 The density. Additionally or alternatively, in one embodiment or in combination with any embodiments mentioned herein, the pyrolysis oil may exhibit a density not exceeding 1 g / cm³ at 15°C. 3 or not exceeding 0.95 g / cm³ 3 or not exceeding 0.9 g / cm³ 3 or not exceeding 0.85 g / cm³ 3 The density. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil exhibits a density of 0.6 to 1 g / cm³ at 15°C. 3 0.65 to 0.95 g / cm³ 3 Or 0.7 to 0.9 g / cm³ 3 .

[0368] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may exhibit an API strength of at least 28, or at least 29, or at least 30, or at least 31, or at least 32, or at least 33 at 15°C. Additionally, or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may exhibit an API strength of no more than 50, or no more than 49, or no more than 48, or no more than 47, or no more than 46, or no more than 45, or no more than 44 at 15°C. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil exhibits an API strength of 28 to 50, 29 to 58, or 30 to 44 at 15°C.

[0369] 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. This value may be measured according to ASTM D-2887 or the procedure described in the working example. If this value is obtained by any method, a medium boiling point having said value is satisfied. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a medium boiling point not exceeding 250°C, or not exceeding 245°C, or not exceeding 240°C, or not exceeding 235°C, or not exceeding 230°C, or not exceeding 225°C, or not exceeding 220°C, or not exceeding 215°C, or not exceeding 210°C, or not exceeding 205°C, or not exceeding 200°C, or not exceeding 195°C, or not exceeding 190°C, or not exceeding 185°C, or not exceeding 180°C, or not exceeding 175°C, or not exceeding 170°C, or not exceeding 165°C, or not exceeding 160°C, or not exceeding 160°C, or not exceeding 55°C, or not exceeding 150°C, or not exceeding 145°C, or not exceeding 140°C, or not exceeding 135°C, or not exceeding 130°C, or not exceeding 125°C, or not exceeding 120°C. These values ​​may be measured according to ASTM D-2887 or the procedures described in the working examples. If this value is obtained by any method, a medium boiling point with said value is satisfied. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a medium boiling point in the range of 75 to 250°C, 90 to 225°C, or 115 to 190°C. As used herein, "medium boiling point" refers to the median boiling point temperature of the pyrolysis oil when 50% by weight of the pyrolysis oil boils above the medium boiling point and 50% by weight of the pyrolysis oil boils below the medium boiling point.

[0370] In one embodiment or in combination with any of the embodiments mentioned herein, the boiling point range of the pyrolysis oil may 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, a procedure according to ASTM D-2887 or described in the working example may be used, and if the value is obtained by any method, then the FBP with said value is satisfied.

[0371] Turning to the pyrolysis gas, the pyrolysis gas 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% by weight. Additionally or alternatively, in one embodiment or in combination with any embodiments mentioned herein, the pyrolysis gas 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% by weight in each case. In one embodiment or in combination with any embodiments mentioned herein, the pyrolysis gas may have a methane content of 1 to 50%, 5 to 50%, or 15 to 45% by weight.

[0372] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C3 hydrocarbon content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 15, or at least 20, or at least 25% by weight in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C3 hydrocarbon content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30% by weight in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C3 hydrocarbon content of 1 to 50% by weight, 5 to 50% by weight, or 20 to 50% by weight.

[0373] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20% by weight in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25% by weight in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of 1 to 50% by weight, 5 to 50% by weight, or 20 to 50% by weight.

[0374] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil of the present invention may be a recycled component pyrolysis oil composition (r-pyrolysis oil).

[0375] The various downstream applications that can utilize the pyrolysis oil and / or pyrolysis gases disclosed above are described in more detail below. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may undergo one or more processing steps before being introduced into a downstream unit such as a cracker. 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.

[0376] Turn now Figure 3 This diagram shows a processing zone for pyrolysis oil according to one embodiment or in combination with any of the embodiments mentioned herein.

[0377] like Figure 3 As shown in the processing zone 220, at least a portion of the r-pyrolysis oil 252 produced from the recycled waste stream 250 in the pyrolysis system 210 can be passed through the processing zone 220, such as a separator, which can separate the r-pyrolysis oil into a light pyrolysis oil fraction 254 and a heavy pyrolysis oil fraction 256. The separator 220 used for this separation can be of any suitable type, including a single-stage vapor-liquid separator or a "flash" column, or a multi-stage distillation column. The vessel may or may not include internal components and may or may not employ reflux and / or boiling flow.

[0378] In one embodiment or in combination with any of the embodiments mentioned herein, the C4-C7 or C8+ content of the heavy fraction may be at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by weight. The light fraction may include at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% of C3 and lighter (C3-) or C7 and lighter (C7-) content. In some embodiments, the separator may concentrate the desired components into the heavy fraction such that the heavy fraction may have a higher C4-C7 or C8+ content than the pyrolysis oil taken from the pyrolysis zone. 8+ Content of at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 7, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150% C4-C7 content or C 8+ Content. For example... Figure 3 As shown, at least a portion of the heavy fraction can be fed to cracker 230 for cracking as part of the r-pyrolysis oil composition or as a component of the pyrolysis oil composition, thereby forming olefin-containing effluent 258, as discussed in further detail below.

[0379] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil is hydrogenated in a processing zone, while in other embodiments, the pyrolysis oil is not hydrogenated before entering a downstream unit such as a cracker. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil is not pretreated at all before any downstream application and can be sent directly from the pyrolysis oil source. The temperature of the pyrolysis oil leaving the pretreatment zone can be in the range of 15 to 55°C, 30 to 55°C, 49 to 40°C, 15 to 50°C, 20 to 45°C, or 25 to 40°C.

[0380] In one embodiment or in combination with any of the embodiments mentioned herein, 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 certain concentration of less desirable compounds (e.g., impurities such as oxygenated compounds, aromatic hydrocarbons, or other compounds described herein), the r-pyrolysis oil can be combined with the cracker feed in an amount such that the total concentration of less desirable compounds in the combined stream is at least 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% less than the original content of the compounds in the r-pyrolysis oil stream (calculated as the difference between the r-pyrolysis oil and the combined stream divided by the r-pyrolysis oil content, expressed as a percentage). In some cases, the amount of non-recovery cracker feed combined with the r-pyrolysis oil stream can be determined by comparing a measured amount of one or more less desirable compounds present in the r-pyrolysis oil with target values ​​for those compounds to determine the difference, and then based on that difference, the amount of non-recovery hydrocarbons to be added to the r-pyrolysis oil stream can be determined. The amounts of r-pyrolysis oil and non-recovered hydrocarbons are within one or more of the ranges described herein.

[0381] At least a portion of γ-ethylene is derived directly or indirectly from the cracking of γ-pyrolysis oil. The process for obtaining γ-olefins from cracking (γ-pyrolysis oil) can be as follows and... Figure 4 As described in [the text].

[0382] Turn Figure 4 This is a flow chart of the steps associated with the cracking furnace 20 and separation zone 30 of a system for producing r-compositions from cracked r-pyrolysis oil. (See also:) Figure 4 As shown, a feed stream containing r-pyrolysis oil (r-pyrolysis oil-containing feed stream) can be introduced into cracker 20, either alone or in combination with a non-recovery cracker feed stream. The pyrolysis unit that generates r-pyrolysis oil can be located in 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.

[0383] In one embodiment or in combination with any of the embodiments mentioned herein, the feed stream containing r-pyrolysis oil may contain, in each case, at a weight percentage 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% by weight and / or not more than 95, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20% of r-pyrolysis oil, based on the total weight of the feed stream containing r-pyrolysis oil.

[0384] In one embodiment or in combination with any embodiment mentioned herein, at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 97, or at least 98, or at least 99, or 100% by weight 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% by weight of r-pyrolysis oil is obtained from the pyrolysis of the waste stream. In one embodiment or in combination with any of the embodiments mentioned herein, at least a portion of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock containing plastic waste. Desiredly, 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 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.

[0385] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have any one or a combination of the compositional features described above regarding pyrolysis oil.

[0386] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may 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% by weight of C4-C 30 Hydrocarbons, and as used herein, include aliphatic, alicyclic, aromatic, and heterocyclic compounds. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may primarily comprise C5-C64 hydrocarbons. 25 C5-C 22 Or C5-C 20 Hydrocarbons, or may contain at least 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight of C5-C 25 C5-C 22 Or C5-C 20 hydrocarbon.

[0387] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil composition may contain C4-C 12 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and alicyclic hydrocarbons) and C 13 -C 22 Aliphatic compounds, in weight ratios 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.

[0388] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil composition may contain C 13 -C 22 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and alicyclic hydrocarbons) and C4-C 12 Aliphatic compounds, in weight ratios 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.

[0389] In one embodiment, the two aliphatic hydrocarbons (branched or unbranched alkanes and alkenes, as well as alicyclic compounds) with the highest concentrations in the r-pyrolysis oil are C5-C 18 Or C5-C 16 Or C5-C 14 Or C5-C 10 , or within the range of C5-C8 (including the endpoints).

[0390] r-pyrolysis oil includes one or more of the following: alkanes, cycloalkanes or cyclic aliphatic hydrocarbons, aromatic hydrocarbons, aromatic hydrocarbons, olefins, oxygen-containing compounds and polymers, heteroatom compounds or polymers, and other compounds or polymers.

[0391] For example, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may contain, in each case, at a weight percentage of at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, and / or not more than 99, or not more than 97 ... 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 alkanes (or straight-chain or branched alkanes), based on the total weight of the r-pyrolysis oil. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an alkane content of 25 to 90, 35 to 90, or 40 to 80, or 40 to 70, or 40 to 65 percent by weight, 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 percent, in each case as wt.% based on the weight of the r-pyrolysis oil composition.

[0392] 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 as a weight percentage, and / or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 15, or not more than 10, or not more than 5, or not more than 2, or not more than 1, or not more than 0.5, or an undetectable amount, in each case as a weight percentage. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have a cycloalkanes content of not more than 5, or not more than 2, or not more than 1 wt.%, or an undetectable amount. Examples of the range of cycloalkanes (or cycloaliphatic hydrocarbons) contained in 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 in wt.% based on the weight of the r-pyrolysis oil composition.

[0393] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have an alkane to olefin weight ratio of at least 0.2:1, or at least 0.3:1, or at least 0.4:1, or at least 0.5:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1:1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have an alkane to olefin weight ratio of no more than 3:1, or no more than 2.5:1, or no more than 2:1, or no more than 1.5:1, or no more than 1.4:1, or no more than 1.3:1. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have an alkane 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.

[0394] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have a n-alkane to isoalkane weight ratio of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have a n-alkane to isoalkane weight ratio of no more than 100:1, or no more than 50:1, or no more than 40:1, or no more than 30:1. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have a weight ratio of n-alkanes to isoalkanes in the range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0395] In one embodiment, the r-pyrolysis oil contains, in each case, 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 by weight, based on the total weight of the r-pyrolysis oil. As used herein, the term "aromatic hydrocarbon" 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% aromatic hydrocarbons by weight, in each case based on the total weight of the r-pyrolysis oil.

[0396] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include an amount of aromatic hydrocarbons, or undetectable amounts, in each case not exceeding 30, or not exceeding 25, or not exceeding 20, or not exceeding 15, or not exceeding 10, or not exceeding 8, or not exceeding 5, or not exceeding 2, or not exceeding 1, by weight, based on the total weight of the r-pyrolysis oil. Aromatic compounds include the aromatic hydrocarbons described above and any compounds containing an aromatic moiety, such as terephthalate residues and fused-ring aromatic hydrocarbons, such as naphthalene and tetrahydronaphthalene.

[0397] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include an amount of olefins in each case as a weight percentage 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, and / or as a weight percentage not exceeding 85, or not exceeding 80, or not exceeding 75, or not exceeding 70, or not exceeding 65, or not exceeding 60, or not exceeding 55, or not exceeding 50, or not exceeding 45, or not exceeding 40, or not exceeding 35, or not exceeding 30, or not exceeding 25, or not exceeding 20, or not exceeding 15, or not exceeding 10, based on the weight of the r-pyrolysis oil. The olefins include monoolefins and dienes. 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, or 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 r-pyrolysis oil.

[0398] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include zero or, in each case, at least 0.01, 0.1, 1, 2, or 5 wt.% of an oxygenated compound or polymer, and / or, in each case, at a weight percentage not exceeding 20, 15, 10, 8, 6, 5, 3, or 2 wt.% of an oxygenated compound or polymer, based on the weight of the r-pyrolysis oil. The oxygenated compound and polymer are those containing oxygen atoms. Examples of suitable ranges include amounts containing oxidized components in the r-pyrolysis oil in the range of 0-20, 0-15, 0-10, 0.01-10, 1-10, 2-10, 0.01-8, 0.1-6, 1-6, or 0.01-5 wt.%.

[0399] In one embodiment or in combination with any embodiment mentioned herein, the amount of oxygen atoms in the r-pyrolysis oil may be no more than 10, or no more than 8, or no more than 5, or no more than 4, or no more than 3, or no more than 2.75, or no more than 2.5, or no more than 2.25, or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.1, or no more than 0.05, in each case as wt.% based on the weight of the r-pyrolysis oil. Examples of the amount of oxygen in r-pyrolysis oil can 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 as wt.% based on the weight of the r-pyrolysis oil.

[0400] 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% by weight, 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% by weight, 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 in determining the amount of heteroatoms, heterocompounds, or heteropolymers present in the r-pyrolysis oil. r-pyrolysis oil may contain heteroatoms in amounts not exceeding 5, or not exceeding 4, or not exceeding 3, or not exceeding 2.75, or not exceeding 2.5, or not exceeding 2.25, or not exceeding 2, or not exceeding 1.75, or not exceeding 1.5, or not exceeding 1.25, or not exceeding 1, or not exceeding 0.75, or not exceeding 0.5, or not exceeding 0.25, or not exceeding 0.1, or not exceeding 0.075, or not exceeding 0.05, or not exceeding 0.03, or not exceeding 0.02, or not exceeding 0.01, or not exceeding 0.008, or not exceeding 0.006, or not exceeding 0.005, or not exceeding 0.003, or not exceeding 0.002, in each case as wt.% based on the weight of r-pyrolysis oil.

[0401] 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 not more than 1.5, or not more than 1, or not more than 0.5, or not more than 0.1, or not more than 0.075, or not more than 0.05, or not more than 0.025, or not more than 0.01, or not more than 0.005, in each case being wt.% water based on the weight of r-pyrolysis oil. Desiredly, the solubility of water in r-pyrolysis oil is not more than 0.1 wt.% based on the weight of 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, preferably 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.

[0402] 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 being wt.% solids based on the weight of the r-pyrolysis oil.

[0403] 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, preferably no more than 0.03, or no more than 0.02, or no more than 0.01, or no more than 0.008, or no more than 0.006, or no more than 0.004, or no more than 0.002, or no more than 0.001, in each case as wt.% based on the weight of the r-pyrolysis oil.

[0404] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have the following component contents:

[0405] 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 at 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 at wt.%, preferably at least 82% and at most 93%, and / or

[0406] 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 being wt.%.

[0407] 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 as wt.%.

[0408] In each case, the weight of the pyrolysis oil is used as the basis.

[0409] In one embodiment or in combination with any of the embodiments mentioned herein, the amount of hydrogen atoms in the r-pyrolysis oil may be in the range of 10-20, or 10-18, or 11-17, or 12-16, or 13-16, or 13-15, or 12-15, in each case in wt.% based on the weight of the r-pyrolysis oil.

[0410] In one embodiment or in combination with any embodiment mentioned herein, the metal content of the r-pyrolysis oil is desired to be low, for example, not more than 2 wt.%, or not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.2, or not more than 0.15, or not more than 0.1, or not more than 0.05, in each case as wt.% based on the weight of the r-pyrolysis oil.

[0411] In one embodiment or in combination with any embodiment mentioned herein, the alkali metal and alkaline earth metal or mineral content of the r-pyrolysis oil is expected to be low, for example, not exceeding 2 wt.%, or not exceeding 1, or not exceeding 0.75, or not exceeding 0.5, or not exceeding 0.25, or not exceeding 0.2, or not exceeding 0.15, or not exceeding 0.1, or not exceeding 0.05, in each case as wt.% based on the weight of the r-pyrolysis oil.

[0412] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of alkanes to cycloalkanes in the r-pyrolysis oil may 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.

[0413] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of the combination of alkanes and cycloalkanes to aromatics may 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 r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, the ratio of alkanes and cycloalkanes to aromatics in the r-pyrolysis oil may be in the range of 50:1-1:1, or 40:1-1:1, or 30:1-1:1, or 20:1-1:1, or 30:1-3:1, or 20:1-1:1, or 20:1-5:1, or 50:1-5:1, or 30:1-5:1, or 1:1-7:1, or 1:1-5:1, 1:1-4:1, or 1:1-3:1.

[0414] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may have a boiling point profile defined by one or more of its 10%, 50%, and 90% boiling points, as defined below. As used herein, “boiling point” means the boiling point of a composition determined by ASTM D2887 or according to the procedure described in the working example. If this value is obtained by either method, a boiling point having said value is satisfied. Additionally, as used herein, “x% boiling point” means that x weight percentage of the composition boils at that boiling point according to any of these methods.

[0415] As used throughout, x% boiling point at said temperature means that at least x% of the composition boils at said temperature. In one embodiment or in combination with any embodiment described herein, the 90% boiling point of the cracker feed stream or composition may not exceed 350, or 325, or 300, or 295, or 285, or 280, or 275, or 270, or 265, or 260, or 255, or 250, or 245, or 240, or 235, or 230, or 22 5, or not more than 220, or not more than 215, not more than 200, not more than 190, not more than 180, not more than 170, not more than 160, not more than 150 or not more than 140, in each case for °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 for °C, and / or not more than 25, 20, 15, 10, 5, or 2 weight percent of r-pyrolysis oil may have a boiling point of 300 °C or higher.

[0416] Refer again Figure 3The r-pyrolysis oil may be introduced into the cracker furnace, coil, or tube alone (e.g., containing at least 85, or at least 90, or at least 95, or at least 99, or 100, in each case as wt.% of the 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 the cracker furnace, coil, or tube together with the non-recovery cracker feed stream, the amount of r-pyrolysis oil present may be at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 12, or at least 15, or at least 20, or at least 25, or at least 30, in each case as wt.%, and / or not exceeding 40, or not exceeding 35, or not exceeding 30, or not exceeding 25, or not exceeding 20, or not exceeding 15, or not exceeding 10, or not exceeding 8, or not exceeding 5, or not exceeding 2, in each case as a weight percentage based on the total weight of the combined stream. Therefore, the non-recovery cracker feed stream or composition may 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 as a weight percentage, and / or not exceeding 99, or not exceeding 95, or not exceeding 90, or not exceeding 85, or not exceeding 80, or not exceeding 75, or not exceeding 70, or not exceeding 65, or not exceeding 60, or not exceeding 55, or not exceeding 50, or not exceeding 45, or not exceeding 40, in each case as a weight percentage based on the total weight of the combined stream. Unless otherwise stated herein, the properties of the cracker feed streams described below apply to non-recovery cracker feed streams prior to (or not present) a combination with a stream containing r-pyrolysis oil, and to combined cracker streams comprising both non-recovery cracker feed and r-pyrolysis oil feed.

[0417] In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed stream may comprise a composition primarily containing C2-C4 hydrocarbons, or primarily containing C5-C4 hydrocarbons. 22Hydrocarbon compositions. As used herein, the term “primarily C2-C4 hydrocarbons” refers to a feed stream or composition containing at least 50% by weight of a C2-C4 hydrocarbon component. Examples of specific types of C2-C4 hydrocarbon streams or compositions include propane, ethane, butane, and LPG. In one embodiment or in combination with any of the embodiments 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, as a wt.% based on the total weight of the feed, and / or no more than 100, or no more than 99, or no more than 95, or no more than 92, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, in each case, as a C2-C4 hydrocarbon or linear alkane weight percentage based on the total weight of the feed. Cracker feed may contain primarily propane, primarily ethane, primarily butane, or a combination of two or more of these components. These components may be non-recoverable. Cracker feed may contain primarily propane, or at least 50 mol% propane, or at least 80 mol% propane, or at least 90 mol% propane, or at least 93 mol% propane, or at least 95 mol% propane (including any recoverable stream mixed with fresh feed). Cracker feed may contain HD5 mass propane as raw or fresh feed. Cracker feed may contain more 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-recoverable.

[0418] In one embodiment or in combination with any of the embodiments described herein, the cracker feed stream may contain primarily C5-C. 22 A composition of hydrocarbons. As used herein, "primarily C5-C". 22 "Hydrocarbon" refers to hydrocarbons containing at least 50% by weight of C5-C64. 22 A stream or composition of hydrocarbon components. Examples include gasoline, naphtha, middle distillate, diesel, and kerosene. In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed stream or composition may contain at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.%, and / or not more than 100, or not more than 99, or not more than 95, or not more than 92, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, in each case C5-C 22 Or C5-C20 Hydrocarbon weight percentage, based on the total weight of the stream or composition. In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed may have a C content of at least 0.5, or at least 1, or at least 2, or at least 5. 15 and heavier (C) 15+ The content, in each case, is a weight percentage, and / or not exceeding 40, or not exceeding 35, or not exceeding 30, or not exceeding 25, or not exceeding 20, or not exceeding 18, or not exceeding 15, or not exceeding 12, or not exceeding 10, or not exceeding 5, or not exceeding 3, in each case, is a weight percentage based on the total weight of the feed.

[0419] The cracker feed can have a boiling point profile defined by one or more of its 10%, 50%, and 90% boiling points, obtained by the method described above. Additionally, as used herein, "x% boiling point" refers to the boiling point at which x weight percentages of the composition boil according to the method described above. In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feed stream or composition can 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 exceeding 270, or not exceeding 265, or not exceeding 260, or not exceeding 255, or not exceeding 250, or not exceeding 245, or not exceeding 240, or not exceeding 235, or not exceeding 230, or not exceeding 225, or not exceeding 220, or not exceeding 215, in each case ℃, 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 ℃.

[0420] In one embodiment or in combination with any embodiment mentioned herein, the 10% boiling point of the cracker feed stream or composition may be at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150 or at least 155 °C in each case, and / or not exceeding 250, not exceeding 240, not exceeding 230, not exceeding 220, not exceeding 210, not exceeding 200, not exceeding 190, not exceeding 180 or not exceeding 170 °C in each case.

[0421] In one embodiment or in combination with any embodiment mentioned herein, the 50% boiling point of the cracker feed stream or composition may 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 °C, in each case °C, and / or not exceeding 300, not exceeding 290, not exceeding 280, not exceeding 270, not exceeding 260, not exceeding 250, not exceeding 240, not exceeding 230, not exceeding 220, not exceeding 210, not exceeding 200, not exceeding 190, not exceeding 180, not exceeding 170, not exceeding 160, not exceeding 150, or not exceeding 145 °C. The 50% boiling point of the cracker feed stream or composition 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 °C in each case.

[0422] In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feedstock 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 feedstock 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 feedstock or stream has a 90% boiling point of at least 350°C, a 10% boiling point of at least 150°C, and a 50% boiling point in the range of 220 to 280°C.

[0423] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil is cracked in a gas furnace. The gas furnace is a furnace having at least one coil that receives (or is operated to receive) a predominantly gaseous feed (more than 50% by weight of the feed is vapor) (“gas coil”) at a coil inlet at the convection zone inlet. In one embodiment or in combination with any of the embodiments mentioned herein, the gas coil may receive a predominantly C2-C4 or predominantly C2-C3 feedstock to the coil inlet in the convection zone, or alternatively, has 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. The gas furnace may have more than one gas coil. In one embodiment or in combination with any embodiment mentioned herein, at least 25% of the coils, or at least 50% of the coils, or at least 60% of the coils, or all of the coils in the convection zone or the convection box of the furnace are gas coils. In one embodiment or in combination with any embodiment mentioned herein, the gas coils receive a vapor phase feed at the coil inlet at the inlet of the convection zone, wherein at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is vapor.

[0424] In one embodiment or in combination with any of the embodiments mentioned herein, r-pyrolysis oil is cracked in a cracking furnace. The cracking furnace is a gas furnace. The cracking furnace includes at least one gas coil and at least one liquid coil within the same furnace, or within the same convection zone, or within the same convection box. The liquid coil is a coil (“liquid coil”) that receives a feed consisting primarily of the liquid phase (greater than 50% of the feed weight is liquid) at the coil inlet at the convection zone inlet. In one embodiment or in combination with any of the embodiments mentioned herein, the liquid coil may receive a feed consisting primarily of C at the inlet of the convection section (“liquid coil”). 5+ The raw materials are fed into the inlet of the coil. In one embodiment or in combination with any of the embodiments mentioned herein, the liquid coil may receive primarily C6-C. 22 The raw materials are mainly C7-C. 16The feedstock is fed to the inlet of the coil in the convection section, or alternatively, has at least one coil that receives more than 50 wt.% naphtha, and / or more than 50% natural gasoline, and / or more than 50% diesel, and / or more than JP-4, and / or more than 50% dry cleaning solvent, and / or more than 50% kerosene, and / or more than 50% fresh creosote, and / or more than 50% JP-8 or Jet-A, and / or more than 50% 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 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.%, in any of these cases, based on the weight of the cracker feed to the liquid coil, or alternatively based on the weight of the cracker feed to the convection zone. In one embodiment or in combination with any embodiment mentioned herein, at least one coil in the convection zone or the convection box of the furnace and no more than 75% of the coils, or no more than 50% of the coils, or no more than at least 40% of the coils are liquid coils. In one embodiment or in combination with any of the embodiments mentioned herein, the liquid coil receives a vapor phase feed at the coil inlet at the inlet of the convection zone, wherein at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is liquid.

[0425] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil is cracked in a hot gas cracker. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil is cracked in a hot steam gas cracker in the presence of steam. Steam cracking refers to the high-temperature cracking (decomposition) of hydrocarbons in the presence of steam. In one embodiment or in combination with any of the embodiments mentioned herein, the r-composition is derived directly or indirectly from the cracking of the 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.

[0426] When a feed stream containing γ-pyrolysis oil is combined with a non-recovery cracker feed, this combination can occur upstream of the cracker, inside the cracker, or within a single coil or tube. Alternatively, the γ-pyrolysis oil feed stream and the non-recovery cracker feed can be introduced into the furnace separately and can pass through part or all of the furnace simultaneously, isolated from each other by feeding into separate tubes within the same furnace (e.g., a cracking furnace). The manner in which the γ-pyrolysis oil feed stream and the non-recovery cracker feed are introduced into the cracker, according to one embodiment or in combination with any of the embodiments mentioned herein, is described in further detail below.

[0427] Turn now Figure 5 The diagram shows a cracking furnace applicable to the embodiments or in combination with any of the embodiments mentioned herein.

[0428] In one embodiment or any combination of embodiments mentioned, a method for preparing one or more olefins is provided, comprising:

[0429] (a) The first cracker feed, which includes a pyrolysis oil composition containing recycled components (r-pyrolysis oil), is fed into the cracker furnace;

[0430] (b) Feeding a second cracker feed into the cracking furnace, wherein the second cracker feed does not contain the r-pyrolysis oil or contains less (by weight) the r-pyrolysis oil than the first cracker feed stream; and

[0431] (c) The feedstocks of the first and second crackers are cracked in the respective first and second tubes to form an olefin-containing effluent stream.

[0432] R-pyrolysis oil can be combined with a 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 feed in steps (a) and / or (b) can be carried out upstream of or within the convection zone. R-pyrolysis oil can be combined with a non-recovery cracker stream to form a combined or first cracker stream and fed to the inlet of the convection zone, or alternatively, r-pyrolysis oil can be fed separately from the non-recovery cracker stream to the inlet of a coil or distributor to form a first cracker stream at the inlet of the convection zone, or r-pyrolysis oil can be fed downstream of the inlet of the convection zone into a tube containing non-recovery cracker feed, but prior to crossing, to prepare a first cracker stream or combined cracker stream in the tube or coil. Any of these methods includes feeding the first cracker stream into the furnace.

[0433] The amount of r-pyrolysis oil added to the non-recovery cracker stream to prepare the first cracker stream or combined cracker stream can be as described above; for example, at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt., in each case as a weight percentage, and / or not exceeding 95, 90, 85, 80, 75, 70, 65, 60, 55, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 1 wt., in each case as a weight percentage, based on the total weight of the first cracker feed or 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.%.

[0434] The first cracker stream is cracked in the first coil or tube. The second cracker stream is cracked in the second coil or tube. The first and second cracker streams, as well as the first and second coils or tubes, can be located in the same cracker furnace.

[0435] The second cracker stream may be free of γ-pyrolysis oil or contain less (by weight) of the γ-pyrolysis oil than the first cracker feed stream. Furthermore, the second cracker stream may contain only non-recoverable cracker feed in a second coil or tube. The second cracker feed stream may be primarily C2 to C4, or hydrocarbons (e.g., non-recoverable 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% by weight, based on the second cracker feed in the second coil or tube. If γ-pyrolysis oil is included in the second cracker feed, the amount of such γ-pyrolysis oil may be at least 10%, 20, 30, 40, 50, 60, 70, 80, 90, 95, 97, or 99% less by weight than the amount of γ-pyrolysis oil in the first cracker feed.

[0436] In one embodiment or in combination with any embodiment described herein, although not shown, an evaporator may be provided to evaporate the condensate feedstock of C2-C5 hydrocarbons 350 to ensure that the feed to the coil inlet in the convection box 312 or the inlet to the convection zone 310 is primarily a gas phase feed.

[0437] Figure 5 The cracking furnace shown includes a convection section or zone 310, a radiant section or zone 320, and a cross section or zone 330 located between the convection and radiant sections 310 and 320. The convection section 310 is part of the furnace 300, receiving heat from the hot flue gas, and includes a row of tubes or coils 324 through which a cracker stream 350 passes. In the convection section 310, the cracker stream 350 is heated by convection from the hot flue gas passing through it. The radiant section 320 is the main section of the furnace 300 that transfers heat to the heater tubes via radiation from the high-temperature gas. The radiant section 320 also includes a plurality of burners 326 for introducing heat into the lower part of the furnace. The furnace includes a combustion chamber 322 that surrounds and houses the tubes within the radiant section 320, and the burners are oriented into this combustion chamber. The cross section 330 includes a conduit for connecting the convection section 310 and the radiation section 320, and can transfer heated cracker flow from inside or outside one section of the furnace 300 to another section.

[0438] As hot combustion gases rise through the furnace body, they can pass through a convection section 310, where at least a portion of the waste heat can be recovered and used to heat the cracker stream passing through the convection section 310. In one embodiment or in combination with any of the embodiments mentioned herein, the cracker 300 may have a single convection (preheating) section 310 and a single radiant section 320, while in other embodiments, the furnace may include two or more radiant sections sharing a common convection section. At least one induced draft (ID) fan 316 near the furnace body controls the flow of hot flue gas and the heating distribution through the furnace, and one or more heat exchangers 340 are available for cooling the furnace effluent 370. In one embodiment or in combination with any of the embodiments mentioned herein (not shown), additional to or replacing Figure 5 The exchangers shown (e.g., delivery line heat exchangers or TLEs) can use liquid quenching to cool the cracked olefin-containing effluent.

[0439] Furnace 300 also includes at least one furnace coil 324 through which the cracker flow passes through the furnace. The furnace coil 324 can be formed of any material that is inert to the cracker flow 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.

[0440] The diameter of the coil or the tube within the coil in the convection section 310 may 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 cm in each case, and / or not exceeding 12, or not exceeding 11.5, or not exceeding 11.1, or not exceeding 0.5, or not exceeding 10, or not exceeding 9.5, or not exceeding 9, or not exceeding 8.5, or not exceeding 8, or not exceeding 7.5, or not exceeding 7, or not exceeding 6.5 cm in each case. All or part of one or more coils may be substantially straight, or one or more coils may include helical, twisted, or spiral segments. One or more coils may also have a U-shaped tube or a split U-shaped tube design. In one embodiment or in combination with any of the embodiments mentioned herein, the interior of the tube may be smooth or substantially smooth, or partially (or entirely) roughened to minimize coking. Alternatively, or additionally, the interior of the tube may include inserts or fins and / or surface metal additives to prevent coke buildup.

[0441] In one embodiment or in combination with any of the embodiments mentioned herein, all or a portion of one or more furnace coils 324 passing through the convection section 310 may be horizontally oriented, while all or at least a portion of the furnace coils passing through the radiation section 322 may be vertically oriented. In one embodiment or in combination with any of the embodiments mentioned herein, a single furnace coil may extend through both the convection section and the radiation section. Alternatively, at least one coil may be split into two or more tubes at one or more points within the furnace, allowing the cracker flow to pass parallel along multiple paths. For example, the cracker flow (including r-pyrolysis oil) 350 may be introduced into multiple coil inlets in the convection section 310, or into multiple tube inlets in the radiation 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 regulated. In one embodiment or in combination with any of the embodiments mentioned herein, r-pyrolysis oil and / or the cracker flow may be introduced into a common header, which then directs the r-pyrolysis oil to multiple coils or tube inlets.

[0442] A single furnace may have at least one, or at least two, or at least three, or at least four, or at least five, or at least six, or at least seven, or at least eight or more, coils in each case. Each coil may be 5 to 100, 10 to 75, or 20 to 50 meters long and may include at least one, or at least two, or at least three, or at least four, or at least five, or at least six, or at least seven, or at least eight, or at least ten, or at least twelve, or at least fourteen or more tubes. The tubes of a single coil may be arranged in many configurations and, in one embodiment or in combination with any embodiment mentioned herein, may be connected by one or more 180° (“U”) bends. Figure 6 An example of a furnace tray tube 410 having multiple tubes 420 is shown.

[0443] An olefins plant may have a single cracking furnace, or it may have at least two, three, four, five, six, seven, eight or more cracking furnaces operating in parallel. Any one or each furnace may be a gas cracker, a liquid cracker, or a cracking furnace. In one embodiment or in combination with any of the embodiments mentioned herein, the furnace is a gas cracker that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, said 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 combinations thereof, based on the weight of all cracker feeds to the furnace. In one embodiment or in combination with any of the embodiments mentioned herein, the furnace is a liquid or naphtha cracker that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, of liquid hydrocarbons having a carbon number of C5-C22 (when measured at 25°C and 1 atm), based on the weight of all cracker feed to the furnace. In one embodiment or in combination with any of the embodiments mentioned herein, the cracker is a cracking furnace that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, or at least 90 wt.%, of ethane, propane, LPG, or combinations 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.%, of liquid and / or r-pyrolysis oil (when measured at 25°C and 1 atm), each based on the weight of all cracker feed to the furnace.

[0444] Turn now Figure 7This illustrates several possible locations for introducing the r-pyrolysis oil-containing feed stream and the non-recovery cracker feed stream into the cracker. In one embodiment, or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil-containing feed stream 550 can be combined with the non-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 r-pyrolysis oil-containing feed 550 can be introduced into a first furnace coil, while the non-recovery cracker feed 552 can be introduced into a separate or second furnace coil, within the same furnace or within the same convection zone. The two streams can then travel parallel to each other through the convection section 510 within the convection box 512, the cross section 530, and the radiation section 520 within the radiation box 522, such that each stream is substantially fluidly isolated from the other for most or all of its travel path from the furnace inlet to the outlet. The pyrolysis stream introduced into any heating zone within the convection section 510 can flow through the convection section 510 and into the radiation chamber 522 as an evaporation stream 514b. In other embodiments, the feed stream 550 containing r-pyrolysis oil can 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 a combined cracker stream 514a, as well as... Figure 7 As shown in the image.

[0445] In one embodiment or in combination with any of the embodiments mentioned herein, as Figure 7 The first or second heating zone shown introduces r-pyrolysis oil 550 into the first furnace coil, or introduces an additional amount into the second furnace coil. The r-pyrolysis oil 550 can be introduced into the furnace coil at these locations via nozzles. A convenient method of introducing the r-pyrolysis oil feed is through one or more dilution steam feed nozzles used to feed steam into the coil in the convection zone. One or more dilution steam nozzles can be used for injecting r-pyrolysis oil, or new nozzles can be attached to a coil specifically designed for injecting r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, both steam and r-pyrolysis oil can be co-fed into the furnace coil via nozzles downstream of the coil inlet and upstream of the intersection, optionally in the first or second heating zone within the convection zone, such as... Figure 7 As shown.

[0446] When introduced into the furnace and / or combined with a feed containing γ-pyrolysis oil, the non-recovery cracker feed stream may be primarily liquid with a vapor fraction of less than 0.25 (by volume) or less than 0.25 (by weight), or may be primarily steam with a vapor fraction of at least 0.75 (by volume) or at least 0.75 (by weight). Similarly, when introduced into the furnace and / or combined with a non-recovery cracker stream, the feed containing γ-pyrolysis oil may be primarily steam or primarily liquid.

[0447] 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 before being introduced into the furnace. For example... Figure 8 As shown, preheating can be performed using an indirect heat exchanger 618 heated by a heat transfer medium (e.g., steam, hot condensate, or a portion of an olefin-containing effluent) or via a direct ignition heat exchanger 618. The preheating step can evaporate all or part of the stream containing r-pyrolysis oil, and can, for example, evaporate at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% by weight of the stream containing r-pyrolysis oil.

[0448] When preheating is performed, the temperature of the stream containing γ-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 γ-pyrolysis oil. Additionally or alternatively, preheating can increase the temperature of the stream containing γ-pyrolysis oil to a temperature at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 100°C lower than the coking temperature of the stream. In one embodiment or in combination with any embodiment mentioned herein, the preheated r-pyrolysis oil stream may have a temperature of at least 200, 225, 240, 250, or 260°C, and / or not exceeding 375, 350, 340, 330, 325, 320, or 315°C, or at least 275, 300, 325, 350, 375, or 400°C, and / or not exceeding 600, 575, 550, 525, 500, or 475°C. When the atomized liquid (described below) is injected into the gas-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.

[0449] 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 or liquid components (if present). The resulting light fraction may then be introduced into the cracker, alone or in combination with one or more other cracker streams as described in the various embodiments herein. For example, in one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil stream may contain at least 1, 2, 5, 8, 10, or 12 weight percent C 15 And heavier components. Separation can remove at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 99% by weight of heavier components from the r-pyrolysis oil stream.

[0450] Back Figure 7The cracker feed stream (alone or in combination 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 of the embodiments 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 feed stream comprising r-pyrolysis oil and non-recovery cracker stream (alone or in combination with steam) can also be introduced into the convection section or upstream of 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 can be combined with r-pyrolysis oil streams and / or cracker streams, and the combined streams can be introduced at one or more of these locations, or steam and r-pyrolysis oil and / or non-recovery cracker streams can be added separately.

[0451] When combined with steam and fed into or near the cross section of the furnace, the r-pyrolysis oil and / or cracker stream may have temperatures of 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670 or 680 °C, and / or not exceeding 850, 840, 830, 820, 810, 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655 or 650 °C. The resulting steam and r-pyrolysis oil streams may have a steam fraction of at least 0.75, 0.80, 0.85, 0.90, or at least 0.95 (by weight), or at least 0.75, 0.80, 0.85, 0.90, and 0.95 (by volume). When combined with steam and fed into or near the inlet of the convection section 510, the r-pyrolysis oil and / or cracker streams may have a temperature of at least 30, 35, 40, 45, 50, 55, 60, or 65°C, and / or not exceeding 100, 90, 80, 70, 60, 50, or 45°C.

[0452] The amount of steam added can vary depending on operating conditions, including feed type and desired product, but can 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 ratio shall not exceed approximately 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, or 0.50:1, or it may be in the range of 0.1:1 to 1.0:1, 0.15:1 to 0.9:1, 0.2:1 to 0.8:1, 0.3:1 to 0.75:1, or 0.4:1 to 0.6:1. When determining the "steam to hydrocarbon" ratio, all hydrocarbon components are included, and the ratio is by weight. In one embodiment or in combination with any embodiment described herein, steam can be used in the same furnace ( Figure 7 Separate boiler feed water / steam pipes (not shown) generate heat in the convection section. Steam can be added to the cracker feed (or any intermediate cracker stream within the furnace) when the cracker stream has a steam fraction of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90.

[0453] When a feed stream containing r-pyrolysis oil is introduced separately from a non-recovery feed stream into a cracker, the molar flow rate of the r-pyrolysis oil and / or the r-pyrolysis oil-containing stream may differ from the molar flow rate of the non-recovery feed stream. In one embodiment or in combination with any other mentioned embodiments, a method for preparing one or more olefins is provided, which involves:

[0454] (a) Feeding the first cracker stream containing r-pyrolysis oil into the first tube inlet in the cracker furnace;

[0455] (b) A second cracker stream containing or primarily containing C2-C4 hydrocarbons is fed into a second tube inlet in the cracker, wherein the second tube is separate from the first tube, and the total molar flow rate of the first cracker stream fed at the first tube inlet is lower than the total molar flow rate of the second cracker stream to the second tube inlet calculated without the influence of steam. The feed in steps (a) and (b) may be to the respective coil inlet.

[0456] For example, when r-pyrolysis oil or the first cracker stream passes through the tubes in the cracker, its molar flow rate can be higher than that of hydrocarbon components (e.g., C2-C4 or C5-C5) in the non-recovery feed stream or the second cracker stream. 22 The flow rate of the component through another or second pipe 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 feed 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).

[0457] In one embodiment or in combination with any of the embodiments mentioned herein, the molar flow rate of r-pyrolysis oil in the feed stream (first cracker stream) containing r-pyrolysis oil within the furnace tube can be higher than that of hydrocarbons (e.g., C2-C4 or C5-C5) in the non-recovery cracker stream (second cracker stream). 22The molar flow rates of the pyrolysis oil and cracker feed streams are 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 lbs / h. In one embodiment or in combination with any of the embodiments mentioned herein, the molar flow rates of the pyrolysis oil and cracker feed streams can be substantially similar, such that the two molar flow rates are within 0.005, 0.001 or 0.0005 kmol lbs / h of each other. The molar flow rate of 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 not exceeding 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, 0.01, or 0.008 kilomol lbs / hour, while the molar flow rate of the hydrocarbon component in one or more other coils may be at least 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, and / or not exceeding 0.30, 0.29, 0.28, 0.27, 0.26, 0.25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15 kilomol lbs / hour.

[0458] In one embodiment or in combination with any of the embodiments mentioned herein, the total molar flow rate of the r-pyrolysis oil-containing stream (first cracker stream) may be at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, or 0.09 lower than, and / or not more than, 0.30, 0.25, 0.20, 0.15, 0.13, 0.10, 0.09, 0.08, 0.07, or 0.06 kmol / lb / h, or the same as, the total molar flow rate of the non-recovery feed stream (second cracker stream). The total molar flow rate of the stream containing γ-pyrolysis oil (first cracker stream) may be at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07 and / or not exceeding 0.10, 0.09, 0.08, 0.07 or 0.06 kmol / h higher than the total molar flow rate of the second cracker stream, while the total molar flow rate of the non-recovery feed stream (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 not exceeding 0.50, 0.49, 0.48, 0.47, 0.46, 0.45, 0.44, 0.43, 0.42, 0.41, 0.40 kilomol pounds per hour.

[0459] In one embodiment or in combination with any of the embodiments mentioned herein, the steam-to-hydrocarbon ratio of the r-pyrolysis oil-containing stream or the first cracker stream differs from that of the non-recovery feed stream or the second cracker stream by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80%. The steam-to-hydrocarbon ratio may be higher or lower. For example, the steam-to-hydrocarbon ratio of the r-pyrolysis oil-containing stream or the first cracker stream may differ from that of the non-recovery feed stream or the second cracker stream by at least 0.01, 0.025, 0.05, 0.075, 0.10, 0.125, 0.15, 0.175, or 0.20 and / or not more than 0.3, 0.27, 0.25, 0.22, or 0.20. The steam-to-hydrocarbon ratio of the stream containing r-pyrolysis oil or the first cracker stream may be at least 0.3, 0.32, 0.35, 0.37, 0.4, 0.42, 0.45, 0.47, 0.5, and / or not more than 0.7, 0.67, 0.65, 0.62, 0.6, 0.57, 0.55, 0.52, or 0.5, and the steam-to-hydrocarbon ratio of the non-recovery cracker feed or the second cracker stream may be at least 0.02, 0.05, 0.07, 0.10, 0.12, 0.15, 0.17, 0.20, 0.25, and / or not more than 0.45, 0.42, 0.40, 0.37, 0.35, 0.32, or 0.30.

[0460] In one embodiment or in combination with any of the embodiments mentioned herein, when the stream is introduced and passed through the furnace alone, the temperature of the feed stream containing r-pyrolysis oil as it passes through the cross section in the cracker may differ from the temperature of the non-recovery cracker feed as it passes through the cross section. For example, the temperature of the r-pyrolysis oil stream as it passes through the cross section may differ from the temperature of the non-recovery hydrocarbon stream (e.g., C2-C4 or C5-C22) passing through the cross 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:

[0461] (r - temperature of pyrolysis oil stream - temperature of non-recovery cracker stream) / (temperature of non-recovery cracker steam), expressed as a percentage.

[0462] This difference can be higher or lower. The average temperature of the r-pyrolysis oil stream at the cross section can be at least 400, 425, 450, 475, 500, 525, 550, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620 or 625 °C, and / or not exceeding 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525 or 500 °C, excluding recycling. The average temperature of the cracker feed can be at least 401, 426, 451, 476, 501, 526, 551, 560, 565, 570, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620 or 625°C, and / or not exceeding 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525 or 500°C.

[0463] Heated cracker streams typically have temperatures 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 not exceeding 850, 840, 830, 820, 810, 800, 790, 780, 770, or 760°C. Temperatures of 750, 740, 730, 720, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655 or 650°C, or in the range of 500 to 710°C, 620 to 740°C, 560 to 670°C or 510 to 650°C, can then be transferred from the convection section of the furnace to the radiation section via the cross section.

[0464] In one embodiment or in combination with any of the embodiments mentioned herein, a feed stream containing r-pyrolysis oil may be added to the cracker stream at a cross section. When introduced into the furnace at the cross section, the r-pyrolysis oil may be at least partially evaporated, for example, by preheating the stream in a direct or indirect heat exchanger. When evaporated or partially evaporated, the r-pyrolysis oil-containing stream 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 by volume in one embodiment or in combination with any of the mentioned embodiments.

[0465] When a stream containing γ-pyrolysis oil is atomized before entering a cross section, one or more atomizing nozzles may be used for atomization. Atomization can be performed inside or outside the furnace. In one embodiment or in combination with any of the embodiments mentioned herein, an atomizing agent may be added to the stream containing γ-pyrolysis oil during or before atomization. The atomizing agent may include vapor, or it may consist primarily of ethane, propane, or combinations thereof. When used, the atomizing agent may be present in the stream to be atomized (e.g., a composition containing γ-pyrolysis oil) in an amount of at least 1, 2, 4, 5, 8, 10, 12, 15, 10, 25, or 30% by weight, and / or no more than 50, 45, 40, 35, 30, 25, 20, 15, or 10% by weight.

[0466] The atomized or vaporized r-pyrolysis oil stream can then be injected into or combined with the cracker stream passing through the cross section. At least a portion of the injection can be performed using at least one nozzle. The r-pyrolysis oil-containing stream can be injected into the cracker feed stream using at least one nozzle, which can be oriented to discharge the atomized stream at an angle of approximately 45, 50, 35, 30, 25, 20, 15, 10, 5, or 0° to the vertical. The nozzle or multiple nozzles can also be oriented to discharge the atomized stream into the coils within the furnace at an angle of approximately 30, 25, 20, 15, 10, 8, 5, 2, or 1° parallel or parallel to the axial centerline of the coil at the inlet point. In the cross and / or convection sections of the furnace, at least two, three, four, five, six, or more nozzles can be used for the injection of atomized r-pyrolysis oil.

[0467] In one embodiment or in combination with any of the embodiments mentioned herein, atomized r-pyrolysis oil may 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 this atomization may be at least 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80°C, and / or not exceeding 120, 110, 100, 90, 95, 80, 85, 70, 65, 60, or 55°C.

[0468] In one embodiment or in combination with any embodiment mentioned herein, the temperature of the atomized or evaporated stream may 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 not exceeding 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 75, 70, 60, 55, 50, 45, 40, 30, or 25°C. The resulting combined cracker stream comprises a continuous gas phase and a discontinuous liquid phase (or droplets or particles) dispersed therein. The atomized liquid phase may contain γ-pyrolysis oil, while the gas phase may primarily contain C2-C4 components, ethane, propane, or combinations 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 by volume in one embodiment or in combination with any of the mentioned embodiments.

[0469] The temperature of the cracker stream through the cross section can be at least 500, 510, 520, 530, 540, 550, 555, 560, 565, 570, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620, 625, 630, 635, 640, 645, 650, 660, 670 or 680°C, and / or not exceeding 850, 840, 830, 820, 810, 800, 790°C. 5, 790, 785, 780, 775, 770, 765, 760, 755, 750, 745, 740, 735, 730, 725, 720, 715, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 645, 640, 635 or 630°C, or in the range of 620 to 740°C, 550 to 680°C, or 510 to 630°C.

[0470] 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) may pass through a vapor-liquid separator to separate the stream into heavy and light fractions before further cracking of the light fractions in the radiant section of the furnace. Figure 8 An example of this situation is shown in the figure.

[0471] 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 across the trays, while 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.

[0472] Within the convection section 610, the temperature of the cracker stream can be increased by at least 50, 75, 100, 150, 175, 200, 225, 250, 275, or 300°C, and / or not exceeding about 650, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, or 275°C, such that the passage of the heated cracker stream exiting the convection section 610 through the steam-liquid separator 640 can be carried out at temperatures of at least 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650°C, and / or not exceeding 800, 775, 750, 725, 700, 675, 650, 625°C. When heavier components are present, at least a portion or almost all of the heavier components can be removed as underflow 642 from the heavier components. At least a portion of the light fraction 644 from separator 640 can be alone or with one or more other cracker streams, such as primarily C5-C. 22 The hydrocarbon feed stream or C2-C4 hydrocarbon stream combination is introduced into the cross section or radiation zone pipe 624 after separation.

[0473] refer to Figure 5 and 6 Cracker feed streams (non-recovery cracker feed streams or, when combined with r-pyrolysis oil feed streams) 350 and 650 may be introduced into the furnace coils at or near the inlet of the convection section. The cracker feed streams may then pass through at least a portion of the furnace coils in the convection sections 310 and 610, and dilution steam 360 and 660 may be added at several points to control the temperature and cracking severity in the radiant sections 320 and 620. The amount of steam added may depend on furnace operating conditions, including feed type and desired product distribution, but may 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 of the embodiments described herein, steam may be used in the same furnace ( Figure 5 Separate boiler feed water / steam pipes heated in the convection section (not shown) generate steam. Steam 360 and 660 can be added to the cracker feed (or any intermediate cracker feed stream in the furnace) when the cracker feed stream has a steam fraction of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90 by weight, or by volume in one embodiment or in combination with any of the mentioned embodiments.

[0474] 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 °C in each case, and / or not exceeding 850, or not exceeding 840, or not exceeding 830, or not exceeding 820, or not exceeding 810, or not exceeding 800, or not exceeding 790, or not exceeding 780, or not exceeding 770 °C. Or not exceeding 760, or not exceeding 750, or not exceeding 740, or not exceeding 730, or not exceeding 720, or not exceeding 710, or not exceeding 705, or not exceeding 700, or not exceeding 695, or not exceeding 690, or not exceeding 685, or not exceeding 680, or not exceeding 675, or not exceeding 670, or not exceeding 665, or not exceeding 660, or not exceeding 655°C, or not exceeding 650°C, in each case being °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 can be passed from the convection section 610 of the furnace through the cross section 630 to the radiation section 620. In one embodiment or in combination with any embodiment mentioned herein, the feed stream 550 containing r-pyrolysis oil can be added to the cracker stream at the cross section 530, such as Figure 6As shown. When introduced into the furnace at the cross section, the r-pyrolysis oil can be at least partially vaporized or atomized before being combined with the cracker stream at the cross section. The temperature of the cracker stream passing through the cross section 530 or 630 can be at least 400, 425, 450, 475, or at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680 °C in each case, and / or not exceeding 850, or not exceeding 840, or not exceeding 830, or not exceeding 820, or not exceeding 8 10, or not exceeding 800, or not exceeding 790, or not exceeding 780, or not exceeding 770, or not exceeding 760, or not exceeding 750, or not exceeding 740, or not exceeding 730, or not exceeding 720, or not exceeding 710, or not exceeding 705, or not exceeding 700, or not exceeding 695, or not exceeding 690, or not exceeding 685, or not exceeding 680, or not exceeding 675, or not exceeding 670, or not exceeding 665, or not exceeding 660, or not exceeding 655°C, or not exceeding 650°C, in each case in °C, or within the range of 620 to 740°C, 550 to 680°C, 510 to 630°C.

[0475] The resulting cracker feed stream then passes through a radiant section, where the feed stream containing γ-pyrolysis oil is thermally cracked to form lighter hydrocarbons, including olefins such as ethylene, propylene, and / or butadiene. The residence time of the cracker feed stream in the radiant section can be at least 0.1, or at least 0.15, or at least 0.2, or at least 0.25, or at least 0.3, or at least 0.35, or at least 0.4, or at least 0.45 seconds in each case, and / or not more than 2, or not more than 1.75, or not more than 1.5, or not more than 1.25, or not more than 1, or not more than 0.9, or not more than 0.8, or not more than 0.75, or not more than 0.7, or not more than 0.65, or not more than 0.6, or not more than 0.5 seconds in each case. 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, ℃, and / or not exceeding 850, or not exceeding 840, or not exceeding 830, or not exceeding 820, or not exceeding 810, or not exceeding 800, or not exceeding 790, or not exceeding 780, or not exceeding 770, or not exceeding 760, or not exceeding 750, or not exceeding 740, or not exceeding 730, or not exceeding 720, or not exceeding 710, or not exceeding 705, or not exceeding 700, or not exceeding 695, or not exceeding 690, or not exceeding 685, or not exceeding 680, or not exceeding 675, or not exceeding 670, or not exceeding 665, or not exceeding 660, or not exceeding 655°C, or not exceeding 650°C, in each case °C, or within 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 °C.

[0476] 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 °C, in each case, and / or not exceeding 1000, or not exceeding 990, or not exceeding 980. Or not exceeding 970, or not exceeding 960, or not exceeding 950, or not exceeding 940, or not exceeding 930, or not exceeding 920, or not exceeding 910, or not exceeding 900, or not exceeding 890, or not exceeding 880, or not exceeding 875, or not exceeding 870, or not exceeding 860, or not exceeding 850, or not exceeding 840, or not exceeding 830, in each case being °C, within the range of 730 to 900 °C, 750 to 875 °C, or 750 to 850 °C.

[0477] Cracking in furnace coils may involve processing the cracker feed stream under a set of processing conditions that include target values ​​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 separate coils in the furnace, one coil may operate under a first set of processing conditions, and at least one of the other coils may operate under a second set of processing conditions. At least one target value of the operating parameter from the first set of processing conditions may differ from the target value of the same parameter in the second set of conditions by at least 0.01, 0.03, 0.05, 0.1, 0.25, 0.5, 1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95%, and / or not 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, and 0.03 to 15%. The percentage is calculated according to the following formula:

[0478] [(Measured value of operating parameter) - (Target value of operating parameter)] / [(Target value of operating parameter)], expressed as a percentage. As used herein, the term "different" means higher or lower.

[0479] The coil outlet temperature can be at least 640, 650, 660, 670, 680, 690, 700, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820°C, and / or not exceeding 1000, 990, 980, 970, 960, 950, 940, 930, 920, 910, 900, 890, 880, 875, 870, 860, 850, 840, 830°C, or within the range of 730 to 900°C, 760 to 875°C, or 780 to 850°C.

[0480] In one embodiment or in combination with any of the embodiments mentioned herein, adding r-pyrolysis oil to the cracker feed stream can cause a change in one or more of the aforementioned operating parameters compared to the values ​​of the operating parameters when processing the same cracker feed stream in the absence of r-pyrolysis oil. For example, the value of one or more of the aforementioned parameters may differ (e.g., be higher or lower) from the value of the same parameter when processing the same feed stream without r-pyrolysis oil by at least 0.01, 0.03, 0.05, 0.1, 0.25, 0.5, 1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95%. The percentage is calculated according to the following formula:

[0481] [(Measured value of operating parameter) - (Target value of operating parameter)] / [(Target value of operating parameter)], expressed as a percentage.

[0482] One example of an operating parameter that can be adjusted by adding r-pyrolysis oil to the cracker stream is the coil outlet temperature. For instance, in one embodiment or in combination with any of the embodiments mentioned herein, the cracker can be operated to achieve a first coil outlet temperature (COT1) when a cracker stream without r-pyrolysis oil is present. Subsequently, 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.

[0483] In some cases, when the r-pyrolysis oil is heavier than the cracker stream, COT2 may be less than COT1; 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 not exceeding 80, 75, 70, 65, 60, 55, or 50%. The percentage is calculated according to the following formula:

[0484] [(°R in r - 50% boiling point of pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0485] 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 exceeding 300, 275, 250, 225, or 200°C. Heavier cracker streams may include, for example, vacuum gas oil (VGO), atmospheric gas oil (AGO), or even coking gas oil (CGO), or combinations thereof.

[0486] 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 not exceeding 80, 75, 70, 65, 60, 55, or 50%. The percentage is calculated according to the following formula:

[0487] [(r - 50% boiling point of pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0488] 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 exceeding 300, 275, 250, 225, or 200 °C. Lighter cracker streams may include, for example, LPG, naphtha, kerosene, natural gasoline, straight-run gasoline, and combinations thereof.

[0489] In some cases, COT1 may differ from COT2 by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 °C, and / or not exceed 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 °C, and / or not exceed 80, 75, 70, 65, 60, 50, 45, or 40% (the percentage here is defined as the difference between COT1 and COT2 divided by COT1, expressed as a percentage). At least one or both of COT1 and COT2 can be at least 730, 750, 77, 800, 825, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, and / or not exceeding 1200, 1175, 1150, 1140, 1130, 1120, 1110, 1100, 1090, 1080, 1070, 1060, 1050, 1040, 1030, 1020, 1010, 1000, 990, 980, 970, 960, 950, 940, 930, 920, 910, or 900°C.

[0490] In one embodiment or in combination with any of the embodiments mentioned herein, the mass velocity of the cracker feed stream through at least one or at least two radiant coils (defined for clarity as spanning the entire coil, in contrast to the tubes within the coil) is between 60 and 165 kg / s per square meter (m²). 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 Within the range of ), when steam is present, the mass velocity is based on the total flow rate of hydrocarbons and steam.

[0491] In one embodiment or in combination with any of the mentioned embodiments, a method for preparing one or more olefins is provided, which involves:

[0492] (a) Cracking cracker flow in the cracking unit at the first coil outlet temperature (COT1);

[0493] (b) Following step (a), a stream containing a recovered pyrolysis oil composition (r-pyrolysis oil) is added to the cracker stream to form a combined cracker stream; and

[0494] (c) The combined cracker stream is cracked in the cracking unit at a second coil outlet temperature (COT2), 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.

[0495] The cause or reason for the decrease in the second coil outlet temperature (COT2) is not limited, as long as COT2 is lower than the first coil outlet temperature (COT1). In one embodiment or in combination with any of the mentioned embodiments, the COT2 temperature on the r-pyrolysis oil feed coil may be set lower than COT1 (“Set” mode), or at least 1, 2, 3, 4, or at least 5°C lower, or it may be allowed to change or float without setting the temperature on the r-pyrolysis oil feed coil (“Free Float” mode).

[0496] In the setup mode, COT2 can be set at least 5°C lower than COT1. All coils in the furnace can be feed streams containing γ-pyrolysis oil, or at least one or at least two coils can be feed streams containing γ-pyrolysis oil. In either case, at least one of the γ-pyrolysis oil coils can be in the setup mode. By reducing the cracking severity of the combined cracking streams, when their average number-average molecular weight is higher than that of the cracker feed stream, such as gaseous C2-C4 feed, the lower thermal energy required for cracking γ-pyrolysis oil can be utilized. While 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 recovering the unconverted C2-C4 feed through the furnace. Optionally, the content of other cracker products, such as aromatics and dienes, can be reduced.

[0497] In one embodiment or in combination with any of the embodiments mentioned, when the hydrocarbon mass flow rate of the combined cracker stream in at least one coil is equal to or less than the hydrocarbon mass flow rate of the cracker stream in step (a) in the coil, the COT2 in the set mode may be fixed below COT1, or at least 1, 2, 3, 4, or at least 5°C lower. The hydrocarbon mass flow rate includes all hydrocarbons (cracker feed and, if present, r-pyrolysis oil and / or natural gasoline or any other type of hydrocarbon) and hydrocarbons other than steam. Fixing COT2 is advantageous when the hydrocarbon mass flow rate of the combined cracker stream in step (b) is equal to or less than the hydrocarbon mass flow rate of the cracker stream in step (a) and the average molecular weight of the pyrolysis oil is higher than the average molecular weight of the cracker stream. At the same hydrocarbon mass flow rate, when the pyrolysis oil has a heavier average molecular weight than the cracker stream, COT2 will tend to increase with the addition of pyrolysis oil because higher molecular weight molecules require less thermal energy to crack. If it is desirable to avoid over-cracking of pyrolysis oil, a lower COT2 temperature can help reduce byproduct formation, while also reducing the single-pass olefin yield. The final olefin yield can be satisfactory or increased by recovering unconverted cracker feed through the furnace.

[0498] In the set mode, the temperature can be fixed or set by adjusting the fuel ratio of the furnace to the burner. In one embodiment or in combination with any other mentioned embodiments, COT2 is in a free-floating mode and is not fixed due to the supply of pyrolysis oil and the fact that COT2 is allowed to rise or fall. In this embodiment, not all coils contain r-pyrolysis oil. The heat energy supplied to the coils containing r-pyrolysis oil can be provided by maintaining a constant burner temperature or fuel feed rate on the coils containing non-recovery cracker feed. Without fixing or setting COT2, COT2 can be lower than COT1 when pyrolysis oil is fed into the cracker stream to form a combined cracker stream with a higher hydrocarbon mass flow rate than the cracker stream in step (a). 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 heating effect of using pyrolysis oil with a higher average molecular weight. These effects can be observed while other cracker conditions remain constant, such as dilution steam ratio, feed location, composition of cracker feed and pyrolysis oil, and fuel feed rate from the tube containing only cracker feed and not pyrolysis oil feed to the combustor in the furnace combustion chamber.

[0499] 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, or 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.

[0500] Regardless of the cause or origin of the temperature drop in COT2, the duration of step (a) is flexible, but ideally, step (a) reaches a steady state before 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 cracker that has never received pyrolysis oil feed or a combination of pyrolysis oil feed and pyrolysis oil feed during operation. Step (b) can be the first time the furnace receives pyrolysis oil feed or a combination cracker feed containing pyrolysis oil. In one embodiment or in combination with any other mentioned embodiments, steps (a) and (b) may be cycled multiple times per year, as measured over a calendar year, such as at least 2x / yr, or at least 3x / yr, or at least 4x / yr, or at least 5x / yr, or at least 6x / yr, or at least 8x / yr, or at least 12x / yr. The preparation of the pyrolysis oil feed represents multiple cycles of steps (a) and (b). When the pyrolysis oil feed supply is depleted or shut off, COT1 is allowed to reach steady-state temperature before engaging step (b). Alternatively, the pyrolysis oil feed to the cracker may be continuous throughout the entire process for at least one calendar year or at least two calendar years.

[0501] In one embodiment or in combination with any other mentioned embodiments, the cracker feed composition used in steps (a) and (b) remains constant, allowing for regular compositional changes to be observed over a calendar year. In one embodiment or in combination with any other mentioned embodiments, the flow of the cracker feed in step (a) is continuous and remains continuous as pyrolysis oil enters the cracker feed to prepare the combined cracker feed. The cracker feed in steps (a) and (b) can be drawn from the same source, such as the same stock or pipeline.

[0502] In one embodiment or in combination with any of the mentioned embodiments, COT2 is at least 1, 2, 3, 4 or at least 5°C below or lower than 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 during which pyrolysis oil is fed to the cracker stream to form the combined cracker stream, the measurement time being when all conditions other than COT remain constant, such as cracker and pyrolysis oil feed rates, steam ratio, feed location, composition of cracker feed and pyrolysis oil, etc.

[0503] In one embodiment or in combination with any of the mentioned embodiments, the hydrocarbon mass flow rate of the combined cracker feed can be increased. A method for preparing one or more olefins is now provided by the following steps:

[0504] (a) Cracking the cracker stream in the cracking unit at a first hydrocarbon mass flow rate (MF1);

[0505] (b) Following step (a), a stream containing a recovered pyrolysis oil composition (r-pyrolysis oil) is added to the cracker stream to form a combined cracker stream having a second hydrocarbon mass flow rate (MF2) higher than MF1; and

[0506] (c) The combined cracker stream is cracked in the cracking unit at MF2 to obtain an olefin-containing effluent having a combined yield of ethylene and propylene that is the same as or higher than the yield of ethylene and propylene obtained by cracking the cracker stream only at MF1.

[0507] Yield refers to the production of the target compound per unit time, expressed by weight, e.g., kg / hr. Increasing the mass flow rate of the cracker stream by adding r-pyrolysis oil can increase the combined yield of ethylene and propylene, thereby increasing furnace production. This is believed to be possible, not theoretically, because the total energy of the reaction with lighter cracker feeds such as propane or ethane is not endothermic. Since the heat flux on the furnace is limited and the total heat of the reaction with the pyrolysis oil is less endothermic, more limited thermal energy per unit time can be obtained to continue cracking the heavier feed. MF2 can be increased by at least 1, 2, 3, 4, 5, 7, 10, 10, 13, 15, 18, or 20% by adding r-pyrolysis oil feed coils, or by at least 1, 2, 3, 5, 7, 10, 10, 13, 15, 18, or 20%, as measured by furnace production, provided that at least one coil handles r-pyrolysis oil. Optionally, the combined production of ethylene and propylene can be increased without changing the heat flux in the furnace, or the outlet temperature of the r-pyrolysis oil feed coil, or the fuel feed rate of the burner used to heat only the coil containing non-recovery feed to the splitter, or the fuel feed rate of any burner in the furnace. Higher hydrocarbon mass flow rates of MF2 in the r-pyrolysis oil-containing coil can be achieved through one or at least one coil in the furnace, or through two or at least two coils in the furnace, or 50% or at least 50%, or 75% or at least 75%, or through all coils in the furnace.

[0508] The olefin-containing effluent may have a total yield of propylene and ethylene from the combined cracker stream at MF2 that is equal to or higher than the yield of propylene and ethylene from the effluent obtained by cracking the same cracker feed but without r-pyrolysis oil by at least 0.5%, or at least 1%, or at least 2%, or at least 2.5%, as determined below:

[0509]

[0510] Omf1 is the combined yield of propylene and ethylene content in the cracker effluent of MF1 produced without the use of r-pyrolysis oil; Omf2 is the combined yield of propylene and ethylene content in the cracker effluent of MF2 produced using r-pyrolysis oil.

[0511] The total yield of propylene and ethylene in the combined cracker stream containing olefins in MF2, expressed as a percentage, is 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% × 100). This can be determined as:

[0512]

[0513] Wherein, 1% is the percentage increase in the combined yield of propylene and ethylene content in the cracker effluent between MF1 produced without r-pyrolysis oil and MF2 produced using r-pyrolysis oil (using the formula above); and

[0514] ΔMF% is the percentage increase of MF2 compared to MF1.

[0515] Optionally, the olefin-containing effluent may have a total wt.% of propylene and ethylene from the combined cracker stream at MF2, which is equal to or higher than the wt.% of propylene and ethylene in the effluent obtained by cracking the same cracker feed but without r-pyrolysis oil by at least 0.5%, or at least 1%, or at least 2%, or at least 2.5%, as determined below:

[0516]

[0517] Emf1 is the combined propylene and ethylene content (wt.%) in the cracker effluent of MF1 obtained without using r-pyrolysis oil; Emf2 is the combined propylene and ethylene content (wt.%) in the cracker effluent of MF2 obtained using r-pyrolysis oil.

[0518] A method for preparing one or more olefins is also provided, the method comprising:

[0519] (a) Cracking the cracker stream in a cracker to provide a first olefin-containing effluent exiting the cracker at a first coil outlet temperature (COT1);

[0520] (b) Following step (a), a stream containing a recovered pyrolysis oil composition (r-pyrolysis oil) is added to the cracker stream to form a combined cracker stream; and

[0521] (c) Cracking the combined cracker stream in the cracking unit to provide a second olefin-containing effluent exiting the cracker at a second coil outlet temperature (COT2).

[0522] Wherein, when the r-pyrolysis oil is heavier than the cracker flow, COT2 is equal to or less than COT1, and

[0523] Wherein, when the r-pyrolysis oil is lighter than the cracker flow, COT2 is greater than or equal to COT1.

[0524] In this method, the above-described embodiments are applicable to COT2, which is at least 5°C lower than COT1. COT2 can be in a set mode or a free-floating mode. In one embodiment or in combination with any other mentioned embodiments, COT2 is in a free-floating mode, and the hydrocarbon mass flow rate of the combined cracker stream in step (b) is higher than the hydrocarbon mass flow rate of the cracker stream in step (a). In one embodiment or in combination with any mentioned embodiments, COT2 is in a set mode.

[0525] In one embodiment or in combination with any of the mentioned embodiments, a method for preparing one or more olefins is provided, which involves:

[0526] (a) Cracking cracker flow in the cracking unit at the first coil outlet temperature (COT1);

[0527] (b) Following step (a), a stream containing a recovered pyrolysis oil composition (r-pyrolysis oil) is added to the cracker stream to form a combined cracker stream; and

[0528] (c) The combined cracker stream is cracked in the cracking unit at a second coil outlet temperature (COT2), wherein the second coil outlet temperature is higher than the first coil outlet temperature. COT2 may be at least 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, or 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.

[0529] In one embodiment or in combination with any other mentioned embodiment, 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 the 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 mentioned embodiment, at least one or at least two coils, or at least 50%, or at least 75% of the coils within the cracker contain only non-recoverable cracker feed, wherein at least one coil in the cracker is fed with r-pyrolysis oil, and at least some of the coils or coils fed with r-pyrolysis oil have a COT2 higher than their respective COT1.

[0530] In one embodiment or in combination with any of the embodiments mentioned, the hydrocarbon mass flow rate of the combined stream in step (b) is substantially equal to or less than the hydrocarbon mass flow rate of the cracker stream in step (a). Substantially equal means a difference of no more than 2%, or no more than 1%, or no more than 0.25%. When the hydrocarbon mass flow rate of the combined cracker stream in step (b) is substantially equal to or less than the hydrocarbon mass flow rate of the cracker stream (a), and COT2 is allowed to operate in free-floating mode (where at least one tube contains the non-recoverable cracker stream), COT2 on the coil containing the r-pyrolysis oil can rise relative to COT1. This is true even if the pyrolysis oil, having a larger number-average molecular weight compared to the cracker stream, requires less energy to crack. Without being bound by theory, it is believed that one factor or combination of factors contributes to the temperature rise, including the following:

[0531] a. Lower thermal energy is required to crack the pyrolysis oil in the combined stream; or

[0532] b. Exothermic reactions occur in the cracking products of pyrolysis oil, such as the Diels-Alder reaction.

[0533] This effect can be observed when other process variables are constant, such as combustion chamber fuel rate, dilution steam ratio, feed location, and cracker feed composition.

[0534] In one embodiment or in combination with any of the mentioned embodiments, COT2 may be set or fixed to a higher temperature than COT1 (setting mode). This is more suitable when the combined cracker stream hydrocarbon mass flow rate is higher than that of the cracker stream hydrocarbon mass flow rate, which would otherwise reduce COT2. A higher second coil outlet temperature (COT2) can contribute to increased harshness and reduced yield of unconverted lighter cracker feeds (e.g., C2-C4 feeds), which can benefit downstream fractionation columns with limited capacity.

[0535] In one embodiment or in combination with any of the mentioned embodiments, regardless of whether COT2 is higher or lower than COT1, the cracker feed composition is the same when compared between COT2 and COT1. Desiredly, the cracker feed composition in step (a) is the same cracker composition used to prepare the combined cracker stream in step (b). Optionally, the cracker composition feed from step (a) is continuously fed into the cracker unit, and the pyrolysis oil from step (b) is added to the continuous cracker feed from step (a). Optionally, the pyrolysis oil feed to the cracker is continuous for at least 1 day, or at least 2 days, or at least 3 days, or at least 1 week, or at least 2 weeks, or at least 1 month, or at least 3 months, or at least 6 months, or at least 1 year.

[0536] In any of the mentioned embodiments, the amount of 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 cracker feed decreased in step (b) may correspond to the amount of pyrolysis oil added by weight. In one embodiment or in combination with any of the mentioned embodiments, the combined cracker feed mass flow rate 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).

[0537] In any or all of the mentioned embodiments, if any one coil in the furnace satisfies the relationship, but may also exist in multiple coils depending on how the pyrolysis oil is fed and distributed, then the cracker feed or combined cracker feed mass flow rate and COT relationship and measurement are satisfied.

[0538] In one embodiment or in combination with any of the embodiments mentioned herein, the burner in the radiant zone provides an average heat flux of 60 to 160 kW / m² to the coil. 2 or 70 to 145 kW / m 2 or 75 to 130 kW / m 2 The highest (hottest) coil surface temperature is in the range of 1035 to 1150°C, or 1060 to 1180°C. The pressure at the inlet of the furnace coil in the radiant section is in the range of 1.5 to 8 bar absolute pressure (bara) or 2.5 to 7 bar, while the outlet pressure of the furnace coil in the radiant section is in the range of 1.03 to 2.75 bar, or 1.03 to 2.06 bar. The pressure drop across the furnace coil in the radiant section can be 1.5 to 5 bar, or 1.75 to 3.5 bar, or 1.5 to 3 bar, or 1.5 to 3.5 bar.

[0539] In one embodiment or in combination with any embodiment mentioned herein, the yield of olefins—ethylene, propylene, butadiene, or combinations thereof—may be at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, in each case as a percentage. As used herein, the term “yield” means product mass / feed mass × 100%. The olefin-containing effluent contains at least about 30, or at least 40, or at least 50, or at least 60, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case as a weight percentage of ethylene, propylene, or ethylene and propylene, based on the total weight of the effluent.

[0540] In one embodiment or in combination with one or more embodiments mentioned herein, the olefin-containing effluent 670 may 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 by weight, based on the weight of the olefin-containing effluent. The effluent may primarily contain ethylene, primarily contain propylene, or primarily contain both ethylene and propylene, based on the weight of the olefins in the olefin-containing effluent, or based on the weight of the C1-C5 hydrocarbons in the olefin-containing effluent, or based on the weight of the olefin-containing effluent stream. The weight ratio of ethylene to propylene in the olefin-containing effluent can be at least about 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1, and / or not exceeding 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 may have a propylene:ethylene ratio higher than that obtained by cracking the same cracker feed but without the same dilution vapor ratio of r-pyrolysis oil, feed location, cracker feed composition (different from r-pyrolysis oil), and by placing the coils fed with r-pyrolysis oil in a floating mode, or by having the propylene:ethylene ratio of the effluent stream obtained at the same temperature prior to the feed of r-pyrolysis oil if all coils in the furnace are fed with r-pyrolysis oil. As described above, this is possible when r-pyrolysis oil is added relative to the original feed of the cracker stream, while keeping the mass flow rate of the cracker feed substantially the same, resulting in a higher hydrocarbon mass flow rate in the combined cracker stream.

[0541] The propylene:ethylene ratio of the olefin-containing effluent may be at least 1%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 10%, or at least 12%, or at least 15%, or at least 17%, or at least 20% higher than that of the effluent obtained through the same cracker feed but without r-pyrolysis oil. Alternatively, the propylene:ethylene ratio of the olefin-containing effluent may be at most 50%, or at most 45%, or at most 40%, or at most 35%, or at most 25%, or at most 20% higher than that of the effluent obtained through the same cracker feed but without r-pyrolysis oil, as determined in each case:

[0542]

[0543] Where E is the propylene:ethylene ratio in the cracker effluent obtained without using r-pyrolysis oil, expressed in wt.%; Er is the propylene:ethylene ratio in the cracker effluent obtained with r-pyrolysis oil, expressed in wt.%.

[0544] In one embodiment or in combination with any of the embodiments mentioned herein, the amounts of ethylene and propylene in the cracked olefin-containing effluent can remain substantially unchanged or increase relative to the effluent without r-pyrolysis oil. Surprisingly, liquid r-pyrolysis oil can be fed into a gas feed furnace that accepts and cracks a predominantly C2-C4 composition to obtain an olefin-containing effluent that, in some cases, remains substantially unchanged or improved relative to a C2-C4 cracker feed without r-pyrolysis oil. The high molecular weight of r-pyrolysis oil can primarily contribute to the formation of aromatics and only a small amount participates in the formation of olefins (particularly ethylene and propylene). However, we have found that at the same hydrocarbon mass flow rate, when r-pyrolysis oil is added to the cracker feed to form a combined cracker feed, the combined weight percentage of ethylene and propylene, and even the yield, does not decrease significantly relative to a cracker feed without r-pyrolysis oil, and in many cases remains the same or may increase. The olefin-containing effluent may have a total wt.% of propylene and ethylene that is equal to or higher than the propylene and ethylene content of the effluent obtained by cracking the same cracker feed but without r-pyrolysis oil by at least 0.5%, or at least 1%, or at least 2%, or at least 2.5%, as determined below:

[0545]

[0546] Where E is the combined wt.% content of propylene and ethylene in the cracker effluent obtained without using r-pyrolysis oil; Er is the combined wt.% content of propylene and ethylene in the cracker effluent obtained using r-pyrolysis oil.

[0547] In one embodiment or in combination with one or more embodiments mentioned herein, the wt.% of propylene in the olefin-containing effluent may be increased when the dilution vapor ratio (steam:hydrocarbon weight ratio) is greater than 0.3, or greater than 0.35, or at least 0.4. When the dilution vapor ratio is at least 0.3, or at least 0.35, or at least 0.4, the increase in propylene wt.% may be at most 0.25 wt.%, or at most 0.4 wt.%, or at most 0.5 wt.%, or at most 0.7 wt.%, or at most 1 wt.%, or at most 1.5 wt.%, or at most 2 wt.%, wherein this increase is measured as a simple difference in propylene wt.% between the olefin-containing effluent prepared with r-pyrolysis oil at a dilution vapor ratio of 0.2 and the olefin-containing effluent prepared with r-pyrolysis oil at a dilution vapor ratio of at least 0.3, all other conditions being equal.

[0548] When the dilution steam ratio is increased as described above, the propylene:ethylene ratio can also be increased, or can be at least 1%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 7%, or at least 10%, or at least 12%, or at least 15%, or at least 17%, or at least 20% higher than that of the propylene:ethylene effluent obtained from r-pyrolysis oil with a dilution steam ratio of 0.2.

[0549] In one embodiment or in combination with one or more embodiments described herein, the olefin-containing effluent may have a reduced methane wt.% when the dilution vapor ratio increases, measured relative to the olefin-containing effluent at a dilution vapor ratio of 0.2. The methane wt.% in the olefin-containing effluent may 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 as the absolute difference in wt.% between the olefin-containing effluent at a dilution vapor ratio of 0.2 and higher dilution vapor ratio values.

[0550] In one embodiment, or in combination with one or more embodiments mentioned herein, the amount of unconverted products in the olefin-containing effluent is reduced when measured relative to a cracker feed without r-pyrolysis oil and under all other identical conditions (including hydrocarbon mass flow rate). For example, the amount of propane and / or ethane can be reduced by adding r-pyrolysis oil. This can benefit from reducing the mass flow rate of the recovery loop, thereby (a) reducing cryogenic energy costs and / or (b) potentially increasing the capacity of the equipment if it is already capacity-limited. Furthermore, it can eliminate bottlenecks in the propylene fractionator if it has reached its capacity limit. The amount of unconverted products in the olefin-containing effluent can be reduced by at least 2%, or at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15%, or at least 18%, or at least 20%.

[0551] In one embodiment or in combination with one or more embodiments mentioned herein, when measured relative to cracker feed without r-pyrolysis oil, the amount of unconverted products (e.g., combined propane and ethane) in the olefin-containing effluent decreases, while the combined yield of ethylene and propylene does not decrease and may even improve. Optionally, all other conditions are the same, including hydrocarbon mass flow rate and temperature, wherein the fuel feed rate to the heating burner to the non-recovery cracker feed coil remains constant, or alternatively, when the fuel feed rate to all coils in the furnace remains constant. Alternatively, the same relationship may hold on a wt.% basis rather than a yield basis.

[0552] For example, the total amount of propane and ethane (yield or wt.%) in olefin-containing effluents may 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 by at most 40%, at most 35%, or at most 30%, while in each case the total amount of ethylene and propylene is not reduced, and may even be accompanied by an increase in the total amount of ethylene and propylene. For example, the amount of propane in olefin-containing effluents may 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 by at most 40%, at most 35%, or at most 30%, while in each case the total amount of ethylene and propylene is not reduced, and may even be accompanied by an increase in the total amount of ethylene and propylene. In any of these embodiments, the cracker feed (different from r-pyrolysis oil and such feed to the inlet of the convection zone) may be primarily propane on a molar basis, or at least 90 mol% propane, or at least 95 mol% propane, or at least 96 mol% propane, or at least 98 mol% propane; or the fresh feed to the cracker may be at least HD5 mass propane.

[0553] In one embodiment or in combination with one or more embodiments mentioned herein, the propane:(ethylene and propylene) ratio in the olefin-containing effluent decreases as r-pyrolysis oil is added to the cracker feed, measured in wt.% or monthly production, relative to the same cracker feed without pyrolysis oil and all other conditions being equal. The propane:(ethylene and propylene) ratio in the olefin-containing effluent may not exceed 0.50:1, or be less than 0.50:1, or not exceed 0.48:1, or not exceed 0.46:1, or not exceed 0.43:1, or not exceed 0.40:1, or not exceed 0.38:1, or not exceed 0.35:1, or not exceed 0.33:1, or not exceed 0.30:1. A low ratio indicates that high amounts of ethylene + propylene can be achieved or maintained, while correspondingly reducing unconverted products such as propane.

[0554] In one embodiment or in combination with one or more embodiments mentioned herein, when r-pyrolysis oil and steam are fed downstream of the convection chamber inlet, or when one or both of the r-pyrolysis oil and steam are fed at an intersection, the amount of C6+ product in the olefin-containing effluent 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 chamber inlet, the amount of C6+ product in the olefin-containing effluent can be increased by 5%, or 10%, or 15%, or 20%, or 30%, all other things being equal, when measured relative to feeding r-pyrolysis oil at the convection chamber inlet. The increase % can be calculated as:

[0555]

[0556] Where Ei is the C6+ content in the olefin-containing cracker effluent prepared by introducing γ-pyrolysis oil at the inlet of the convection box; Ed is the C6+ content in the olefin-containing cracker effluent obtained by introducing pyrolysis oil and steam downstream of the convection box inlet.

[0557] In one embodiment or in combination with any of the embodiments described herein, the cracked olefin-containing effluent may contain relatively small amounts of aromatic hydrocarbons and other heavy components. For example, the olefin-containing effluent may contain at least 0.5, 1, 2, or 2.5 wt% 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 wt% of aromatic hydrocarbons, based on the total weight of the stream. We have found that the C6+ content in the olefin-containing effluent may be no more than 5 wt.%, or no more than 4 wt.%, or no more than 3.5 wt.%, or no more than 3 wt.%, or no more than 2.8 wt.%, or no more than 2.5 wt.%. 6+ The substances include all aromatic hydrocarbons, as well as all alkanes and cyclic compounds with 6 or more carbon atoms. As used throughout, the amount of aromatic hydrocarbons mentioned can be determined by C... 6+ The amount of substance is expressed because the amount of aromatic hydrocarbons will not exceed the amount of C6+.

[0558] 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, 2 The weight ratio of olefins to aromatic hydrocarbons is 7:1, 28:1, 29:1, or 30:1, and / or not exceeding 100:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1, 35:1, 30:1, 25:1, 20:1, 15:1, 10:1, or 5:1. As used herein, “olefins to aromatic hydrocarbons” is the ratio of the total weight of C2 and C3 olefins to the total weight of aromatic hydrocarbons as defined above. In one embodiment or in combination with any of the embodiments mentioned herein, the effluent stream may have an olefin-aromatic mixture of at least 2.5:1, 2.75:1, 3.5:1, 4.5:1, 5.5:1, 6.5:1, 7.5:1, 8.5:1, 9.5:1, 10.5:1, 11.5:1, 12.5:1 or 13:5:1.

[0559] Olefin-containing effluents may have olefins: C 6+ The ratio (by weight) is at least 8.5:1, or at least 9.5:1, or at least 10:1, or at least 10.5:1, or at least 12:1, or at least 13:1, or at least 15:1, or at least 17:1, or at least 19:1, or at least 20:1, or at least 25:1, or at least 28:1, or at least 30:1. Additionally or alternatively, the olefin-containing effluent may have an olefin: C 6+ The ratio is at most 40:1, or at most 35:1, or at most 30:1, or at most 25:1, or at most 23:1. As used herein, “olefins to aromatics” is the ratio of the total weight of C2 and C3 olefins to the total weight of aromatics as defined above.

[0560] Additionally or alternatively, the olefin-containing effluent may contain olefins and C 6+The ratios are at least approximately 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 0.5∶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.

[0561] In one embodiment or in combination with any of the embodiments mentioned herein, the olefin:aromatic hydrocarbon content decreases with increasing amount of γ-pyrolysis oil added to the cracker feed. Because the γ-pyrolysis oil cracks at a lower temperature, it will crack earlier than propane or ethane, and therefore has more time to react and produce other products, such as aromatic hydrocarbons. Although the aromatic hydrocarbon content in the olefin-containing effluent increases with increasing pyrolysis oil content, as stated above, the amount of aromatic hydrocarbons produced is significantly low.

[0562] The olefin-containing composition may also include trace amounts of aromatic hydrocarbons. For example, the composition may have a benzene content of at least 0.25, 0.3, 0.4, or 0.5% by weight, and / or no more than about 2, 1.7, 1.6, or 1.5% by weight. Additionally or alternatively, the composition may have a toluene content of at least 0.005, 0.010, 0.015, or 0.020% by weight and / or no more than 0.5, 0.4, 0.3, or 0.2% by weight. Both percentages are based on the total weight of the composition. Alternatively or additionally, the effluent may have a benzene content of at least 0.2, 0.3, 0.4, 0.5, or 0.55% by weight, and / or no more than about 2, 1.9, 1.8, 1.7, or 1.6% by weight, and / or a toluene content of at least 0.01, 0.05, or 0.10% by weight, and / or no more than 0.5, 0.4, 0.3, or 0.2% by weight.

[0563] In one embodiment or in combination with any of the embodiments mentioned herein, the olefin-containing effluent taken from a cracker that has cracked a composition containing r-pyrolysis oil may contain increased amounts of one or more compounds or byproducts 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-olefins) may include increased amounts of 1,3-butadiene, 1,3-cyclopentadiene, dicyclopentadiene, or combinations of these components. In one embodiment or in combination with any of the embodiments mentioned herein, the total amount (by weight) of these components may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% higher than that of 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 feed stream of the same cracker under the same conditions and at the same 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 feed stream of the same cracker under the same conditions and at the same 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 that of the same cracker feed stream under the same conditions and at the same mass feed rate but without r-pyrolysis oil treatment. The percentage difference is calculated by dividing the difference in 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:

[0564]

[0565] Where E is the wt.% of the components in the cracker effluent obtained without using r-pyrolysis oil; Er is the wt.% of the components in the cracker effluent obtained with r-pyrolysis oil.

[0566] In one embodiment or in combination with any of the embodiments mentioned herein, the olefin-containing effluent may contain acetylene. The amount of acetylene may be at least 2000 ppm, at least 5000 ppm, at least 8000 ppm, or at least 10,000 ppm, based on the total weight of the effluent from the furnace. It may also be no more than 50,000 ppm, no more than 40,000 ppm, no more than 30,000 ppm, or no more than 25,000 ppm, or no more than 10,000 ppm, or no more than 6,000 ppm, or no more than 5000 ppm.

[0567] In one embodiment or in combination with any of the embodiments mentioned herein, the olefin-containing effluent may contain methylacetylene and propadiene (MAPD). The amount of MAPD may be at least 2 ppm, at least 5 ppm, at least 10 ppm, at least 20 ppm, at least 50 ppm, at least 100 ppm, at least 500 ppm, at least 1000 ppm, at least 5000 ppm, or at least 10,000 ppm, based on the total weight of the effluent. It may also not exceed 50,000 ppm, not exceed 40,000 ppm, or not exceed 30,000 ppm, or not exceed 10,000 ppm, or not exceed 6,000 ppm, or not exceed 5,000 ppm.

[0568] In one embodiment or in combination with any of the embodiments mentioned herein, the olefin-containing effluent may contain a small amount or no carbon dioxide. The olefin-containing effluent may have a carbon dioxide content, in wt.%, not exceeding the amount of carbon dioxide in an effluent obtained by cracking the same cracker feed under equivalent conditions but without r-pyrolysis oil, or not exceeding 5% or 2% of the carbon dioxide content, or the same amount as a comparative effluent without r-pyrolysis oil. Alternatively or additionally, the olefin-containing effluent may have a carbon dioxide content not exceeding 1000 ppm, or not exceeding 500 ppm, or not exceeding 100 ppm, or not exceeding 80 ppm, or not exceeding 50 ppm, or not exceeding 25 ppm, or not exceeding 10 ppm, or not exceeding 5 ppm.

[0569] Now go to Figure 9 This diagram illustrates the main components of the furnace effluent processing section. (Example) Figure 9 As shown, the olefin-containing effluent stream from cracker 700 (including recovered components) is rapidly cooled (e.g., quenched) in the delivery line exchange (“TLE”) 680, such as Figure 8As shown, this is to prevent the generation of large amounts of undesirable byproducts and to minimize scaling in downstream equipment, as well as the generation of 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 to a temperature of 35 to 485°C, 35 to 375°C, or 90 to 550°C to 500 to 760°C. The cooling step occurs immediately after the effluent stream leaves the furnace, for example 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 quenching zone 710 via a heat exchanger (sometimes referred to as a delivery line exchanger, such as...) Figure 5 The TLE 340 is shown in the middle and Figure 8 In the embodiment shown in TLE 680, heat exchange is performed indirectly with high-pressure water or steam, while in other embodiments, the quenching step is performed by bringing the effluent into direct contact with the quenching liquid 712 (e.g., Figure 9 (As generally shown in the diagram). The temperature of the quench liquid can be at least 65, or at least 80, or at least 90, or at least 100 °C in each case, and / or not exceeding 210, or not exceeding 180, or not exceeding 165, or not exceeding 150, or not exceeding 135 °C in each case. When using a quench liquid, contact can be carried out in a quench tower, and the liquid stream containing gasoline and other similar boiling-range hydrocarbon components can be removed from the quench tower. In some cases, a quench liquid can be used when the cracker feed is primarily liquid, and a heat exchanger can be used when the cracker feed is primarily steam.

[0570] The resulting cooled effluent is then subjected to vapor-liquid separation, and the vapor is compressed in compression zone 720, for example, in a gas compressor having, for example, 1 to 5 compression stages, with optional interstage cooling and liquid removal. The gas flow pressure at the outlet of the first set of compression stages is in the range of 7 to 20 barg, 8.5 to 18 psig (0.6 to 1.3 barg), or 9.5 to 14 barg.

[0571] The resulting compressed stream is then processed in acid gas removal zone 722 to remove acid gases, including CO, CO2, and H2S, by contact with an acid gas removal agent. Examples of acid gas removal agents 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.

[0572] The processed, compressed olefin-containing stream can then 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. The resulting stream 730 can then be sent to a fractionation section, where olefins and other components can be separated into various high-purity products or intermediate streams.

[0573] Now go to Figure 10 The diagram provides a schematic representation of the main steps of the fractionation section. In one embodiment or in combination with any of the embodiments mentioned herein, the initial column of the fractionation system may not be a demethanizer 810, but may be a deethaner 820, a depropanizer 840, or any other type of column. As used herein, the term "demethanizer" refers to a column whose light bond is methane. Similarly, "deethaner" and "depropanizer" refer to columns having ethane and propane as light bond components, respectively.

[0574] like Figure 10As shown, the feed stream 870 from the quench section can be introduced into a demethanizer (or other) 810, where methane and lighter (CO, CO2, H2) components 812 are separated from ethane and heavier components 814. The demethanizer operates at a temperature of at least -145, or at least -142, or at least -140, or at least -135 °C in each case, and / or not exceeding -120, -125, -130, -135 °C. The bottom stream 814 from the demethanizer is then introduced into the deethaner 820, where C2 and lighter components 816 are separated from C3 and heavier components 818 by fractionation. The bottom stream comprises at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99% of the total amount of ethane and heavier components introduced into the column, in each case as a percentage. The deethanizer 820 can operate at a top temperature of at least -35, or at least -30, or at least -25, or at least -20 °C in each case, and / or not exceeding -5, -10, -10, -200 °C, and at least 3, or at least 5, or at least 7, or at least 8, or at least 10, in each case, in barg, and / or not exceeding 20, or not exceeding 18, or not exceeding 17, or not exceeding 15, or not exceeding 14, or not exceeding 13, in each case, in 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, the percentage of the total amount of C2 and lighter components introduced into the column in the overhead stream. In one embodiment or in combination with any of the embodiments mentioned herein, the overhead stream 816 removed from the de-ethaner contains 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 percentages of ethane and ethylene, based on the total weight of the overhead stream.

[0575] like Figure 10As shown, C2 and the lighter overhead stream 816 from the deethaner 820 are further separated in the ethane-ethylene fractionation column (ethylene fractionation column) 830. In the ethane-ethylene fractionation column 830, ethylene and the lighter component stream 822 can be taken from the overhead distillate of column 830 or as a side stream from the top, while ethane and any remaining heavier components are removed in the bottom stream 824. The ethylene fractionation column 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 °C in each case, and / or not exceeding -15, or not exceeding -20, or not exceeding -25, or in each case, °C, and at a top pressure of at least 10, or at least 12, or at least 15, or in each case, barg, and / or not exceeding 25, 22, 20 barg. The ethylene-rich overhead stream 822 may 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, as a weight percentage of ethylene based on the total weight of the stream, and may be sent to downstream processing units for further processing, storage, or sale. The overhead ethylene stream 822 generated during the cracking of a cracker feedstock 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 may be used to prepare one or more petrochemical products.

[0576] The bottoms stream of the ethane-ethylene fractionation column 824 may include, in each case, 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% ethane by weight, based on the total weight of the bottoms stream. As previously mentioned, all or part of the recovered ethane may be recycled to the cracker as an additional feedstock, either alone or in combination with a feed stream containing r-pyrolysis oil.

[0577] The liquid bottom stream 818 discharged from the deethaner may be rich in C3 and heavier components, which can be separated in the depropaner 840, such as... Figure 10As shown. In the depropanizer 840, C3 and lighter components are removed as overhead vapor stream 826, while C4 and heavier components may exit the column in liquid bottom stream 828. The depropanizer 840 may operate at a top temperature of at least 20, or at least 35, or at least 40 °C in each case, and / or not exceeding 70, 65, 60, 55 °C, and at a top pressure of at least 10, or at least 12, or at least 15 barg in each case, and / or not exceeding 20, or at least 17, or not exceeding 15 barg in each case. The depropanizer 840 receives 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, as a percentage of the total amount of C3 and lighter components introduced into the column in overhead stream 826. In one embodiment or in combination with any of the embodiments mentioned herein, the overhead stream 826 removed from the propane stripper 840 contains 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, a weight percentage of propane and propylene, based on the total weight of the overhead stream 826.

[0578] The overhead stream 826 from the propane stripper 840 is introduced into the propane-propylene fractionation column (propylene fractionation column) 860, where propylene and any lighter components are removed in the overhead stream 832, while propane and any heavier components exit the column in the bottom stream 834. The propylene fractionation column 860 can operate at a top temperature of at least 20, or at least 25, or at least 30, or at least 35 °C in each case, and / or not exceeding 55, 50, 45, 40 °C, and at a top pressure of at least 12, or at least 15, or at least 17, or at least 20, or in each case, barg, and / or not exceeding 20, or not exceeding 17, or not exceeding 15, or not exceeding 12, or in each case, barg. The propylene-rich overhead stream 860 may 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, as a weight percentage of propylene based on the total weight of the stream, and may be sent to downstream processing units for further processing, storage, or sale. The overhead propylene stream generated during the cracking of a cracker feedstock containing r-pyrolysis oil is an r-propylene composition or stream. In one embodiment or in combination with any of the embodiments mentioned herein, this stream may be used to prepare one or more petrochemical products.

[0579] The bottom stream 834 from the propane-propylene fractionation column 860 may include, in each case, 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% of propane, based on the total weight of the bottom stream 834. As previously mentioned, all or part of the recovered propane may be recycled to the cracking furnace as an additional feedstock, either alone or in combination with r-pyrolysis oil.

[0580] Refer again Figure 10 The bottom stream 828 from the propane stripper 840 can be fed into the butane stripper 850 for the separation of C4 components, including butene, butane, and butadiene, from C4 components. 5+ Component separation. The debutanizer can operate at a top temperature of at least 20, or at least 25, or at least 30, or at least 35, or at least 40 °C in each case, and / or not exceeding 60, or not exceeding 65, or not exceeding 60, or not exceeding 55, or not exceeding 50 °C in each case, and a top pressure of at least 2, or at least 3, or at least 4, or at least 5, or in each case, barg, and / or not exceeding 8, or not exceeding 6, or not exceeding 4, or not exceeding 2, or 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, the percentage of the total amount of C4 and lighter components introduced into the column in the top stream 836. In one embodiment or in combination with any of the embodiments 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, a weight percentage of butadiene based on the total weight of the overhead stream. The overhead stream 836 generated during cracking of a cracker feedstock containing r-pyrolysis oil is an r-butadiene composition or stream. The bottom stream 838 from the debutanizer primarily 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 percentages of C5 and heavier components based on the total weight of the stream. The bottom stream 838 from the debutanizer may be sent for further separation, processing, storage, sale, or use.

[0581] Any conventional separation method, such as extraction or distillation, can be used to recover a more concentrated butadiene stream from the overhead stream 836 or C4 of the butane dehydrogenator.

[0582] Chemical intermediates, polyester reactants and their preparation methods

[0583] Recycled components of polyester can be provided via recycled polyester reactants. In examples, polyester reactants are compounds capable of reacting to form residues in the polyester. In examples, reactants can be glycol monomers. In examples, the glycol monomer is cyclobutanediol. In examples, cyclobutanediol is TMCD.

[0584] A method for preparing a recycled component compound, such as isobutyraldehyde, isobutyric acid, or isobutyric anhydride, for use as an intermediate or polyester reactant begins by feeding a recycled propylene composition (“r-propylene”) into a reactor in a reaction scheme for preparing intermediates and / or polyester reactants, wherein the r-propylene is derived directly or indirectly from cracked r-pyrolysis oil.

[0585] As used herein, “r-isobutyraldehyde” refers to a composition containing isobutyraldehyde with a recycled component. As used herein, “r-isobutyric acid” refers to a composition containing i...

Claims

1. A process for preparing recycled polyester, i.e., r-polyester, comprising: (1) obtaining a recovered propylene composition, i.e., r-propylene, directly or indirectly derived from a cracked recovered component pyrolysis oil composition, i.e., r-pyrolysis oil; (2) using r-propylene as a starting material in a reaction scheme to produce at least one polyester reactant for making polyester; and (3) reacting the at least one polyester reactant to produce at least one polyester; wherein the r-pyrolysis oil is prepared from a waste plastics-containing stream comprising at least 30 wt % of waste plastics, the waste plastics being selected from the group consisting of high-density polyethylene, low-density polyethylene, polypropylene, other polyolefins other than the above, polystyrene, and any combination thereof; Based on the weight of the r-pyrolysis oil, the r-pyrolysis oil contains at least 95 wt.% C5-C 25 hydrocarbons, the r-pyrolysis oil comprising at least 10 wt.% and not more than 35 wt.% of olefins, the r-pyrolysis oil comprising not more than 35 wt.% of aromatic hydrocarbons; Wherein, the cracking of step (1) comprises simultaneously cracking the r-pyrolysis oil and non-recovered propane in a cracker, wherein The feed stream containing r-pyrolysis oil comprises at least 5 wt.% and no more than 50 wt.% of r-pyrolysis oil and at least 50 wt.% of propane, based on the total weight of the feed stream, The r-pyrolysis oil is not hydrotreated before the cracking, In the radiant section of the cracker, the feed stream containing r-pyrolysis oil is thermally cracked, the residence time of the feed stream in the radiant section is at least 0.15 seconds and not more than 1 second, the temperature at the inlet of the furnace coil of the radiant section is at least 500°C and not more than 650°C, and the coil outlet temperature of the radiant section is at least 640°C and not more than 830°C.

2. The process according to claim 1, wherein The at least one polyester reactant is TMCD, and Wherein, the at least one polyester is selected from TMCD-modified PCT, TMCD-modified PET or a combination thereof.

3. The process according to claim 1, wherein: The reaction scheme for producing at least one polyester reactant includes one or more of the following reactions: (1) converting the r-propylene into a recovered isobutyraldehyde composition, i.e., r-isobutyraldehyde; (2) converting the r-propylene into a first recovery component, i.e., first r-isobutyric acid; (3) converting the r-isobutyraldehyde into a second recovered component, isobutyric acid, i.e., a second r-isobutyric acid; (4) converting the first r-isobutyric acid and / or the second r-isobutyric acid into a recovery component, i.e., r-isobutyric anhydride; (5) In the reaction scheme, the r-isobutyric anhydride is converted into the recovery component TMCD, i.e., r-TMCD.

4. A method for obtaining recycled content in polyester, comprising: a. obtaining a TMCD composition designated as having a recycled component, and b. feeding TMCD and one or more dicarboxylic acids or derivatives thereof and optionally one or more other diols to a reactor under conditions effective to produce a polyester, and wherein, whether or not the designation so indicates, at least a portion of the TMCD composition is derived directly or indirectly from a cracked recovered pyrolysis oil composition, i.e., r-pyrolysis oil; wherein the r-pyrolysis oil is prepared from a waste plastics-containing stream comprising at least 30 wt% waste plastics, the waste plastics being selected from the group consisting of high density polyethylene, low density polyethylene, polypropylene, other polyolefins other than those mentioned above, polystyrene, and any combination thereof; Based on the weight of the r-pyrolysis oil, the r-pyrolysis oil contains at least 95 wt.% C5-C 25 hydrocarbons, the r-pyrolysis oil comprising at least 10 wt.% and not more than 35 wt.% of olefins, the r-pyrolysis oil comprising not more than 35 wt.% of aromatic hydrocarbons; wherein the cracking comprises simultaneously cracking the r-pyrolysis oil and non-recovered propane in a cracker, wherein The feed stream containing r-pyrolysis oil comprises at least 5 wt.% and no more than 50 wt.% of r-pyrolysis oil and at least 50 wt.% of propane, based on the total weight of the feed stream, The r-pyrolysis oil is not hydrotreated before the cracking, In the radiant section of the cracker, the feed stream containing r-pyrolysis oil is thermally cracked, the residence time of the feed stream in the radiant section is at least 0.15 seconds and not more than 1 second, the temperature at the inlet of the furnace coil of the radiant section is at least 500°C and not more than 650°C, and the coil outlet temperature of the radiant section is at least 640°C and not more than 830°C.

5. The process according to any one of claims 1 to 3, wherein The process is an integrated process for preparing a polyester composition, comprising: a. providing a TMCD manufacturing facility and preparing a recycled component TMCD composition, i.e., r-TMCD, from a feed composition, at least a portion of which is obtained by a reaction scheme starting from r-propylene, and b. providing a polyester manufacturing facility comprising a reactor receiving TMCD, said reactor containing one or more dicarboxylic acids or derivatives thereof and optionally one or more other diols; and c. Feeding r-TMCD from the TMCD manufacturing facility to the polyester manufacturing facility through a system of fluid communication between the facilities.

6. The method according to claim 4, wherein: The method also includes introducing or establishing recycled content in the polyester by: a. obtaining a recovered propylene composition, ie, an r-propylene allocation or credit, b. conversion of propylene in a synthesis process to produce isobutyric acid and / or to isobutyraldehyde, which is then converted into isobutyric acid, c. optionally converting isobutyric acid in a synthesis process to prepare isobutyric anhydride, d. converting isobutyric anhydride and / or isobutyric acid in a synthesis process to prepare dimethyl ketene, e. Converting dimethyl ketene to produce TMCD in a synthetic process scheme, f. Converting TMCD in a synthetic process to prepare polyesters, g. designating at least a portion of the polyester to correspond to at least a portion of the r-propylene allocation or credit, and optionally h. Promising to sell or selling polyester containing or obtained with the following recycled content, the recycled content corresponding to the designation.

7. The process according to any one of claims 1 to 3, in, Step (1) comprises: a. preparing r- pyrolysis oil by pyrolysis recovery feed; and b. cracking r-pyrolysis oil to produce a first round of r-propylene, at least a portion of which is obtained from cracking r-pyrolysis oil; and Wherein, step (2) comprises: a. converting at least a portion of the r-propylene in a synthesis process to produce isobutyric acid and / or to produce isobutyraldehyde, and converting the isobutyraldehyde to produce isobutyric acid, and b. optionally converting at least a portion of the isobutyric acid in a synthesis process to produce isobutyric anhydride, c. converting at least a portion of the isobutyric anhydride and / or isobutyric acid in a synthesis process to produce dimethyl ketene, d. converting dimethyl ketene to produce TMCD in a synthetic process scheme, and Wherein, step (3) comprises: a. In a synthetic process, TMCD is reacted with a dicarboxylic acid or its derivatives to prepare polyesters.

8. The process according to any one of claims 1 to 3, wherein The r-propylene is derived directly or indirectly from cracking r-pyrolysis oil in a gas furnace.

9. The process according to any one of claims 1 to 3, wherein The r-propylene is derived directly or indirectly from cracking r-pyrolysis oil in a cracking furnace.

10. The process according to claim 8, wherein: The r-propylene is derived directly or indirectly from cracking r-pyrolysis oil in a hot steam gas furnace.

11. The process according to any one of claims 1 to 3, wherein The r-pyrolysis oil contains no more than 30 wt% aromatic hydrocarbons, based on the total weight of the r-pyrolysis oil.

12. The process according to any one of claims 1 to 3, wherein The r-pyrolysis oil comprises olefins present in an amount of 40 wt.% to 85 wt.%, based on the weight of the r-pyrolysis oil.

13. The process according to any one of claims 1 to 3, wherein The weight ratio of the combination of paraffinic hydrocarbons and cycloparaffinic hydrocarbons to aromatic hydrocarbons in the r-pyrolysis oil may be 1:1-7:

1.

14. The process according to any one of claims 1 to 3, wherein The cracker feed stream or composition to the cracker furnace comprises said r-pyrolysis oil and 90% of the boiling point of the cracker feed stream or composition to the cracker furnace does not exceed 350°C.

15. The process according to any one of claims 1 to 3, comprising: A cracker feed stream comprising r-pyrolysis oil is fed into a furnace, wherein the furnace includes a gas coil that receives a propane feedstock to an inlet of the gas coil in a convection section.

16. The process of claim 8, wherein: The gas furnace has more than one gas coil.

Images