Pyrolysis process and system for recovering waste

Abstract

Pyrolysis processes and systems are provided that utilize a multi-stage dehalogenation process to effectively remove halogen-containing compounds present in an initially recycled plastic feedstock. More particularly, multi-stage dehalogenation systems and processes may include physically sorting a plastic feedstock, melting and separating the feedstock, and two-stage pyrolysis of the feedstock and removal of intermediate HCl.

Description

[0001] This application is a divisional application of the invention patent application with a priority date of October 31, 2019, an application date of October 29, 2020, an application number of 202080075893.X, and an invention name of “Pyrolysis method and system for waste recycling”. Background Art

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

[0003] While some waste materials are relatively easy and inexpensive to recycle, others require extensive and expensive processing for reuse. Furthermore, different types of waste materials often require different types of recycling processes. In many cases, expensive physical sorting of the waste is required to separate it into relatively pure, single-component waste volumes.

[0004] To maximize recycling efficiency, it is desirable for large-scale production facilities to be able to process feedstock with recycled content derived from various waste materials. Commercial facilities involved in the production of non-biodegradable products can greatly benefit from using recycled content feedstock, as the positive environmental impact of using recycled content feedstock can offset the negative environmental impact of producing non-biodegradable products.

[0005] Unfortunately, many pyrolysis oils produced from various waste plastics may contain high halogen (e.g., chlorine) content due to the presence of certain halogen-containing plastics in the initial pyrolysis feed. Typically, the halogen content of the cracker feed must be kept below a certain level to prevent stress cracking in high-nickel alloys, which can lead to catastrophic failure of the cracking equipment. In addition, higher halogen levels in the cracker feed can accelerate the likelihood of stress cracking and poison catalysts used in downstream processes. Therefore, in many cases, high halogen levels in the cracker feed may require expensive metallurgical processes to prevent the aforementioned stress cracking and corrosion.

[0006] We have discovered that a multi-stage dehalogenation system and process, which can include physical sorting of plastic feedstock, melting and separating the feedstock, and two-stage pyrolysis with intermediate HCl removal, facilitates the removal of undesirable halogen-containing compounds from the resulting pyrolysis oil. More specifically, we have discovered that a two-stage pyrolysis process can effectively remove halogens from recycled plastic feedstock, thereby generating a halogen-containing waste gas that can be easily removed from the pyrolysis system. This can thus avoid the expensive metallurgical costs associated with downstream processing of the pyrolysis oil. Summary of the Invention

[0007] In certain embodiments, the present invention relates to the large-scale production of one or more materials having recycled content. The recycled content of the product can be derived from recycled waste and / or from recycled content pyrolysis oil (r-pyrolysis oil) produced by pyrolysis of recycled waste. In certain embodiments, the pyrolysis unit that produces the r-pyrolysis oil can be co-located with the production facility. In other embodiments, the r-pyrolysis oil can be derived from a remote pyrolysis unit and transported to the production facility.

[0008] In certain embodiments, the present invention relates to a method for preparing pyrolysis oil. Generally, the method comprises: (a) providing a plastic-containing feed comprising at least one halogen-containing waste plastic; (b) dehalogenating at least a portion of the plastic-containing feed, thereby forming a halogen waste stream and a dehalogenated feed; and (c) pyrolyzing at least a portion of the dehalogenated feed, thereby forming a pyrolysis effluent comprising pyrolysis oil. In addition, the pyrolysis oil: (i) comprises an aromatic hydrocarbon content of less than 25% by weight; (ii) comprises an alkane content of at least 25% by weight; and (iii) exhibits a carbon content of less than 0.9 g / cm at 15°C. 3 density.

[0009] In certain embodiments, the present invention relates to a method for preparing pyrolysis oil. Generally, the method comprises: (a) providing a plastic-containing feed comprising at least one halogen-containing waste plastic; (b) heating the plastic-containing feed to a temperature sufficient to thereby release a halogen-containing waste stream and form a dehalogenated feed; and (c) pyrolyzing at least a portion of the dehalogenated feed, thereby forming a pyrolysis effluent comprising pyrolysis oil. In addition, the pyrolysis oil: (i) comprises an aromatic hydrocarbon content of less than 25% by weight; (ii) comprises an alkane content of at least 25% by weight; and (iii) exhibits a carbon content of less than 0.9 g / cm at 15°C. 3 density.

[0010] In certain embodiments, the present invention relates to a method for preparing pyrolysis oil. Generally, the method comprises: (a) providing a plastic-containing feed comprising at least one halogen-containing waste plastic; (b) introducing at least a portion of the plastic-containing feed into a pyrolysis unit; (c) pyrolyzing at least a portion of the plastic-containing feed, thereby forming a pyrolysis effluent comprising pyrolysis oil and a halogen-containing waste stream; and (d) separating at least a portion of the halogen-containing waste stream from the pyrolysis effluent. In addition, the pyrolysis oil: (i) comprises an aromatic hydrocarbon content of less than 25% by weight; (ii) comprises an alkane content of at least 25% by weight; and (iii) exhibits a carbon content of less than 0.9 g / cm3 at 15°C. 3 density. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 is a schematic diagram of a process for preparing one or more recycled content compositions into an r-composition using a recycled content pyrolysis oil composition (r-pyrolysis oil).

[0012] Figure 2 is a schematic representation of an exemplary pyrolysis system for at least partially converting one or more recycled wastes, particularly recycled plastic wastes, into various useful r-products.

[0013] Figure 3 is a schematic diagram of a pyrolysis process to produce an olefin-containing product.

[0014] Figure 4 is a block flow diagram showing the steps associated with the cracking furnace and separation zones of a system for producing an r-composition obtained from cracking r-pyrolysis oil and non-recovered cracker feed.

[0015] Figure 5 is a schematic diagram of a cracking furnace suitable for receiving r-pyrolysis oil.

[0016] Figure 6 A furnace coil configuration with multiple tubes is shown.

[0017] Figure 7 Various feed positions of r-pyrolysis oil into the cracking furnace are shown.

[0018] Figure 8 A cracking furnace with a vapor liquid separator is shown.

[0019] Figure 9 is a block diagram illustrating the process of recovering constituent furnace effluent.

[0020] Figure 10 A fractionation scheme is shown for separating and isolating the main r-compositions including r-propylene, r-ethylene, r-butene, etc., including a demethanizer, a deethanizer, a depropanizer, and a fractionator.

[0021] Figure 11 A laboratory scale cracking unit design is shown.

[0022] Figure 12 Design features for a plant-based experimental feeding of r-pyrolysis oil to a gas-fed cracking furnace are described.

[0023] Figure 13 is a boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis with 74.86% C8+, 28.17% C15+, 5.91% aromatics, 59.72% paraffins and 13.73% unidentified components.

[0024] Figure 14 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0025] Figure 15 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0026] Figure 16 The boiling point curve of r-pyrolysis oil obtained by distillation in the laboratory and chromatography analysis.

[0027] Figure 17 This is a graph of the boiling points of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350°C, 50% boils between 95°C and 200°C, and at least 10% boils at 60°C.

[0028] Figure 18 The boiling point curve of r-pyrolysis oil distilled in the laboratory is shown, where at least 90% boils at 150°C, 50% boils between 80°C and 145°C, and at least 10% boils at 60°C.

[0029] Figure 19 This is a graph of the boiling points of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350°C, at least 10% boils at 150°C, and 50% boils between 220°C and 280°C.

[0030] Figure 20 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with 90% boiling point between 250-300°C.

[0031] Figure 21 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with 50% boiling point between 60-80°C.

[0032] Figure 22 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with an aromatic content of 34.7%.

[0033] Figure 23 is a boiling point graph of r-pyrolysis oil having an initial boiling point of about 40°C.

[0034] Figure 24 is a graph of the carbon distribution of the pyrolysis oil used in the plant trials.

[0035] Figure 25 is a graph of the carbon distribution of the pyrolysis oil used in the plant trials.

[0036] Figure 26 is a schematic diagram of pyrolysis processing by separating dehalogenated pyrolysis gas and pyrolysis effluent streams. DETAILED DESCRIPTION

[0037] The words "containing" and "including" are synonymous with comprising. When indicating a numerical sequence, it should be understood that each number is modified to be the same as the first or last number in the numerical sequence or sentence, for example, each number is "at least" or "up to" or "not more than" as the case may be; and each number is in an "or" relationship. For example, "at least 10, 20, 30, 40, 50, 75 wt.% ..." means the same as "at least 10 wt.%, or at least 20 wt.%, or at least 30 wt.%, or at least 40 wt.%, or at least 50 wt.%, or at least 75 wt.%", etc.; and "not more than 90 wt.%, 85, 70, 60 ..." means the same as "not more than 90 wt.%, or not more than 85 wt.%, or not more than 70 wt.% ...", etc.; and "at least 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by weight...", etc. ” means the same as “at least 1 wt.%, or at least 2 wt.%, or at least 3 wt.%…” etc.; and “at least 5, 10, 15, 20 and / or no more than 99, 95, 90 weight percent” means the same as “at least 5 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, and / or no more than 99 wt.%, or no more than 95 wt.%, or no more than 90 weight percent…” etc.; or “at least 500, 600, 750°C…” means the same as “at least 500°C, or at least 600°C, or at least 750°C…” etc.

[0038] In some aspects, methods are provided for producing pyrolysis oil and / or pyrolysis gas from a plastic-containing feedstock containing some halogen content, including systems or processes for reducing the halogen content of the feedstock and / or pyrolysis oil and / or pyrolysis gas.

[0039] Pyrolysis / cracking systems and processes

[0040] Unless otherwise indicated, all concentrations or amounts are by weight. "Olefin-containing effluent" is the furnace effluent obtained by cracking a cracker feed containing r-pyrolysis oil. "Non-recovered olefin-containing effluent" is the furnace effluent obtained by cracking a cracker feed that does not contain r-pyrolysis oil. Hydrocarbon mass flow rates, MF1 and MF2, are in thousands of pounds per hour (klb / hr) unless otherwise indicated as molar flow rates.

[0041] As used herein, "containing" and "including" are open ended and synonymous with "comprising."

[0042] The term "recycled content" is used herein as a noun to i) refer to a physical component (e.g., a compound, molecule, or atom), at least a portion of which is derived directly or indirectly from recycled waste, or ii) as an adjective modifying a specific composition (e.g., a compound, polymer, feedstock, product, or stream), at least a portion of which is derived directly or indirectly from recycled waste.

[0043] As used herein, "recycled content composition," "recycled composition," and "r-composition" refer to a composition having recycled content.

[0044] The term "pyrolysis recovery component" is used herein as a noun to i) refer to a physical component (e.g., a compound, molecule, or atom) at least a portion of which is derived directly or indirectly from the pyrolysis of a recovery waste, or ii) as an adjective modifying a specific composition (e.g., a feedstock, product, or stream) at least a portion of which is derived directly or indirectly from the pyrolysis of a recovery waste. For example, the pyrolysis recovery component can be derived directly or indirectly from a recovery component pyrolysis oil, a recovery component pyrolysis gas, or cracking of a recovery component pyrolysis oil, for example, by a thermal steam cracker or a fluid catalytic cracker.

[0045] As used herein, "pyrolysis recycled content composition," "pyrolysis recycled composition," and "pr-composition" refer to a composition (e.g., a compound, polymer, feedstock, product, or stream) having recycled content from pyrolysis. pr-compositions are a subset of r-compositions, wherein at least a portion of the recycled content of the r-composition is derived directly or indirectly from the pyrolysis of recycled waste.

[0046] As used herein, a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "directly derived" or "derived directly" from recycled waste has at least one physical component traceable to the recycled waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from recycled waste has a recycled content quota associated with it and may or may not contain physical components traceable to the recycled waste.

[0047] As used herein, a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "directly derived" or "derived directly" from the pyrolysis of recycled waste has at least one physical component traceable to the pyrolysis of recycled waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from the pyrolysis of recycled waste has a recycled content quota associated with it and may or may not contain a physical component traceable to the pyrolysis of recycled waste.

[0048] As used herein, "pyrolysis oil" or "pyoil" refers to a composition of matter that is liquid when measured at 25°C and 1 atm and at least a portion of which is obtained by pyrolysis.

[0049] As used herein, "recycled content pyrolysis oil," "recycled pyrolysis oil," "pyrolysis recycled content pyrolysis oil," and "r-pyrolysis oil" refer to pyrolysis oil, at least a portion of which is obtained from pyrolysis and has recycled content.

[0050] As used herein, "pyrolysis gas" and "pyrolysis gas ("pyrolysis gas") refer to a composition of matter that is a gas when measured at 25°C and 1 atm, at least a portion of which is obtained from pyrolysis.

[0051] As used herein, "recycled content pyrolysis gas," "recycled pyrolysis gas," "pyrolysis content pyrolysis gas," and "r-pyrolysis gas" refer to pyrolysis gas that is at least partially obtained from pyrolysis and has recycled content.

[0052] As used herein, "Et" is the ethylene component (eg, feedstock, product, or stream), and "Pr" is the propylene component (eg, feedstock, product, or stream).

[0053] As used herein, "recycled content ethylene," "r-ethylene," and "r-Et" refer to Et with a recycled content; "recycled content propylene," "r-propylene," and "r-Pr" refer to Pr with a recycled content.

[0054] As used herein, "pyrolysis recovered ethylene" and "pr-Et" refer to r-Et with pyrolysis recovered components; "pyrolysis recovered propylene" and "pr-Pr" refer to r-Pr with pyrolysis recovered components.

[0055] As used throughout, general descriptions of compounds, compositions, or streams do not require the presence of their substance, but do not exclude and may include their substance. For example, "Et" or "any Et" may include ethylene produced by any process and may or may not have recycled content, and may or may not include r-Et or pr-Et. Similarly, r-Et may or may not include pr-Et, although reference to r-Et does require that it have recycled content.

[0056] "Recycled pyrolysis components" are a specific subset / type (category) of "recycled components" (genus). Wherever "recycled components" and "r-" are used herein, such use should be interpreted as explicitly disclosing and providing claim support for "recycled pyrolysis components" and "pr-", even if not explicitly stated as such. For example, whenever the term "recycled component ethylene" or "r-Et" is used herein, it should be interpreted as also explicitly disclosing and providing claim support for "recycled pyrolysis components" and "pr-Et".

[0057] As used throughout, whenever reference is made to cracking of r-pyrolysis oil, such cracking can be carried out by a thermal cracker or a hot steam cracker in a liquid feed furnace or in a gas feed furnace or in any cracking process. In one embodiment or in combination with any of the embodiments mentioned, the cracking is not catalytic or is carried out in the absence of an added catalyst, or is not a fluid catalytic cracking process.

[0058] As used throughout, whenever reference is made to pyrolysis of recycled waste or r-pyrolysis oil, all embodiments also include the option of (i) cracking the effluent of the pyrolysis recycled waste or cracking the r-pyrolysis oil and / or (ii) using the cracked effluent or r-pyrolysis oil as feed to the tubes of a gas feed furnace or gas furnace / cracker.

[0059] As used throughout, a "family of entities" means at least one person or entity that directly or indirectly controls, is controlled by, or is under common control with another person or entity, where control means ownership of at least 50% of the voting stock, or shared management, common use of facilities, equipment, and employees, or a family interest. As used throughout, references to a person or entity provide claim support to, and include, any person or entity in the family of entities.

[0060] In one embodiment or in combination with any other mentioned embodiment, reference to r-Et also includes pr-Et, or pr-Et obtained directly or indirectly from cracking of r-pyrolysis oil or from r-pyrolysis gas.

[0061] In one embodiment or in combination with any of the above embodiments, a method is provided for preparing an r-composition by reacting an olefin-containing effluent (e.g., Et and / or Pr) in a reaction scheme. For example, in the case of Et, the Et can be r-Et, pr-Et, or dr-Et. In one embodiment, the method for preparing an r-composition begins by feeding r-Et into a reactor for preparing the r-composition (or an intermediate in a reaction scheme for first preparing the r-composition).

[0062] Figure 1 is a schematic diagram illustrating an embodiment of a process for preparing one or more recycled content compositions (e.g., ethylene, propylene, butadiene, hydrogen and / or pyrolysis gasoline) (r-composition) using a recycled content pyrolysis oil composition (r-pyrolysis oil), or in combination with any embodiment mentioned herein.

[0063] like Figure 1 As shown in , the recycled waste can be subjected to pyrolysis in a pyrolysis unit 10 to produce a pyrolysis product / effluent comprising a recycled component pyrolysis oil composition (r-pyrolysis oil). The r-pyrolysis oil can be fed to a cracker 20 along with non-recycled cracker feed (e.g., propane, ethane, and / or natural gasoline). A recycled component cracked effluent (r-cracked effluent) can be produced from the cracker and then separated in a separation train 30. In one embodiment, or in combination with any of the embodiments mentioned herein, the r-composition can be separated and recovered from the r-cracked effluent. The r-propylene stream can contain primarily propylene, while the r-ethylene stream can contain primarily ethylene.

[0064] As used herein, a furnace includes a convection zone and a radiant zone. The convection zone includes the tubes and / or coils inside the convection box, which may also continue outside the convection box downstream of the coil inlet at the inlet of the convection box. For example, Figure 5 As shown, the convection zone 310 includes coils and tubing within a convection box 312 and may optionally extend outside of the convection box 312 and return to or interconnect with tubing 314 within the convection box 312. The radiant zone 320 includes radiant coils / tubes 324 and burners 326. The convection zone 310 and the radiant zone 320 may be contained in a single integral box or in separate discrete boxes. The convection box 312 does not have to be a separate, discrete box. Figure 5 As shown, the convection box 312 is integrated with the combustion chamber 322 .

[0065] Unless otherwise indicated, all component amounts provided herein (eg, for feeds, materials, streams, compositions, and products) are expressed on a dry basis.

[0066] As used herein, "r-pyoil" or "r-pyrolysis oil" are interchangeable and refer to a composition of matter that is liquid when measured at 25° C. and 1 atmosphere, and at least a portion of which is obtained from pyrolysis and has recycled content. In embodiments, at least a portion of the composition is obtained from pyrolysis of recycled waste (e.g., waste plastic or waste streams).

[0067] In an embodiment, "r-ethylene" can be a composition comprising: (a) ethylene obtained from cracking a cracker feed containing r-pyrolysis oil, or (b) ethylene with a recovery content value attributable to at least a portion of the ethylene; and "r-propylene" can be a composition comprising: (a) propylene obtained from cracking a cracker feed containing r-pyrolysis oil, or (b) propylene with a recovery content value attributable to at least a portion of the propylene.

[0068] References to "r-ethylene molecules" refer to ethylene molecules derived directly or indirectly from recycled waste and references to "pr-ethylene molecules" refer to ethylene molecules derived directly or indirectly from r-pyrolysis oil effluent (r-pyrolysis oil or r-pyrolysis gas).

[0069] As used herein, "site" means the largest contiguous geographic boundary owned by a product (e.g., ethylene oxide) manufacturer, or by a person or entity, or a combination of persons or entities within its family of entities, wherein the geographic boundary contains one or more manufacturing facilities, at least one of which is a product (e.g., ethylene oxide) manufacturing facility.

[0070] As used herein, the term "predominantly" means greater than 50 weight percent, unless expressed in mole percent, in which case it means greater than 50 mol%. For example, a stream, composition, feedstock, or product that is predominantly propane is a stream, composition, feedstock, or product that contains greater than 50 weight percent propane, or if expressed in mol%, refers to a product that contains greater than 50 mol% propane.

[0071] As used herein, a composition "directly derived from" cracked pyrolysis oil has at least one physical component traceable to an r-composition, at least a portion of which was obtained by or in conjunction with cracking r-pyrolysis oil, while a composition "indirectly derived from" cracked r-pyrolysis oil has a recycled content quota associated therewith and may or may not contain physical components traceable to an r-composition, at least a portion of which was obtained by or in conjunction with cracking r-pyrolysis oil.

[0072] As used herein, "recycled content value" and "r-value" refer to units of measurement that represent the amount of material that is derived from recycled waste. The r-value can be derived from any type of recycled waste processed in any type of process.

[0073] As used herein, the terms "pyrolysis recovered content value" and "pr-value" refer to units of measurement representing the amount of material derived from the pyrolysis of recycled waste. pr-values are a specific subset / type of r-values associated with the pyrolysis of recycled waste. Therefore, the term r-value encompasses, but does not require, pr-values.

[0074] The specific recovery component value (r-value or pr value) can be by mass or percentage or any other unit of measurement, and can be determined according to the standard system for the recovery component in various compositions for tracing back to the past, distributing and / or depositing and lending.The recovery component value can be deducted from the recovery component inventory and applied to product or composition, so that the recovery component is attributed to product or composition. Unless otherwise stated, the recovery component value is not necessarily derived from manufacturing or cracking r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned, at least a portion of the r-pyrolysis oil from which a quota is obtained is also cracked in the cracking furnace as described in one or more embodiments throughout this paper.

[0075] In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the recycled content credit or recycled content value deposited into the recycled content inventory is obtained from the r-pyrolysis oil. Desirably, at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or up to 100% of:

[0076] a. quota, or

[0077] b. deposited into recycled content inventory, or

[0078] c. The recycled content value in the recycled content inventory, or

[0079] d. Recycled content values applied to compositions to prepare recycled content products, intermediates, or articles (recycled PIA) are obtained from r-pyrolysis oil.

[0080] A recycled PIA is a product, intermediate, or article that may include a compound or a composition containing a compound or polymer, and / or an article with an associated recycled content value. A PIA does not have a recycled content value associated with it. PIAs include, but are not limited to, ethylene or propylene.

[0081] As used herein, "recycled content quota" or "quota" means a recycled content value of:

[0082] a. Transferring from a starting composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which is obtained from recycled waste, or has at least a portion of its recycled content value derived from recycled waste, optionally from r-pyrolysis oil, to a receiving composition (a composition receiving an allowance, such as a compound, polymer, feedstock, product, or stream), the starting composition having at least a portion thereof obtained from recycled waste, or having at least a portion of its recycled content value derived from recycled waste, optionally from r-pyrolysis oil, the receiving composition having or not having physical components traceable to a composition at least a portion of which is obtained from recycled waste; or

[0083] b. Depositing into a recycling inventory a starting composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which was obtained from, or has at least a portion of, a recycled content value or pr value derived from recycled waste.

[0084] As used herein, "pyrolysis recovery component quota" and "pyrolysis quota" or "pr-quota" means a recovery component value of:

[0085] a. from a starting composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which was obtained from the pyrolysis of recycled waste, or has at least a portion of its recycled content value derived from the pyrolysis of recycled waste, to a receiving composition (e.g., a compound, polymer, feedstock, product, or stream), which may or may not have physical components traceable to a composition at least a portion of which was obtained from the pyrolysis of recycled waste; or

[0086] b. Deposited into a recycling inventory from a starting composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which was obtained from, or has at least a portion of its recycled content value derived from, the pyrolysis of recycling waste.

[0087] A pyrolysis recovery credit is a specific type of recovery credit associated with the pyrolysis of recycled waste. Thus, the term recovery credit includes pyrolysis recovery credits.

[0088] In one embodiment or in combination with any of the mentioned embodiments, the thermal pyrolysis recovery component quota or pyrolysis quota can have a recovery component value of:

[0089] a. from a starting composition (e.g., a compound, polymer, feedstock, product or stream) that was obtained at least in part from the cracking of r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), or was transferred from recycled waste used to prepare cracked r-pyrolysis oil, or was transferred from cracked or to be cracked r-pyrolysis oil, or which has at least a portion of its recycled content value derived from the cracking of r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), to a receiving composition (e.g., a compound, polymer, feedstock, product or stream or PIA), the starting composition being obtained at least in part from the cracking of r-pyrolysis oil; or

[0090] b. deposited into the recovered content inventory and obtained from a composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which was obtained from, or has at least a portion of its recovered content value derived from, the cracking (e.g., liquid or gaseous thermal steam cracking) of an r-pyrolysis oil (whether or not the r-pyrolysis oil was cracked when the allowance was deposited into the recovered content inventory, provided that the r-pyrolysis oil from which the allowance was withdrawn was ultimately cracked).

[0091] A quota can be an allotment or a credit.

[0092] The recycled content quota may include a recycled content allocation or a recycled content credit obtained by diverting or using raw materials. In one embodiment or in combination with any of the aforementioned embodiments, the composition receiving the recycled content quota may be a non-recycled composition, thereby converting the non-recycled composition into an r-composition.

[0093] As used herein, "non-recycled" refers to a composition (eg, compound, polymer, feedstock, product, or stream) that is not derived directly or indirectly from recycled waste.

[0094] As used herein, "non-recycled feed" in the context of a feed to a cracker or furnace refers to a feed that is not obtained from a recycled waste stream. Once the non-recycled feed receives a recycled content allowance (e.g., through a recycled content credit or recycled content allotment), the non-recycled feed becomes a recycled content feed, composition, or recycled PIA.

[0095] As used herein, the term "recycled component allotment" refers to a type of recycled component quota where an entity or individual that supplies a composition sells or transfers the composition to a receiving individual or entity, and the individual or entity that prepares the composition has an allotment, 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 entity or individual or family of entities or by different families of entities. In embodiments, the recycled component allotment travels with the composition and downstream derivatives of the composition. In embodiments, the allotment may be deposited into a recycled component stock and withdrawn from the recycled component stock as an allotment and applied to a composition to prepare an r-composition or recycle PIA.

[0096] As used herein, "recycled content credit" and "credit" means a recycled content credit wherein the credit is not limited to being associated with compositions made from cracked r-pyrolysis oil or downstream derivatives thereof, but rather has the flexibility to be derived from r-pyrolysis oil and is (i) applied to compositions or PIAs made from processes other than cracking feedstock in a furnace, or (ii) applied to downstream derivatives of compositions made from processes other than cracking feedstock in a furnace through one or more intermediate feedstocks, or (iii) may be sold or transferred to a person or entity other than the credit owner, or (iv) may be sold or transferred by a person other than the supplier of the composition to which it is transferred. For example, a quota may be a credit when it is taken from r-pyrolysis oil and applied by the quota owner to a BTX composition or fraction thereof that is manufactured by the owner or within its family of entities and is obtained by refining and fractionating petroleum rather than from 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 components of the third party.

[0097] Credits may be available for sale, transfer or use, or be sold, transferred or used, or:

[0098] a. not sell the composition, or

[0099] b. sell or transfer the composition, but the quota is not related to the sale or transfer of the composition, or

[0100] c. Deposits into or withdrawals from recycled content stock that does not trace back molecules of recycled content raw materials to molecules of resulting compositions made with recycled content raw materials, or that has such traceability but does not trace back specific quotas applied to compositions.

[0101] In one embodiment or combination with any of the embodiments mentioned, a credit can be deposited into a recycled content inventory, and credits or allocations can be withdrawn from the inventory and applied to a composition. This would be the case where a credit is generated by preparing a first composition from pyrolysis of recycled waste, or from r-pyrolysis oil or cracking of r-pyrolysis oil, or by any other method of preparing a first composition from recycled waste, and the allocation associated with the first composition is deposited into a recycled content inventory, and the recycled content value is deducted from the recycled content inventory and applied to a second composition that is not a derivative of the first composition or was not actually prepared from the first composition as a feedstock. In this system, there is no need to trace the source of the reactants to the cracking of the pyrolysis oil or any atoms contained in the olefin-containing effluent, but rather any reactant produced by any process can be used and a recycled content credit associated with such reactant.

[0102] In one embodiment or in combination with any of the above embodiments, the composition receiving the quota is used as a feedstock to prepare a downstream derivative of the composition, and such composition is a product of cracking the cracker feedstock in a cracker furnace. In one embodiment or in combination with any of the above embodiments, a process is provided wherein:

[0103] a. Obtain r-pyrolysis oil,

[0104] b. Obtaining recovered component values (or quotas) from r-pyrolysis oil and

[0105] i. Deposit to recycled content stock, withdraw allowances (or credits) from recycled content stock

[0106] and apply it to any composition to obtain an r-composition, or

[0107] ii. Direct application to any composition without depositing into the recycling stock to obtain

[0108] r-composition; and

[0109] c. cracking at least a portion of the r-pyrolysis oil in a cracking furnace, optionally according to any of the designs or processes described herein; and

[0110] d. Optionally, at least a portion of the composition in step b is derived from a cracker feed in a cracker furnace, optionally having been obtained by any of the feedstocks comprising r-pyrolysis oil and the methods described herein.

[0111] Steps b. and c. do not have to occur simultaneously. In one embodiment or in combination with any of the embodiments mentioned, they occur within one year of each other, or within six (6) months of each other, or within three (3) months of each other, or within one (1) month of each other, or within two (2) weeks of each other, or within one (1) week of each other, or within three (3) days of each other. The process allows for the passage of time between the time an entity or person receives the r-pyrolysis oil and generates a quota (which may occur upon receipt or possession of the r-pyrolysis oil or deposit into inventory) and the actual processing of the r-pyrolysis oil in the cracking furnace.

[0112] As used herein, "recycle content inventory" and "inventory" mean a group or collection of quotas (allotments or credits) from which the deposits and deductions of quotas under any unit can be traced. The inventory can be in any form (electronic or paper), using any one or more software programs, or using various modules or applications (which together as a whole trace deposits and deductions). Desirably, the total amount of recycled content removed (or applied to the composition) does not exceed the total amount of recycled content quotas or deposits in the recycled content inventory (from any source, not just from cracking of r-pyrolysis oil). However, if a deficit in recycled content value is achieved, the recycled content inventory is rebalanced to achieve zero or positive available recycled content value. The timing of the rebalancing can be determined and managed according to the rules of the particular certification system adopted by the olefin-containing effluent manufacturer or a member of its family of entities, or alternatively, it can be rebalanced within one (1) year, or within six (6) months, or within three (3) months, or within one (1) month of achieving the deficit. The timing of depositing the credit into the recycled content inventory, applying the credit (or credit) to the composition to prepare the r-composition, and cracking the r-pyrolysis oil need not be simultaneous or in any particular order. In one embodiment or in combination with any of the aforementioned embodiments, the step of cracking a specific volume of r-pyrolysis oil occurs after depositing the recycled content value or credit from that volume of r-pyrolysis oil into the recycled content inventory. Furthermore, the credit or recycled content value removed from the recycled content inventory need not be traceable to r-pyrolysis oil or cracked r-pyrolysis oil, but rather can be obtained from any waste recovery stream and from any method of processing a recycled waste stream. Desirably, at least a portion of the recycled content value in the recycled content inventory is obtained from r-pyrolysis oil, optionally at least a portion of which is processed in one or more cracking processes as described herein, optionally within one year of each other, and optionally at least a portion of the volume of r-pyrolysis oil from which the recycled content value is deposited into the recycled content inventory is also processed by any one or more of the cracking processes described herein.

[0113] The determination of whether an r-composition is derived directly or indirectly from cracked r-pyrolysis oil is not based on the presence or absence of intermediate steps or entities in the supply chain, but rather on whether at least a portion of the r-composition fed to the reactor used to make the final product (e.g., such as ethylene oxide ("EO") or ethylene glycol ("EG")) can be traced back to an r-composition made from recycled waste.

[0114] Determining whether a PR composition is derived directly or indirectly from the pyrolysis of recycled waste (e.g., derived from cracking of r-pyrolysis oil or derived from r-pyrolysis gas) is not based on the presence or absence of intermediate steps or entities in the supply chain, but rather on whether at least a portion of the PR composition fed to the reactor used to prepare the final product (e.g., EO) can be traced back to a PR composition prepared from the pyrolysis of recycled waste.

[0115] As described above, a final product is considered to be directly derived from cracked r-pyrolysis oil or recycled waste if at least a portion of the atoms or molecules in the reactant feedstock used to prepare the product can be traced, optionally via one or more intermediate steps or entities, to constituting at least a portion of an r-composition produced from the cracking of the recycled waste or r-pyrolysis oil fed to or as an effluent from the cracking furnace.

[0116] The r-composition as an effluent may be in the form of a crude product that requires refinement to isolate a specific r-composition. The r-composition manufacturer, typically after refining and / or purifying and compressing to produce the desired grade of the specific r-composition, may sell the r-composition to an intermediate entity, which then sells the r-composition or one or more derivatives thereof to another intermediate entity for use in preparing an intermediate product, or directly to a product manufacturer. Any number of intermediates and intermediate derivatives may be prepared prior to preparing the final product.

[0117] The actual volume of r-composition, whether condensed as a liquid, supercritical, or stored as a gas, can remain in the facility where it was prepared, or can be transported to a different location, or held in an off-site storage facility before use by an intermediate or product manufacturer. For tracking purposes, once an r-composition produced by recycling waste (e.g., by cracking r-pyrolysis oil or from r-pyrolysis gas) is mixed with another volume of composition (e.g., r-ethylene mixed with non-recycled ethylene) in, for example, a storage tank, salt dome, or cavern, then the entire tank, dome, or cavern becomes the source of r-composition, and for tracking purposes, withdrawals from such storage facilities are withdrawn from the source of r-composition until the entire volume or inventory of the storage facility is turned over or withdrawn and / or replaced with non-recycled composition after the feed of r-composition to the tank is stopped. Similarly, this also applies to any downstream storage facilities used to store derivatives of the r-composition, such as r-Et and pr-Et compositions.

[0118] An R-composition is considered to be indirectly derived from recycled waste or the pyrolysis of recycled waste or the cracking of R-pyrolysis oil if the R-composition is associated with a recycled content quota and may or may not contain physical components of the R-composition that are traceable to the cracking of R-pyrolysis oil obtained from recycled waste or the pyrolysis of recycled waste. For example, (i) a product manufacturer may operate within a legal framework, or an association framework, or an industry-recognized framework to claim recycled content through a system of credits, such as credits, that are transferred to the product manufacturer regardless of where or from whom the R-composition, or its derivatives, or reactant feedstocks for making the product is purchased or transferred, or (ii) a supplier of the R-composition or its derivatives ("Supplier") operates within a quota framework that allows a recycled content value or PR value to be associated with or applied to some or all of the compounds in the olefin-containing effluent or its derivatives to prepare the R-composition and transfer that recycled content value or quota to the product manufacturer or any intermediary that receives a supply of the R-composition from the Supplier. In this system, there is no need to trace the source of the olefin volume for making r-compositions from recycled waste / pyrolyzed recycled waste, but rather any olefin (e.g., ethylene) composition produced by any process can be used and have a recycled component quota associated with such olefin composition, or the r-product manufacturer does not need to trace the source of the r-product raw material for the composition obtained by cracking r-pyrolysis oil or pyrolyzed recycled waste, but rather can use any olefin or product raw material obtained from any source as a raw material to prepare the product and have a recycled component quota associated with such product to prepare the r-product.

[0119] Examples of how recycled content can be obtained from Et compositions used to prepare EO (in the event the producer / seller desires to have recycled content EO) include:

[0120] (i) a cracker facility in which the gamma-olefins (e.g., gamma-ethylene) produced in the facility, by cracking gamma-pyrolysis oil or obtained from gamma-pyrolysis gas, can be in fluid communication, directly or indirectly, through interconnected pipelines, optionally through one or more storage vessels and valves or interlocks, with an olefin derivative petrochemical (e.g., EO) forming facility (which can be a storage vessel to the olefin derivative petrochemical facility or directly to the olefin derivative petrochemical forming reactor), and the gamma-olefin (e.g., gamma-ethylene) feedstock is fed through the interconnected pipelines:

[0121] ar-olefins (e.g., r-ethylene) are withdrawn from a cracker facility during or after the r-olefins (e.g., r-ethylene) are piped to an olefin derivative (e.g., EO) petrochemical formation facility; or

[0122] b. withdrawn from one or more storage tanks at any time, provided that at least one storage tank is fed with an r-olefin (e.g., r-ethylene), as long as the entire volume of the one or more storage tanks is replaced by a feed that does not contain an r-olefin (e.g., r-ethylene); or

[0123] (ii) transporting propylene containing or fed with an r-olefin (e.g., r-ethylene) from a storage vessel, vault, or facility, or in an isotainer, by truck or rail or ship or other means other than pipeline, until the entire volume of the vessel, vault, or facility has been replaced by an olefin (e.g., ethylene) feedstock that does not contain an r-olefin (e.g., r-ethylene); or

[0124] (iii) a manufacturer of olefin-derived (e.g., EO) petrochemical products certifies, represents, or advertises to its consumers or the public that its olefin-derived petrochemical products contain recycled content or are derived from a feedstock derived from recycled content, where such recycled content claim is based in whole or in part on the acquisition of r-olefins (e.g., ethylene feedstock associated with an allowance for ethylene produced from cracked r-pyrolysis oil or obtained from r-pyrolysis gas); or

[0125] (iv) Manufacturers of olefin-derived (e.g., EO) petrochemical products have acquired:

[0126] a. Based on the certified, represented or advertised amount of olefins (such as ethylene or propylene) produced from the r-pyrolysis oil, or

[0127] b. has transferred credits or allocations for olefin supply to manufacturers of olefin-derived (e.g., EO) petrochemical products to meet certification requirements or make representations or advertising thereof, or

[0128] c. The olefins have an associated recovery component value, wherein the recovery component value is obtained from r-pyrolysis oil or cracked r-pyrolysis oil or the olefins obtained from cracked r-pyrolysis oil or from r-pyrolysis gas through one or more intermediate independent entities.

[0129] As mentioned above, the recycled content may be a pyrolysis recycled content derived directly or indirectly from recycled waste, for example from cracked r-pyrolysis oil or from r-pyrolysis gas.

[0130] In one embodiment or in combination with any of the aforementioned embodiments, various methods are provided for allocating recovered components among various olefin-containing effluent volumes or compounds thereof produced by any one or combination of entities in a family of olefin-containing effluent entities. For example, a cracking furnace owner or operator of an olefin-containing effluent, or any one of a family of entities or sites thereof, may:

[0131] a. A symmetrical distribution of recovered content values between at least two compounds in the olefin-containing effluent or between PIAs based on the same fractional percentage of recovered content in one or more feedstocks or based on the amount of quota received. For example, if 5 wt% of the total cracker feedstock fed to the furnace is r-pyrolysis oil, then one or more compounds in the olefin-containing effluent may contain a 5 wt% recovered content value, or one or more compounds may contain a 5 wt% recovered content value minus any yield losses, or one or more PIAs may contain a 5% recovered content value. In this case, the amount of recovered content in the compound is proportional to all other products that receive a recovered content value; or

[0132] b. employing an asymmetric distribution of recovered component values among the compounds in the olefin-containing effluent or among their PIAs. In this case, the recovered component value associated with a compound or PIA may exceed the recovered component value associated with other compounds or PIAs. For example, one volume or batch of olefin-containing effluent may receive a greater amount of recovered component value than another batch or volume of olefin-containing effluent, or one or a combination of compounds in the olefin-containing effluent may receive a disproportionately higher amount of recovered component value relative to other compounds in the olefin-containing effluent or other PIAs, some of which may receive no recovered component value. One volume of the olefin-containing effluent or PIA may contain 20% by mass recycled content, and another volume or PIA may contain 0% recycled content, even though the two volumes may be identical in composition and produced continuously, provided that the value of recycled content withdrawn from the recycled content inventory and applied to the olefin-containing effluent does not exceed the value of recycled content deposited into the recycled content value inventory, or if a shortfall occurs, the overdraft is rebalanced to zero or a positive credit available as described above, or if there is no recycled content value inventory, provided that the total amount of recycled content associated with any one or more compounds in the olefin-containing effluent does not exceed the quota obtained from r-pyrolysis oil or exceeds the quota, and rebalance is performed. In an asymmetric distribution of recycled content, the manufacturer can adapt the recycled content to the volume of the olefin-containing effluent or to the compounds of interest in the olefin-containing effluent or PIA sold according to customer needs, thereby providing flexibility among customers, some of whom may require more recycled content than other customers in the r-compound or recycled PIA.

[0133] In one embodiment or in combination with any of the embodiments mentioned herein, the symmetrical and asymmetrical distribution of recovered components can be proportional on a site-wide basis or on a multi-site basis. In one embodiment or in combination with any of the embodiments mentioned, the recovered components obtained from the r-pyrolysis oil can be within a site, and the recovered component value from the r-pyrolysis oil can be applied to one or more olefin-containing effluent volumes or one or more compounds in an olefin-containing effluent volume or to one or more PIAs prepared from compounds in the olefin-containing effluent at the same site. The recovered component value can be applied symmetrically or asymmetrically to one or more different olefin-containing effluent volumes or one or more compounds in an olefin-containing effluent or PIA prepared at the site.

[0134] In one embodiment or in combination with any of the embodiments mentioned, a recovery component input or generation (recovery component feedstock or quota) can be to or at a first site, and the recovery component value from the input is transferred to a second site and applied to one or more compositions prepared at the second site. The recovery component value can be applied to the composition symmetrically or asymmetrically at the second site. The recovery component value of directly or indirectly "derived from cracked r-pyrolysis oil" or "obtained from cracked r-pyrolysis oil" or the recovery component value derived from cracked r-pyrolysis oil does not imply when the recovery component value or quota is taken, captured, deposited in the recovery component inventory or the time of transfer. The timing of depositing a quota or recovery component value in the recovery component inventory or realizing, identifying, capturing or transferring it is flexible and can be as early as receiving r-pyrolysis oil at a site within the entity family that owns it or by an entity or individual that owns or operates a cracking facility bringing r-pyrolysis oil into inventory or carrying out within the entity family. Thus, a quota or recovered content value for a volume of r-pyrolysis oil can be obtained, captured, deposited into a recovered content inventory, or transferred to a product without that volume being fed to a cracker and cracked. Such quota can also be obtained during the feeding of r-pyrolysis oil to a cracker, during cracking, or when preparing an r-composition. The quota taken when r-pyrolysis oil is owned, possessed, or received and deposited into a recovered content inventory is a quota associated with, obtained from, or derived from cracked r-pyrolysis oil, even if the r-pyrolysis oil has not yet been cracked at the time the quota is taken or deposited, provided that the r-pyrolysis oil is cracked at some point in the future.

[0135] In embodiments, the r-composition, or a downstream reaction product thereof, or a recycled PIA has associated therewith, or contains, or is labeled, advertised, or certified as containing, recycled content in an amount of at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, or at least 0.5 wt.%, or at least 0.75 wt.%, or at least 1 wt.%, or at least 1.25 wt.%, or at least 1.5 wt.%, or at least 1.75 wt.%, or at least 2 wt.%, or at least 2.25 wt.%, or at least 2.5 wt.%, or at least 2.75 wt.%, or at least 3 wt.%, or at least 3.5 wt.%, or at least 4 wt.%, or at least 4.5 wt.%, or at least 5 wt.%, or at least 6 wt.%, or at least 7 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%, %, or at least 45 wt.%, or at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.%, or at least 65 wt.% and / or the amount may be at most 100 wt.%, or at most 95 wt.%, or at most 90 wt.%, or at most 80 wt.%, or at most 70 wt.%, or at most 60 wt.%, or at most 50 wt.%, or at most 40 wt.%, or at most 30 wt.%, or at most 25 wt.%, or at most 22 wt.%, or at most 20 wt.%, or at most 18 wt.%, or at most 16 wt.%, or at most 15 wt.%, or at most 14 wt.%, or at most 13 wt.%, or at most 11 wt.%, or at most 10 wt.%, or at most 8 wt.%, or at most 6 wt.%, or at most 5 wt.%, or at most 4 wt.%, or at most 3 wt.%, or at most 2 wt.%, or at most 1 wt.%, or at most 0.9 wt.%, or at most 0.8 wt.%, or at most 0.7 wt.%. The recycled content value associated with an r-composition, r-compound, or its downstream reaction products can be associated by applying a quota (credit or allocation) to any manufactured or sold composition, compound, PIA. The quota can be included in a quota inventory created, maintained, or operated by or for the recycling of PIA or r-composition manufacturers. The quota can be obtained from any source along any manufacturing chain of the product, as long as it is derived from cracking a feedstock containing r-pyrolysis oil.

[0136] In one embodiment or in combination with any of the mentioned embodiments, a recycled PIA manufacturer can manufacture recycled PIA by processing reactants (e.g., any compound of an olefin-containing cracker effluent) obtained from any source from a supplier (e.g., a cracker manufacturer or one of its family of entities), whether or not such reactants have any recycled content, to manufacture recycled PIA, and:

[0137] i. also receive a recycling quota for that reactant from the same reactant supplier, or

[0138] ii. Receive a Recovery Content Credit from any person or entity without providing reactants from the person or entity to which the Recovery Content Credit is transferred.

[0139] The quota in (i) is obtained from the reactant supplier, and the reactant supplier is also to reclaiming the PIA manufacturer or supplying reactant in its entity family. The situation described in (i) allows the recovery PIA manufacturer to obtain the supply of non-recovery component reactant, also obtains the recovery component quota from the supplier. In one embodiment or in combination with any embodiment mentioned, reactant (for example, propylene, ethylene, butylene etc.) supplier transfers the recovery component quota to reclaim the PIA manufacturer, and the supply of reactant is transferred to reclaim the PIA manufacturer, wherein the recovery component quota is not associated with the reactant supplied, or even not associated with any reactant prepared by the reactant supplier. The recovery component quota need not be contacted with the reactant supplied or for the preparation of the amount of the recovery component in the reactant of recovery PIA. This makes the reactant supplier and the recovery PIA manufacturer flexibly distribute the recovery component between the various products of their respective preparations. Yet, in each of these situations, the recovery component quota is associated with cracking r-pyrolysis oil.

[0140] In one embodiment or in combination with any embodiment mentioned, the reactant supplier transfers the recovery component quota to reclaim the PIA manufacturer, and the supply of reactant is transferred to reclaim the PIA manufacturer, wherein the recovery component quota is associated with the reactant. The transfer of this quota can be carried out only by supplying the reactant with associated recovery components. Alternatively, the reactant supplied is the r-compound separated from the olefin-containing effluent obtained by cracking r-pyrolysis oil, and at least a portion of the recovery component quota is associated with the r-compound (or r-reactant). The recovery component quota transferred to reclaim the PIA manufacturer can be provided in advance with reactant, optionally provided in batches, or with each batch of reactants, or distributed between the parties as needed.

[0141] The quota in (ii) is obtained from any individual or entity by reclaiming PIA manufacturer (or its entity family), and the supply of reactant is not obtained from this individual or entity.This individual or entity can be the reactant manufacturer that does not provide reactant to reclaim PIA manufacturer or its entity family, or this individual or entity can be the manufacturer that does not manufacture reactant.In either case, the situation of (ii) allows reclaiming PIA manufacturer to obtain the recovery component quota, and need not buy any reactant from the entity or individual that reclaims the component quota of supply.For example, individual or entity can transfer the recovery component quota to reclaim PIA manufacturer or its entity family by buy / sell mode or contract, and does not need to buy or sell quota (for example, as the product exchange of the product that is not reactant), or individual or entity can directly sell quota to reclaim PIA manufacturer or one of its entity family.Alternatively, individual or entity can transfer the product except reactant together with its associated recovery component quota to reclaim PIA manufacturer.This is attractive for the recovery PIA manufacturer with the diversified business of preparing various PIA rather than requiring the PIA manufactured by the reactant provided.

[0142] The quota can be deposited into a recycled content inventory (e.g., a quota inventory). In one embodiment or in combination with any of the embodiments mentioned, the quota is generated by a manufacturer of an olefin-containing effluent. The manufacturer can also manufacture a PIA regardless of whether recycled content is applied to the PIA and whether the recycled content (if applied to the PIA) is taken from the recycled content inventory. For example, a manufacturer of an olefin-containing effluent can:

[0143] a. deposit the allowance into the stock and only deposit it; or

[0144] b. the olefin-containing effluent deposits the allowance into inventory and applies the allowance from the inventory to one or more compounds within the olefin-containing effluent or to any PIA produced by the manufacturer, or

[0145] c. Selling or transferring the allowances from the recycled content stock to a third party, wherein at least one allowance acquired as described above is deposited into the recycled content stock.

[0146] If desired, any recovery component quota of any amount can be deducted, and be applied to PIA to prepare recovery PIA, or be applied to containing non-recovery olefin effluent to prepare containing olefin effluent.For example, can generate the quota with the various sources for creating quota.Some recovery component quotas (credits) can be derived from the methanol decomposition of reclaimed waste, or be derived from the gasification of other types of reclaimed waste, or be derived from the mechanical recovery of waste plastics or metal recovery, or be derived from any other chemical or mechanical recovery technology.Recovery component inventory can be tracked or not tracked the source or basis of obtaining recovery component value, or this inventory can not allow the source or basis of quota to be associated with the quota being applied to r-composition. It is sufficient that the allowance is deducted from the recovered content inventory and applied to the PIA or non-recovered olefin-containing effluent, regardless of the source of the allowance, so long as the recovered content allowance obtained from the r-pyrolysis oil is present in the recovered content inventory at the time of withdrawal, or the recovered content allowance is obtained from the recycled PIA manufacturer as specified in step (i) or step (ii), regardless of whether the recovered content allowance is actually deposited in the recovered content inventory.

[0147] In one embodiment or in combination with any of the aforementioned embodiments, the recovered component credit obtained in step (i) or (ii) is deposited into a credit inventory. In one embodiment or in combination with any of the aforementioned embodiments, the recovered component credit deducted from the recovered component inventory and applied to the PIA or non-recovered olefin-containing effluent (or any compound therein) is derived from r-pyrolysis oil.

[0148] As used throughout, the recovery component inventory can be owned or owned by the owner of the cracking furnace of processing r-pyrolysis oil or one of its entity family, containing olefin effluent, or by recovery PIA manufacturer, or operated by any of them, or owned or operated by any of them but at least partially benefited by any of them, or licensed by any of them or licensed to any of them.Equally, cracker containing olefin effluent manufacturer or recovery PIA manufacturer can also include any of their entity family.For example, although any of them may not own or operate inventory, one of its entity family can own such platform, or license it from an independent supplier, or operate it for any of them.Alternatively, an independent entity can own and / or operate inventory, and operates and / or manages at least a portion of the inventory for any of them for a service fee.

[0149] In one embodiment or in combination with any of the aforementioned 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 aforementioned embodiments, at least a portion of the quota obtained by the recycled PIA manufacturer is:

[0150] a. Applied to PIA prepared by supplying reactants;

[0151] b. Applied to PIAs made from the same type of reactants, but not from the volume of reactants supplied, such as PIAs made from the same type of reactants already made and stored in inventory or to PIAs manufactured in the future; or

[0152] c. credited to inventory, deducted from inventory the allowance applicable to PIA made from a different reactant type than that supplied, or

[0153] d. Deposit into inventory and store.

[0154] It is not necessary in all embodiments to use r-reactants to prepare recovery PIA, or to obtain recovery PIA from recovery component quotas associated with reactants. In addition, it is not necessary to apply quotas to feedstocks to prepare recovery PIA to which recovery components are applied. On the contrary, as described above, even if associated with reactants when they are obtained, the quota can be deposited into an electronic inventory. However, in one embodiment or in combination with any of the embodiments mentioned, the reactants associated with the quota are used to prepare recovery PIA. In one embodiment or in combination with any of the embodiments mentioned, recovery PIA is obtained from recovery component quotas associated with r-reactants or r-pyrolysis oil or with cracked r-pyrolysis oil.

[0155] In one embodiment or in combination with any of the mentioned embodiments, the olefin-containing effluent manufacturer generates an allowance from r-pyrolysis oil, and:

[0156] a. applying the quota to any PIA made directly or indirectly (e.g. via a reaction scheme with several intermediates) from cracked r-pyrolysis oil; or

[0157] b. applying the quota to any PIA not produced directly or indirectly from cracked r-pyrolysis oil, such as where PIA has already been produced and stored in a stockpile or is produced in the future; or

[0158] c. is credited to the stock, deducting from the stock any allowances applicable to the PIA; and the allowances credited may or may not be associated with a specific allowance applicable to the PIA; or

[0159] d. is deposited into inventory and stored for later use.

[0160] There is also now provided a package or combination of a recycled PIA and a recycled content identifier associated with the recycled PIA, wherein the identifier is or includes an indication that the recycled PIA includes, is derived from, or is associated with recycled content. The package may be any suitable package for containing polymers and / or articles, such as a plastic or metal drum, railroad car, isotainer, tote, polytote, bale, IBC tote, bottle, compressed bale, jerry can, plastic bag, spool, roving, twine, or cardboard packaging. The identifier can be a certification document, a product insert stating recycled content, a label, a logo or certification mark from a certification body that indicates that the article or packaging contains the content or that the recycled PIA contains the content, or is made from a source or is associated with recycled content, or it can be an electronic statement from the recycled PIA manufacturer accompanying a purchase order or product, or posted on a website as a statement, display, or mark indicating that the recycled PIA contains or is associated with recycled content or is made from a source that contains recycled content, or it can be an advertisement transmitted electronically, by or in a website, by email, or by television, or through a trade show, in each case associated with the recycled PIA. The identifier need not state or indicate that the recycled content is derived from r-pyrolysis oil. Instead, the identifier can simply convey or communicate that the recycled PIA has or is derived from recycled content, regardless of the source. However, the recycled PIA has a recycled content quota that is at least partially associated with r-pyrolysis oil.

[0161] In one embodiment or in combination with any of the embodiments mentioned, information about the recycled content of the recycled PIA can be communicated to a third party, wherein such recycled content information is based on or derived from at least a portion of an allocated amount or credit. The third party can be a customer of an olefin-containing effluent manufacturer or a recycled PIA manufacturer, or can be any other individual or entity or government organization other than the entity that owns any of them. The transmission can be electronic, by document, by advertisement, or by any other means of communication.

[0162] In one embodiment or in combination with any of the mentioned embodiments, there is provided a system or package comprising:

[0163] a. Recycling PIA, and

[0164] b. An identifier, such as a credit, label, or certificate associated with the PIA, wherein the identifier is an indication that the PIA has or is derived from recycled content (which does not necessarily identify the source of the recycled content or credit), provided that the recycled PIA prepared therefrom has a credit, or is prepared from reactants, at least in part associated with r-pyrolysis oil.

[0165] The system can be a physical assembly, such as a package having at least some recycled PIA as its contents, and the package having a label, such as a logo, that identifies the component having or derived from recycled content. Alternatively, the label or certificate can be issued to a third party or customer as part of the entity's standard operating procedure whenever it transfers or sells recycled PIA having or derived from recycled content. The identifier does not have to be physically on the recycled PIA or on the packaging, and does not have to be on any physical document accompanying the recycled PIA or associated with the recycled PIA or packaging. For example, the identifier can be an electronic document, certificate, or identification mark associated with the sale of the recycled PIA to a customer. The identifier itself only needs to convey or communicate that the recycled PIA has or is derived from recycled content, regardless of the source. In one embodiment or in combination with any of the mentioned embodiments, the article manufactured from the recycled PIA can have an identifier, such as a stamp or logo embedded in or adhered to the article or packaging. In one embodiment or in combination with any of the mentioned embodiments, the identifier is an electronic recycled content credit from any source. In one embodiment or in combination with any of the mentioned embodiments, the identifier is an electronic recycled content credit sourced from r-pyrolysis oil.

[0166] Recycled PIA can be made from reactants, whether or not the reactants are recycled content reactants. Once a PIA is prepared, it can be designated as having recycled content based on and derived from at least a portion of a quota. The quota can be taken from or deducted from the recycled content inventory. The amount deducted and / or applied to the PIA can correspond to any method, such as a mass balance method.

[0167] In one embodiment, recycled PIA can be prepared by having a stock of recycled components, reacting reactants in a synthesis process to prepare PIA, extracting a quota from the stock of recycled components having a recycled component value, and applying the recycled component value to PIA to obtain recycled PIA. The amount of quota deducted from the stock is flexible and will depend on the amount of recycled components applied to PIA. If it is not a complete amount, it is sufficient to correspond to at least a portion of the recycled components applied to PIA. The recycled component quota applied to PIA does not necessarily have to be derived from r-pyrolysis oil, but can be derived from any other method of generating a quota from recycled waste, such as by methanolysis or gasification of recycled waste, as long as the recycled component stock also contains a quota or has a quota deposit, which is derived from r-pyrolysis oil. However, in one embodiment or in combination with any of the mentioned embodiments, the recycled component quota applied to PIA is a quota obtained from r-pyrolysis oil.

[0168] The following are examples of applications of recycled content to PIA or to effluents or compounds containing non-recycled olefins:

[0169] 1. The PIA manufacturer applies at least a portion of the quota to the PIA to obtain recycled PIA, wherein the quota is associated with r-pyrolysis oil and the reactants used to prepare the PIA do not contain any recycled content; or

[0170] 2. The PIA manufacturer applies at least a portion of the quota to PIA to obtain recycled PIA, where the quota is obtained from recycled component reactant, regardless of whether the reactant volume is used to prepare the recycled PIA; or

[0171] 3. The PIA manufacturer applies at least a portion of the quota to the PIA to produce recycled PIA, wherein the quota is obtained from the r-pyrolysis oil, and:

[0172] a. Apply all recovered components in the r-pyrolysis oil to determine the amount of recovered components in the recovered PIA, or

[0173] b. applying only a portion of the recycled content in the r-pyrolysis oil feedstock to determine the amount of recycled content in the recycled PIA, with the remainder stored in a recycled content inventory for future use or for application to other PIAs, or for increasing the recycled content on an existing recycled PIA, or a combination thereof, or

[0174] The recovered content in the cr-pyrolysis oil feedstock is not applied to the PIA but is instead stored in an inventory, and the recovered content from any source is deducted from the inventory and applied to the PIA to prepare the recovered PIA; or

[0175] 4. A recycled PIA manufacturer applies at least a portion of a quota to reactants used to make the recycled PIA, thereby obtaining the PIA, wherein the quota was obtained by transferring or purchasing the same reactants used to make the PIA and the quota is associated with the recycled content in the reactants; or

[0176] 5. A recycled PIA manufacturer applies at least a portion of a quota to reactants used to make the recycled PIA, thereby obtaining the PIA, wherein the quota is obtained by transferring or purchasing the same reactants used to make the PIA and the quota is not associated with the recycled content of the reactants but is associated with the recycled content of the monomers used to make the reactants; or

[0177] 6. A recycled PIA manufacturer applies at least a portion of a quota to reactants used to make the recycled PIA, thereby obtaining the PIA, wherein the quota is not obtained through the transfer or purchase of the reactants and the quota is associated with the recycled content in the reactants; or

[0178] 7. A recycled PIA manufacturer applies at least a portion of an allocation to reactants used to make the PIA, thereby obtaining recycled PIA, wherein the allocation is not obtained through the transfer or purchase of reactants and the allocation is not associated with the recycled content of the reactants but rather with the recycled content of any monomer used to make the reactants; or

[0179] 8. Recycling PIA manufacturers are given quotas derived from r-pyrolysis oil, and:

[0180] a. not applying a portion of the quota to the reactants to prepare PIA, but applying at least a portion of the quota to PIA to prepare recovered PIA; or

[0181] b. Less than all of the portion is applied to the reactants used to prepare the recovered PIA, while the remainder is stored in inventory or applied to future prepared PIA or to existing recovered PIA in inventory to increase its recovered component value.

[0182] In one embodiment or in combination with any of the aforementioned embodiments, recycled PIA or articles made therefrom can be offered for sale or sold as recycled PIA containing recycled content or obtained with recycled content. The sale or offer for sale can be accompanied by a certification or representation of a recycled content claim associated with the recycled PIA.

[0183] Designation of at least a portion of the recycled PIA or olefin-containing effluent as corresponding to at least a portion of the quota (e.g., an allotment or credit) can be performed in a variety of ways and according to the system employed by the recycled PIA manufacturer or olefin-containing effluent manufacturer, which can vary from manufacturer to manufacturer. For example, the designation can occur solely internally, through a log entry in the books or files of the manufacturer or other inventory software program, or through instructions, packaging, advertising or statements on the product, through labeling associated with the product, through a certification declaration associated with the product as sold, or through a formula that calculates the amount to be deducted from the inventory relative to the amount of recycled content applied to the product.

[0184] Alternatively, the recycled PIA may be sold. In one embodiment or in combination with any of the aforementioned embodiments, there is provided a method of offering for sale or selling a polymer and / or article by:

[0185] a. A recycled PIA manufacturer or an olefin-containing effluent manufacturer or any of their family of entities (collectively, the "Manufacturers") obtains or generates a recycled content allowance, which may be obtained by any of the methods described herein and deposited into the recycled content inventory, wherein the source of the recycled content allowance is r-pyrolysis oil,

[0186] b. converting a reactant in a synthetic process to prepare PIA, and the reactant may be any reactant or r-reactant,

[0187] c. designating (e.g., assigning or associating) recycled content to at least a portion of a PIA from a stock of recycled content to prepare the recycled PIA, wherein the stock contains at least one entry as a quota associated with r-pyrolysis oil. The designation can be an amount of the quota deducted from the stock, or an amount of recycled content declared or determined by the recycled PIA manufacturer in its accounts. Thus, the amount of recycled content does not necessarily have to be physically applied to the recycled PIA product. The designation can be an internal designation made to or by the manufacturer, or a service provider having a contractual relationship with the manufacturer, and

[0188] d. Offering or selling recycled PIA containing or obtained with the following recycled content, where the recycled content at least partially corresponds to the designation. The amount of recycled content expressed as contained in the recycled PIA offered or sold has a relationship or association with the designation. The amount of recycled content may be a 1:1 relationship between the amount of recycled content declared on the recycled PIA offered or sold and the amount of recycled content allocated or designated to the recycled PIA by the recycled PIA manufacturer.

[0189] The steps do not have to be sequential and can be independent of each other. For example, step a) of obtaining a quota and the step of preparing recycled PIA can be performed simultaneously.

[0190] As used throughout, the step of deducting the quota from the recycling component inventory does not need to be applied to the recycling PIA product. Deduction does not mean that the quantity disappears or is removed from the inventory log. Deduction can be an adjustment entry, a withdrawal, an addition as a debit entry, or any other algorithm that adjusts input and output based on the amount of the recycling component associated with the product and one or the accumulated deposited quota amount in the inventory. For example, deduction can be a simple step of deducting / debiting entries from one column and adding / crediting to another column within the same program or book, or an algorithm that automates deductions and entries / additions and / or applies or is assigned to the product information board. The step of applying the quota to PIA (wherein such a quota is deducted from the inventory) does not need to physically apply the quota to the recycling PIA product or to any document issued in association with the recycling PIA product sold. For example, a recycling PIA manufacturer can ship the recycling PIA product to a customer and satisfy the "application" of the quota to the recycling PIA product by electronically transmitting the recycling component credit to the customer.

[0191] Also provided is a use of r-pyrolysis oil, comprising converting the r-pyrolysis oil in a gas cracking furnace to produce an olefin-containing effluent. Also provided is a use of r-pyrolysis oil, comprising converting reactants in a synthesis process to produce PIA, and applying at least a portion of a quota to the PIA, wherein the quota is associated with the r-pyrolysis oil or is derived from a quota stock, wherein at least one of the deposits into the stock is associated with the r-pyrolysis oil.

[0192] In one embodiment or in combination with any of the mentioned embodiments, there is provided recovered PIA obtained by any of the methods described above.

[0193] The reactants can be stored in storage containers and transported by truck, pipeline, or ship to a PIA production facility for recycling, or, as further described below, an olefin-containing effluent production facility can be integrated with a PIA facility. The reactants can be transported or transferred to an operator or facility for producing polymers and / or articles.

[0194] In one embodiment, the method for preparing the recovered PIA can be an integrated method. One such example is a method for preparing the recovered PIA by the following steps:

[0195] a. cracking r- pyrolysis oil to prepare an olefin-containing effluent containing olefins; and

[0196] b. separating the compounds in the olefin-containing effluent to obtain separated compounds; and

[0197] c. reacting any reactants during the synthesis to prepare PIA;

[0198] d. depositing the allowance into the allowance stock, the allowance being derived from r-pyrolysis oil; and

[0199] e. Apply any allowance from the stock to the PIA, thereby obtaining recycled PIA.

[0200] In one embodiment or in combination with any of the above embodiments, two or more facilities can be integrated to produce and recover PIA. The facilities for producing and recovering PIA or olefin-containing effluents can be independent facilities or integrated facilities. For example, a system for producing and consuming reactants can be established as follows:

[0201] a. Providing an olefin-containing effluent manufacturing facility configured to produce a reactant;

[0202] b. providing a PIA manufacturing facility having a reactor configured to receive reactants from the olefin-containing effluent manufacturing facility; and

[0203] c. a supply system providing fluid communication between the two facilities and capable of supplying reactants from the olefin-containing effluent production facility to the PIA production facility, wherein the olefin-containing effluent production facility generates or participates in a process for generating quota and cracked r-pyrolysis oil, and:

[0204] (i) applying the quota to the reactants or to the PIA, or

[0205] (ii) depositing the quota into a quota stock and optionally withdrawing a share from the stock and applying it to the reactants or to the PIA.

[0206] A recovered PIA manufacturing facility may prepare recovered PIA by accepting any reactants from an olefin-containing effluent manufacturing facility and applying the recovered components to the recovered PIA made with the reactants by deducting allowances from their inventory and applying them to the PIA.

[0207] In one embodiment or in combination with any of the mentioned embodiments, there is also provided a system for producing recycled PIA as follows:

[0208] a. providing an olefin-containing effluent production facility configured to produce an output composition comprising an olefin-containing effluent;

[0209] b. providing a reactant manufacturing facility configured to receive the compound separated from the olefin-containing effluent and to produce one or more downstream products of the compound through a reaction scheme to produce an output composition comprising the reactant;

[0210] c. Providing a PIA manufacturing facility having a reactor configured to receive reactants and produce an output composition comprising PIA;

[0211] d. A supply system providing fluid communication between at least two of these facilities and capable of supplying the output composition of one manufacturing facility to one or more of the other manufacturing facilities.

[0212] PIA production equipment can produce recycled PIA. In this system, the olefin-containing effluent manufacturing facility can have its output connected to the reactant composition manufacturing facility fluid, and conversely, the reactant compound or composition manufacturing facility can have its output connected to the PIA manufacturing facility fluid. Alternatively, the manufacturing facilities of a) and b) can be connected to the fluid separately, or only b) and c) can be connected to the fluid. In the latter case, the PIA manufacturing facility can produce recycled PIA by deducting quotas from the recovered component inventory and applying them to the PIA. The quotas obtained and stored in the inventory can be obtained by any of the above methods.

[0213] Fluid communication can be gaseous or liquid or both. Fluid communication does not need to be continuous and can be interrupted by storage tanks, valves or other purification or treatment facilities, as long as the fluid can be transported from the manufacturing facility to subsequent facilities through an interconnected pipeline network and without the use of trucks, trains, ships or aircraft. In addition, facilities can share the same site, or in other words, a site can contain two or more facilities. In addition, facilities can also share storage tank sites or storage tanks for auxiliary chemicals, or can also share utilities, steam or other heat sources, etc., but because their unit operations are separated, they are also considered to be discrete facilities. Facilities are usually defined by device boundaries.

[0214] In one embodiment or combination with any of the recited embodiments, the integrated process comprises at least two facilities co-located within 5 miles, or within 3 miles, or within 2 miles, or within 1 mile of each other (as measured in a straight line). In one embodiment or combination with any of the recited embodiments, at least two facilities are owned by the same family of entities.

[0215] In one embodiment, an integrated recycled PIA production and consumption system is also provided. The system includes:

[0216] a. providing an olefin-containing effluent production facility configured to produce an output composition comprising an olefin-containing effluent;

[0217] b. providing a reactant manufacturing facility configured to receive the compound separated from the olefin-containing effluent and to produce one or more downstream products of the compound through a reaction scheme to produce an output composition comprising the reactant;

[0218] c. Providing a PIA manufacturing facility having a reactor configured to receive reactants and produce an output composition comprising PIA;

[0219] d. A piping system interconnecting at least two of the facilities, optionally with intermediate processing equipment or storage facilities, the piping system being capable of withdrawing an output composition from one facility and receiving the output at any one or more of the other facilities.

[0220] The system does not necessarily need the fluid communication between the two facilities, although fluid communication is desirable.For example, from containing the compound separated from the olefin effluent, can be transported to the reactant facility by the interconnected pipeline network, described interconnected pipeline network can be interrupted by other processing equipment, described other processing equipment such as processing, purifying, pump, compression or be suitable for merging the equipment or storage facilities of stream, and all these facilities comprise optional metering, valve or interlocking device.This equipment can be fixed to the ground or be fixed to the structure that is fixed on the ground.The interconnected pipeline does not need to be connected to reactant reactor or cracker, but is connected to the transportation and receiving point at the facility place respectively.The interconnected pipeline system does not need all three facilities to be connected to each other, but the interconnected pipeline system can be at the facility a)-b) between, or b)-c) between, or a)-b)-c) between.

[0221] A ring manufacturing method is also provided, the method comprising:

[0222] a. Provide r-pyrolysis oil, and

[0223] b. cracking the r-pyrolysis oil to produce an olefin-containing effluent, and

[0224] (i) reacting compounds separated from said olefin-containing effluent to produce recovered PIA, or

[0225] (ii) combining a recovery component quota obtained from the r-pyrolysis oil with PIA prepared from compounds separated from a non-recovered olefin-containing effluent to produce recovered PIA; and

[0226] c. Removing at least a portion of any of the recovered PIA or any other product, compound, or polymer produced from the recovered PIA as a feedstock to produce the r-pyrolysis oil.

[0227] In the above process, a fully circular or closed loop process is provided, wherein the recovered PIA can be recycled multiple times.

[0228] Examples of articles included in the PIA are fibers, yarns, tows, continuous filaments, staple fibers, rovings, fabrics, textiles, foils, films (eg, polyolefin films), sheets, composite sheets, plastic containers, and consumer articles.

[0229] In one embodiment or in combination with any of the mentioned embodiments, the recovered PIA is of the same family or class of polymers or articles as the polymers or articles used to prepare the r-pyrolysis oil.

[0230] 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).

[0231] The waste stream of recovery is the flow or accumulation of recovered waste from industrial and consumer sources, which is at least partially recovered. The waste stream of recovery includes materials, products and articles (collectively referred to as "materials" when used alone). The recovered waste can be solid or liquid. Examples of solid recovered waste streams include plastics, rubber (including tires), textiles, wood, biowaste, modified cellulose, wet laid (wetlaid) products and any other materials capable of pyrolysis. Examples of liquid waste streams include industrial sludge, oil (including those derived from plants and petroleum), recovered lubricating oils, or vegetable or animal oils and any other chemical streams from industrial plants.

[0232] In one embodiment or in combination with any of the aforementioned embodiments, the recycled waste stream that is pyrolyzed comprises a stream that contains at least in part post-industrial material, or post-consumer material, or both. In one embodiment or in combination with any of the aforementioned embodiments, post-consumer material is material that has been used for its intended application at least once for any duration, regardless of wear and tear, or material that has been sold to an end-use consumer, or material that has been discarded into a recycling bin by any person or entity other than the manufacturer or business that manufactured or sold the material.

[0233] In one embodiment or in combination with any of the aforementioned embodiments, post-industrial materials are materials that have been manufactured and not used for their intended application, or not sold to an end-use customer, or are discarded by the manufacturer or any other entity involved in the sale of the materials. Examples of post-industrial materials include reprocessed, regrind, scrap, off-cuts, off-specification materials, and finished materials that have been transferred from the manufacturer to any downstream customer (e.g., manufacturer to wholesaler to distributor) but have not yet been used or sold to an end-use customer.

[0234] The form of the recycled waste stream that can be fed to the pyrolysis unit is not limited and can include any form of article, product, material, or portion thereof. The portion of the article can take the form of a sheet, extruded profile, molded article, film, laminate, foam piece, chips, flakes, particles, fibers, agglomerates, briquettes, powder, chips, strips, or pieces of any shape having various shapes, or any other form other than the original form of the article, and suitable for feeding to the pyrolysis unit.

[0235] In one embodiment or in combination with any of the above embodiments, the recycled waste is reduced in size. Reduction can be performed by any means including shredding, shredding, harrowing, grinding, pulverizing, cutting the material, molding, compressing, or dissolving in a solvent.

[0236] The recycled waste plastics can be separated as a single type of polymer stream, or can be a stream of mixed recycled waste plastics. Plastics can be any organic synthetic polymer that is solid at 25°C and 1 atm. Plastics can be thermosetting, thermoplastic, or elastomeric plastics. Examples of plastics include high-density polyethylene and its copolymers, low-density polyethylene and its copolymers, polypropylene and its copolymers, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyesters (including polyethylene terephthalate), copolyesters and terephthalate copolyesters (e.g., containing residues of TMCD, CHDM, propylene glycol or NPG monomers), polyethylene terephthalate, polyamides, poly(methyl methacrylate), polytetrafluoroethylene, acrylonitrile-butadiene-styrene (ABS), polyurethanes, cellulose and its derivatives, such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate; regenerated cellulose products such as viscose and rayon, epoxy resins, polyamides, phenolic resins, polyacetals, polycarbonates, polyphenyl alloys, polypropylene and its copolymers, polystyrene, styrene compounds, vinyl compounds, styrene-acrylonitrile, thermoplastic elastomers, urea-based polymers, and melamine-containing polymers.

[0237] Suitable recycled waste plastics also include any of those having resin ID codes 1-7 within the chasing arrow triangle established by SPI. In one embodiment or in combination with any of the mentioned embodiments, r-pyrolysis oil is made from a recycled waste stream, at least a portion of which contains plastics that are not typically recycled. These include plastics with the numbers 3 (polyvinyl chloride), 5 (polypropylene), 6 (polystyrene), and 7 (other). In one embodiment or in combination with any of the mentioned embodiments, the recycled waste stream that is pyrolyzed contains less than 10 weight percent, or no more than 5 weight percent, or no more than 3 weight percent, or no more than 2 weight percent, or no more than 1 weight percent, or no more than 0.5 weight percent, or no more than 0.2 weight percent, or no more than 0.1 weight percent, or no more than 0.05 weight percent of No. 3 plastic (polyvinyl chloride), or alternatively No. 3 and No. 6 plastics, or alternatively No. 3, 6, and No. 7 plastics.

[0238] Examples of recycled rubber include natural and synthetic rubber. The form of the rubber is not limited and includes tires.

[0239] Examples of recycled waste wood include softwood and hardwood, chipped wood, pulp or finished products. A large amount of recycled waste wood comes from industry, construction or demolition.

[0240] Examples of recycled biorecycled waste include household biorecycled waste (eg, food), green or garden biorecycled waste, and biorecycled waste from the industrial food processing industry.

[0241] The example of the textiles of recovery comprises natural and / or synthetic fiber, roving, yarn, nonwoven web, cloth, fabric and the product made or comprising any of the above-mentioned articles by any of the above-mentioned articles.Textiles can be woven, knitted, knotted, sewed, tufted, fiber pressed together, for example, carried out in a felting operation, embroidered, lace, crocheted, braided or nonwoven web and material.Textiles comprise fabric and fiber, waste material or off-spec fiber or yarn or textiles separated from textiles or other products comprising fiber, or any other loose fiber and yarn source.Textiles also comprise staple fiber, continuous fiber, line, tow band, twisting and / or spun yarn, the greige cloth made by yarn, the finished product textiles made by wet processing greige cloth and the clothing made by finished product textiles or any other textiles.Textiles comprise clothing, interior furnishings and industrial type textiles.

[0242] Examples of recycled textiles in the apparel category (things worn by humans or made for the body) include sport coats, suits, pants and casual or work pants, shirts, socks, sportswear, dresses, intimate apparel, outerwear such as raincoats, cold-weather jackets and coats, sweaters, protective clothing, uniforms, and accessories such as scarves, hats, and gloves. Examples of textiles in the furnishings category include furniture upholstery and furniture coverings, carpets and rugs, curtains, bedding such as sheets, pillowcases, duvets, comforters, mattress covers; linens, tablecloths, towels, and blankets. Examples of industrial textiles include transportation (car, plane, train, bus) seats, floor mats, trunk liners, and headliners; outdoor furniture and mats, tents, backpacks, luggage, ropes, conveyor belts, calendar roller felt, polishing cloths, rags, soil erosion textiles and geotextiles, agricultural mats and screens, personal protective equipment, bulletproof vests, medical bandages, sutures, tapes, etc.

[0243] The nonwoven web of recovery can also be a dry-laid nonwoven web.The example of the suitable goods that can be formed by the dry-laid nonwoven web as described herein can include those for the end-use of individual, consumer, industry, food service, medical treatment and other types.Specific example can include but not limited to baby wipes, flushable wipes, disposable diapers, training pants, feminine hygiene products such as sanitary towel and tampon, adult incontinence pad, underwear or underpants and pet training pad.Other examples include multiple different dry or wet wipes, including those wipes used for consumer (such as personal care or family) and industry (such as food service, health care or professional).Nonwoven web also can be used as pillow, mattress and furniture decoration, for the cotton batting of quilt and quilt cover.In medical treatment and industrial field, nonwoven web of the present invention can be used for medical treatment and industrial face mask, protective clothing, hat and shoe cover, disposable bed sheet, surgical gown, curtain, bandage and medical dressing. In addition, nonwoven webs can be used for environmental textiles, such as geotextiles and tarpaulins, oil pads and chemical absorbent pads, and building materials, such as sound insulation or heat insulation, tents, timber and soil coverings and sheets. Nonwoven webs can also be used for other consumer end uses, such as packaging, heat insulation or sound insulation and various types of clothing for carpet backing, consumer goods, industrial products and agricultural products. Dry-laid nonwoven webs can also be used for multiple filtering applications, including transportation (such as, automobile or aviation), business, residential, industrial or other professional applications. Example can include filter elements for consumer or industrial air or liquid filters (such as, gasoline, oil, water), including nanofiber webs for microfiltration and end uses such as tea bags, coffee filters and dryer sheets. In addition, nonwoven webs can be used for forming the various components for automobiles, including but not limited to brake pads, trunk linings, carpet tufting and bottom filling.

[0244] Recycled textiles can include a single type or multiple types of natural fibers and / or a single type or multiple types of synthetic fibers. Examples of textile fiber combinations include all natural, all synthetic, two or more types of natural fibers, two or more types of synthetic fibers, one type of natural 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.

[0245] Examples of recycled wet-laid products include paperboard, office paper, newsprint and magazines, printing and writing paper, toilet paper, tissue / paper toweling, packaging / containerboard, specialty papers, apparel, bleached paperboard, corrugated medium, wet-laid molded products, unbleached kraft paper, decorative laminates, bond paper and currency, oversized graphics, specialty products, and food and beverage products.

[0246] Examples of modified cellulose include cellulose acetate, cellulose diacetate, cellulose triacetate, regenerated cellulose such as viscose, rayon and Lyocel TM Products in any form, such as tow ribbons, staple fibers, continuous fibers, films, sheets, molded or stamped products, and contained in or on any articles such as cigarette filter rods, ophthalmic products, screwdriver handles, optical films and coatings.

[0247] Examples of recycled vegetable or animal oils include oils recovered from animal processing facilities and recycled waste from restaurants.

[0248] The sources of post-consumer or post-industrial recycled waste from which recycling is obtained are not limited and may include recycled waste present in and / or separated from the municipal solid recycled waste stream ("MSW"). For example, the MSW stream may be processed and sorted into a number of discrete components, including textiles, fibers, paper, wood, glass, metals, etc. Other sources of textiles include those obtained by collection agencies, or those obtained by or for or on behalf of textile brand owners or alliances or organizations, or those obtained by brokers, or those obtained from post-industrial sources, such as scrap from mills or commercial production facilities, unsold textiles from wholesalers or distributors, from mechanical and / or chemical sorting or separation facilities, from landfills, or stranded at docks or on ships.

[0249] In one embodiment or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit can contain at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99 weight percent of at least one, or at least two, or at least three, or at least four, or at least five, or at least six different types of recycled waste. Reference to "type" is identified by resin ID codes 1-7. In one embodiment or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit contains less than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 1 weight percent of polyvinyl chloride and / or polyethylene terephthalate in each case. In one embodiment or in combination with any of the embodiments mentioned, the recycled waste stream contains at least one, two, or three plasticized plastics.

[0250] Figure 2 An exemplary pyrolysis system 110 is described that can be used to at least partially convert one or more recycled wastes, particularly recycled plastic wastes, into various useful pyrolysis-derived products. Figure 2The pyrolysis system shown in is merely one example of a system in which the present disclosure may be implemented. The present invention may be applied to various other systems in which it is desired to effectively and efficiently pyrolyze recycled waste, particularly recycled plastic waste, into various desired end products. Figure 2 An exemplary pyrolysis system is shown in FIG.

[0251] like Figure 2 As shown, the pyrolysis system 110 may include a waste plastic source 112 for supplying one or more waste plastics to the system 110. The plastic feedstock 112 may be, for example, a hopper, a storage bin, a rail car, a long-haul trailer, or any other device that can hold or store waste plastics. In one embodiment or in combination with any of the embodiments described herein, the waste plastics supplied by the plastic source 112 may be in the form of solid particles, such as chips, flakes, or powder. Although in Figure 2 Not depicted in FIG, pyrolysis system 110 may also include additional sources of other types of recycled waste, which may be used to provide other feed types to system 110.

[0252] In one embodiment or in combination with any of the embodiments mentioned herein, the waste plastic can include one or more post-consumer waste plastics, such as high-density polyethylene, low-density polyethylene, polypropylene, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyethylene terephthalate, polyamide, poly(methyl methacrylate), polytetrafluoroethylene, or a combination thereof. In one embodiment or in combination with any of the embodiments mentioned herein, the waste plastic can include high-density polyethylene, low-density polyethylene, polypropylene, or a combination thereof. As used herein, "post-consumer" refers to non-virgin plastics that have been previously introduced into the consumer market.

[0253] In one embodiment or in combination with any of the embodiments mentioned herein, a feed comprising waste plastic can be supplied from a plastic source 112. In one embodiment or in combination with any of the embodiments mentioned herein, the feed comprising waste plastic can comprise, consist essentially of, or consist of high-density polyethylene, low-density polyethylene, polypropylene, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyethylene terephthalate, polyamide, poly(methyl methacrylate), polytetrafluoroethylene, or combinations thereof.

[0254] 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 weight percent of at least one, two, three, or four different types 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 weight percent of polyvinyl chloride and / or polyethylene terephthalate in each case. In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastics may contain at least one, two, or three plasticized plastics. Reference to "type" is determined by resin ID codes 1-7.

[0255] like Figure 2 As shown, a solid waste plastic feed from a plastic source 112 can be supplied to a feedstock pretreatment unit 114. In the feedstock pretreatment unit 114, the introduced waste plastic can undergo a number of pretreatments to promote the subsequent pyrolysis reaction. Such pretreatments can include, for example, washing, mechanical agitation, flotation, size reduction, or any combination thereof. In one embodiment or in combination with any embodiment mentioned herein, the introduced plastic waste can be subjected to mechanical agitation or to a size reduction operation to reduce the particle size of the plastic waste. Such mechanical agitation can be provided by any mixing, shearing, or grinding device known in the art, which can reduce the average particle size of the introduced plastic by at least 10%, or at least 25%, or at least 50%, or at least 75%.

[0256] Next, the pre-treated plastic feedstock can be introduced into a plastic feed system 116. The plastic feed system 116 can be configured to introduce the plastic feed into the pyrolysis reactor 118. The plastic feed system 116 can include any system known in the art capable of feeding solid plastic into the pyrolysis reactor 118. In one embodiment or in combination with any of the embodiments mentioned herein, the plastic feed system 116 can include an auger, a hopper, a pneumatic conveying system, a mechanical metal bar or chain, or a combination thereof.

[0257] While in the pyrolysis reactor 118, at least a portion of the plastic feed can undergo a pyrolysis reaction that produces a pyrolysis effluent comprising pyrolysis oil (e.g., r-pyrolysis oil) and pyrolysis gas (e.g., r-pyrolysis gas). The pyrolysis reactor 118 can be, for example, an extruder, a tubular reactor, a tank, a stirred tank reactor, a riser reactor, a fixed bed reactor, a fluidized bed reactor, a rotary kiln, a vacuum reactor, a microwave reactor, an ultrasonic or supersonic reactor, or an autoclave, a membrane reactor, or a combination of these reactors.

[0258] Generally, pyrolysis is a process involving the chemical and thermal decomposition of an introduced feed. Although all pyrolysis processes can generally be characterized by a reaction environment that is substantially free of oxygen, pyrolysis processes can be further defined by, for example, the pyrolysis reaction temperature within the reactor, the residence time in the pyrolysis reactor, the reactor type, the pressure within the pyrolysis reactor, and the presence or absence of a pyrolysis catalyst.

[0259] In one embodiment or in combination with any of the embodiments described herein, the pyrolysis reaction can include heating and converting the plastic feedstock in an atmosphere that is substantially free of oxygen or that contains less oxygen than ambient air. In one embodiment or in combination with any of the embodiments described herein, the atmosphere within the pyrolysis reactor 118 can contain oxygen in an amount of 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%, in each case.

[0260] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis process can be carried out in the presence of an inert gas such as nitrogen, carbon dioxide, and / or steam. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis process can be carried out in the presence of a reducing gas such as hydrogen and / or carbon monoxide.

[0261] In one embodiment or in combination with any embodiment mentioned herein, the temperature in the pyrolysis reactor 118 can be adjusted to promote the production of certain end products. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 can be at least 325°C, or at least 350°C, or at least 375°C, or at least 400°C, or at least 425°C, or at least 450°C, or at least 475°C, or at least 500°C, or at least 525°C, or at least 550°C, or at least 575°C, or at least 600°C, or at least 625°C, or at least 650°C, or at least 675°C, or at least 700°C, or at least 725°C, or at least 750°C, or at least 775°C, or at least 800°C, additionally or alternatively In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 can be no more than 1,100°C, or no more than 1,050°C, or no more than 1,000°C, or no more than 950°C, or no more than 900°C, or no more than 850°C, or no more than 800°C, or no more than 750°C, or no more than 700°C, or no more than 650°C, or no more than 600°C, or no more than 550°C, or no more than 525°C, or no more than 500°C, or no more than 475°C, or no more than 450°C, or no more than 425°C, or no more than 400°C. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 can be in the range of 325 to 1,100°C, 350 to 900°C, 350 to 700°C, 350 to 550°C, 350 to 475°C, 500 to 1,100°C, 600 to 1,100°C, or 650 to 1,000°C.

[0262] In one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be at least 1 second, or at least 2 seconds, or at least 3 seconds, or at least 4 seconds, or at least 10, or at least 20 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes, or at least 75 minutes, or at least 90 minutes. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be no more than 6 hours, or no more than 5 hours, or no more than 4 hours, or no more than 3 hours, or no more than 2 hours, or no more than 1 hour, or no more than 0.5 hours. In one embodiment or in combination with any embodiment mentioned herein, the residence time of the pyrolysis reaction can be in the range of 30 minutes to 4 hours, or 30 minutes to 3 hours, or 1 hour to 3 hours, or 1 hour to 2 hours.

[0263] In one embodiment or in combination with any embodiment mentioned herein, the pressure within the pyrolysis reactor 118 can be maintained at a pressure of at least 0.1 bar, or at least 0.2 bar, or at least 0.3 bar, and / or no more than 60 bar, or no more than 50 bar, or no more than 40 bar, or no more than 30 bar, or no more than 20 bar, or no more than 10 bar, or no more than 8 bar, or no more than 5 bar, or no more than 2 bar, or no more than 1.5 bar, or no more than 1.1 bar. In one embodiment or in combination with any embodiment mentioned herein, the pressure within the pyrolysis reactor 18 can be maintained at about atmospheric pressure or in a range of 0.1 to 100 bar, or 0.1 to 60 bar, or 0.1 to 30 bar, or 0.1 to 10 bar, or 1.5 bar, 0.2 to 1.5 bar, or 0.3 to 1.1 bar.

[0264] In one embodiment or in combination with any of the embodiments mentioned herein, a pyrolysis catalyst can be introduced into the plastic feed prior to introduction into the pyrolysis reactor 118 and / or introduced directly into the pyrolysis reactor 118 to produce r-catalytic pyrolysis oil or r-pyrolysis oil prepared by a catalytic pyrolysis process. In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the catalyst can comprise: (i) a solid acid such as a zeolite (e.g., ZSM-5, mordenite, beta, ferrierite, and / or zeolite-Y); (ii) a superacid such as sulfonated, phosphated, or fluorinated forms of zirconia, titania, alumina, silica-alumina, and / or clay; (iii) a solid base such as a metal oxide, mixed metal oxide, metal hydroxide, and / or metal carbonate, particularly those of alkali metals, alkaline earth metals, transition metals, and / or rare earth metals; (iv) hydrotalcites and other clays; (v) metal hydrides, particularly those of alkali metals, alkaline earth metals, transition metals, and / or rare earth metals; (vi) alumina and / or silica-alumina; (vii) a homogeneous catalyst such as a Lewis acid, a metal tetrachloroaluminate, or an organic ionic liquid; (viii) activated carbon; or (ix) combinations thereof.

[0265] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 occurs in the substantial absence of a catalyst, particularly the catalysts described above. In such an embodiment, non-catalytic, heat-retaining inert additives, such as sand, may still be introduced into the pyrolysis reactor 118 to facilitate heat transfer within the reactor 118.

[0266] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 can occur in the substantial 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.

[0267] Reference again Figure 2 The pyrolysis effluent 120 exiting the pyrolysis reactor 118 typically includes pyrolysis gases, pyrolysis vapors, and residual solids. As used herein, vapors produced during the pyrolysis reaction may be interchangeably referred to as "pyrolysis oil," which refers to the vapors when condensed into their liquid state. In one embodiment or in combination with any of the embodiments mentioned herein, the solids in the pyrolysis effluent 20 may include particles of char, ash, unconverted plastic solids, other unconverted solids from the feedstock, and / or spent catalyst (if a catalyst is used).

[0268] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can comprise at least 20, or at least 25, or at least 30, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80 weight percent, in each case, of pyrolysis vapor, which can subsequently be condensed into a resulting pyrolysis oil (e.g., r-pyrolysis oil). Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can comprise no more than 99, or no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30 weight percent, in each case, of pyrolysis vapor. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can comprise 20 to 99 weight percent, 40 to 90 weight percent, or 55 to 90 weight percent pyrolysis vapor.

[0269] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can comprise at least 1, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12 weight percent of pyrolysis gas (e.g., r-pyrolysis gas) in each case. As used herein, "pyrolysis gas" refers to a composition produced by pyrolysis and is a gas at standard temperature and pressure (STP). Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 20 can comprise no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15 weight percent of pyrolysis vapor in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can comprise 1 to 90 weight percent, or 5 to 60 weight percent, or 10 to 60 weight percent, or 10 to 30 weight percent, or 5 to 30 weight percent pyrolysis gases.

[0270] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can contain no more than 15, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6, or no more than 5, or no more than 4, or no more than 3 weight percent residual solids, in each case.

[0271] In one embodiment or in any combination of the embodiments mentioned, a cracker feed composition comprising r-pyrolysis oil is provided, and the r-pyrolysis oil composition comprises a recycled component catalytic pyrolysis oil (r-catalytic pyrolysis oil) and a recycled component pyrolysis oil (r-pyrolysis oil). R-pyrolysis oil is a pyrolysis oil prepared without adding a pyrolysis catalyst. The cracker feed may comprise at least 5, 10, 15 or 20 weight percent of r-catalytic pyrolysis oil, which may optionally be hydrotreated. The t-pyrolysis oil and r-catalytic pyrolysis oil containing r-pyrolysis oil may be cracked according to any process described herein to provide an olefin-containing effluent stream. The r-catalytic pyrolysis oil may be blended with the r-pyrolysis oil to form a blended stream that is cracked in the cracker unit. Alternatively, the mixed stream may contain no more than 10, 5, 3, 2, or 1 weight percent of r-catalytic pyrolysis oil that has not been hydrotreated.

[0272] In one embodiment or in combination with any of the mentioned embodiments, the r-pyrolysis oil is free of r-catalytic pyrolysis oil.

[0273] 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 embodiment described herein, the solids separator 122 removes a majority of the solids from the conversion effluent 120. In one embodiment or in combination with any embodiment described 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 hot regenerated solids 128 can be introduced directly into the pyrolysis reactor 118. In one embodiment or in combination with any embodiment described herein, at least a portion of the solid particles 124 recovered in the solids separator 122 can be introduced directly back into the pyrolysis reactor 118, particularly if the solid particles 124 contain a significant amount of unconverted plastic waste. The solids can be removed from the regenerator 126 via line 145 and discharged from the system.

[0274] Back to Figure 2 , the remaining gas and vapor conversion products 130 from the solid separator 122 can be introduced into a fractionation column 132. In the fractionation column 132, at least a portion of the pyrolysis oil vapor can be separated from the cracked gas to form a cracked gas product stream 134 and a pyrolysis oil vapor stream 136. Suitable systems for use as the fractionation column 132 may include, for example, a distillation column, a membrane separation unit, a quench tower, a condenser, or any other known separation unit known in the art. In one embodiment or in combination with any embodiment mentioned herein, any residual solids 146 accumulated in the fractionation column 132 can be introduced into the optional regenerator 126 for additional processing.

[0275] In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the pyrolysis oil vapor stream 136 can be introduced into a quenching unit 138 to at least partially quench the pyrolysis vapors into their liquid form (i.e., pyrolysis oil). The quenching unit 138 can include any suitable quenching system known in the art, such as a quenching tower. The resulting liquid pyrolysis oil stream 140 can be removed from the system 110 and used in other downstream applications described herein. In one embodiment or in combination with any embodiment mentioned herein, the liquid pyrolysis oil stream 140 can be not subjected to any additional processing, such as hydrotreating and / or hydrogenation, before being used in any downstream application described herein.

[0276] In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the pyrolysis oil vapor stream 136 can be introduced into a hydroprocessing unit 142 for further refining. The hydroprocessing unit 142 can include a hydrocracker, a catalytic cracker operated using a hydrogen feed stream, a hydroprocessing unit, and / or a hydrogenation unit. In the hydroprocessing unit 142, the pyrolysis oil vapor stream 136 can be treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil and remove undesirable by-products from the pyrolysis oil. The resulting hydrotreated pyrolysis oil vapor stream 144 can be removed and introduced into a quenching unit 138. Alternatively, the pyrolysis oil vapor can be cooled, liquefied, and then treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil. In this case, the hydrogenation or hydroprocessing is carried out in the liquid phase pyrolysis oil. In this embodiment, the post-hydrogenation or post-hydroprocessing does not require a quenching step.

[0277] The pyrolysis system 110 described herein can produce pyrolysis oil (e.g., r-pyrolysis oil) and pyrolysis gas (e.g., r-pyrolysis gas), which can be directly used in various downstream applications based on their desired formulation. Various characteristics and properties of the pyrolysis oil and pyrolysis gas are described below. It should be noted that while all of the following characteristics and properties can be listed individually, it is contemplated that each of the following characteristics and / or properties of the pyrolysis oil or pyrolysis gas are not mutually exclusive and can be present in any combination.

[0278] The pyrolysis oil may primarily contain hydrocarbons having 4 to 30 carbon atoms per molecule (e.g., C4 to C 30 As used herein, the term "Cx" or "Cx hydrocarbons" refers to hydrocarbon compounds comprising x total carbons per molecule and includes all olefins, paraffins, aromatic hydrocarbons, and isomers having that number of carbon atoms. For example, each of the n-, iso-, and tert-butane and butene and butadiene molecules would fall within the general description "C4."

[0279] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil fed to the cracking furnace can have a C4-C5 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 weight percent in each case. 30 Hydrocarbon content, based on the weight of the pyrolysis oil.

[0280] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the furnace may comprise primarily C5-C 25 , C5-C22 or C5-C 20 hydrocarbons, or may contain at least about 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent of C5-C25 、C5-C 22 or C5-C 20 Hydrocarbons, based on the weight of the pyrolysis oil.

[0281] The gas furnace can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock, thereby avoiding the necessity of subjecting the pyrolysis oil feedstock to separation techniques to deliver smaller or lighter hydrocarbon fractions to the cracking furnace. In one embodiment or any of the mentioned embodiments, after delivery from the pyrolysis manufacturer, the pyrolysis oil does not undergo a separation process for separating the heavy hydrocarbon fractions from the lighter hydrocarbon fractions relative to each other before feeding the pyrolysis oil to the cracker furnace. Feeding the pyrolysis oil to the gas furnace allows for the use of pyrolysis oil containing heavy tails or higher carbon numbers equal to or higher than 12. In one embodiment or any of the mentioned embodiments, the pyrolysis oil fed to the cracking furnace is C5-C 25 A hydrocarbon stream containing at least 1 wt.%, or at least 3 wt.%, or at least 5 wt.%, or at least 8 wt.%, or at least 10 wt.%, or at least 12 wt.%, or at least 15 wt.%, or at least 18 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%, or at least 45 wt.%, or at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.% of a hydrocarbon stream in C 12 to C 25 (including the end value), or in the range of C 14 to C 25 (including the end value), or in the range of C 16 to C 25 Hydrocarbons within the range of (including the end value).

[0282] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55 weight percent C6-C 12 Hydrocarbon content, based on the weight of the pyrolysis oil. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have, in each case, a weight percent of no more than 98.5, 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 C6-C 12 Hydrocarbon content. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have 10 to 95 weight percent, 20 to 80 weight percent, or 35 to 80 weight percent C6-C 12 Hydrocarbon content.

[0283] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a C 13 -C 23 Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a C content of no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, in each case by weight. 13 to C 23 In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have 1 to 80 weight percent, 5 to 65 weight percent, or 10 to 60 weight percent C 13 to C 23 Hydrocarbon content.

[0284] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil or r-pyrolysis oil fed to the cracking furnace, or the r-pyrolysis oil fed to the cracking furnace that receives a predominantly C2-C4 feedstock prior to feeding the pyrolysis oil (and references to r-pyrolysis oil or pyrolysis oil throughout include any of these embodiments) can have, in each case, at least 1, or at least 2, or at least 3, or at least 4, or at least 5 weight percent of C 24+ Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a C content of no more than 15, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6. 24+ In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have 1 to 15 weight percent, 3 to 15 weight percent, 2 to 5 weight percent, or 5 to 10 weight percent hydrocarbon content. 24+ Hydrocarbon content.

[0285] The pyrolysis oil may also include various amounts of olefins, aromatics, and other compounds. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil comprises at least 1, or at least 2, or at least 5, or at least 10, or at least 15, or at least 20 weight percent olefins and / or aromatics in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may comprise no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 2, or no more than 1 weight percent olefins and / or aromatics in each case.

[0286] In one embodiment or in combination with any of the embodiments mentioned herein, the aromatic hydrocarbon content of the pyrolysis oil can 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 weight percent. In one embodiment or in combination with any of the embodiments mentioned, the aromatic hydrocarbon content of the pyrolysis oil is no more than 15, or no more than 10, or no more than 8, or no more than 6, in each case as weight percent.

[0287] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a cycloparaffin content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a cycloparaffin content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 10, or no more than 5, or no more than 2, or no more than 1, or no more than 0.5, or undetectable amounts in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a cycloparaffin content of no more than 5, or no more than 2, or no more than 1 wt.%, or undetectable amounts. Alternatively, the pyrolysis oil may contain 1 to 50 weight percent, 5 to 50 weight percent, or 10 to 45 weight percent cycloparaffins, particularly if the r-pyrolysis oil is subjected to a hydrotreating process.

[0288] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a paraffin content of at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent, in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a paraffin content of no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55 weight percent, in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a paraffin content of 25 to 90 weight percent, 35 to 90 weight percent, or 40 to 80 weight percent, or 40 to 70 weight percent, or 40 to 65 weight percent.

[0289] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have an n-paraffin content of at least 5, or at least 10, or at least 15, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent, in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have an n-paraffin content of no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55 weight percent, in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have an n-paraffin content of 25 to 90 weight percent, 35 to 90 weight percent, or 40 to 70 weight percent, or 40 to 65 weight percent, or 50 to 80 weight percent.

[0290] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin to olefin weight ratio of at least 0.2: 1, or at least 0.3: 1, or at least 0.4: 1, or at least 0.5: 1, or at least 0.6: 1, or at least 0.7: 1, or at least 0.8: 1, or at least 0.9: 1, or at least 1: 1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin to olefin weight ratio of no more than 3: 1, or no more than 2.5: 1, or no more than 2: 1, or no more than 1.5: 1, or no more than 1.4: 1, or no more than 1.3: 1. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin to olefin weight ratio of 0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1:4.5:1, or 0.2:1 to 4:1, or 0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

[0291] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of at least 0.001: 1, or at least 0.1: 1, or at least 0.2: 1, or at least 0.5: 1, or at least 1: 1, or at least 2: 1, or at least 3: 1, or at least 4: 1, or at least 5: 1, or at least 6: 1, or at least 7: 1, or at least 8: 1, or at least 9: 1, or at least 10: 1, or at least 15: 1, or at least 20: 1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of no more than 100: 1, 7, or no more than 5: 1, or no more than 50: 1, or no more than 40: 1, or no more than 30: 1. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a normal-to-isoparaffin weight ratio ranging from 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0292] It should be noted that all of the above hydrocarbon weight percentages can be determined using gas chromatography-mass spectrometry (GC-MS).

[0293] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can exhibit a viscosity of at least 0.6 g / cm2 at 15°C. 3 , or at least 0.65g / cm 3 , or at least 0.7g / cm 3 Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may exhibit a density of no more than 1 g / cm at 15°C. 3 , or not more than 0.95g / cm 3 , or not more than 0.9g / cm 3 , or not more than 0.85g / cm 3 In one embodiment or combination with any embodiment mentioned herein, the pyrolysis oil exhibits a density of 0.6 to 1 g / cm at 15°C. 3 , 0.65 to 0.95 g / cm 3 or 0.7 to 0.9 g / cm 3 .

[0294] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can exhibit an API gravity at 15° C. of at least 28, or at least 29, or at least 30, or at least 31, or at least 32, or at least 33. Additionally, or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can exhibit an API gravity at 15° C. 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. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil exhibits an API gravity at 15° C. of between 28 and 50, between 29 and 58, or between 30 and 44.

[0295] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can 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. These values can be measured according to ASTM D-2887 or the procedure described in the working examples. If this value is obtained in either method, then the medium boiling point having the stated value is satisfied. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a median boiling point of no more than 250° C., or no more than 245° C., or no more than 240° C., or no more than 235° C., or no more than 230° C., or no more than 225° C., or no more than 220° C., or no more than 215° C., or no more than 210° C., or no more than 205° C., or no more than 200° C., or no more than 195° C., or no more than 190° C., or no more than 185° C., or no more than 180° C., or no more than 175° C., or no more than 170° C., or no more than 165° C., or no more than 160° C., 1° C., or no more than 55° C., or no more than 150° C., or no more than 145° C., or no more than 140° C., or no more than 135° C., or no more than 130° C., or no more than 125° C., or no more than 120° C. These values can be measured according to ASTM D-2887 or the procedure described in the working examples. If this value is achieved in any of the methods, then the median boiling point having the stated value is satisfied. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a median boiling point in the range of 75 to 250°C, 90 to 225°C, or 115 to 190°C. As used herein, "median boiling point" refers to the median boiling point temperature of the pyrolysis oil when 50 weight percent of the pyrolysis oil boils above the median boiling point and 50 weight percent of the pyrolysis oil boils below the median boiling point.

[0296] In one embodiment or in combination with any embodiment mentioned herein, the boiling point range of the pyrolysis oil can be such that no more than 10% of the pyrolysis oil has a final boiling point (FBP) of 250°C, 280°C, 290°C, 300°C, or 310°C. To determine the FBP, the procedure according to ASTM D-2887 or as described in the working examples can be used, and if the value is obtained under either method, then the FBP having the stated value is satisfied.

[0297] Turning to the pyrolysis gases, the pyrolysis gases can have a methane content of at least 1, or at least 2, or at least 5, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20 weight percent. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gases can have a methane content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25 weight percent, in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gases can have a methane content of 1 to 50 weight percent, 5 to 50 weight percent, or 15 to 45 weight percent.

[0298] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas can have a C3 hydrocarbon content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 15, or at least 20, or at least 25 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas can have a C3 hydrocarbon content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas can have a C3 hydrocarbon content of 1 to 50 weight percent, 5 to 50 weight percent, or 20 to 50 weight percent.

[0299] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas can have a C4 hydrocarbon content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20 weight percent, in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas can have a C4 hydrocarbon content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25 weight percent, in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas can have a C4 hydrocarbon content of 1 to 50 weight percent, 5 to 50 weight percent, or 20 to 50 weight percent.

[0300] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil of the present invention can be a recycled content pyrolysis oil composition (r-pyrolysis oil).

[0301] Various downstream applications that can utilize the pyrolysis oil and / or pyrolysis gas disclosed above are described in more detail below. In one embodiment or in combination with any of the embodiments described herein, the pyrolysis oil can undergo one or more processing steps before being introduced into a downstream unit such as a cracking furnace. Examples of suitable processing steps can 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.

[0302] Now turn Figure 3 , shows a schematic diagram of a processing zone for pyrolysis oil, according to one embodiment or in combination with any embodiment mentioned herein.

[0303] like Figure 3 As shown in the processing zone 220 shown in FIG, 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 a processing zone 220, such as a separator, which can separate the r-pyrolysis oil into a light pyrolysis oil fraction 254 and a heavy pyrolysis oil fraction 256. The separator 220 used for this separation can be of any suitable type, including a single-stage vapor-liquid separator or "flash" 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.

[0304] In one embodiment or in combination with any embodiment mentioned herein, the heavy fraction can have a C4-C7 content or a C8+ content of at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 weight percent. The light fraction can include at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% C3 and lighter (C 3- ) or C7 and lighter (C 7- In some embodiments, the separator can concentrate the desired components into the heavy fraction, so that the heavy fraction can have a C4-C7 content or C7 content higher than the pyrolysis oil taken out from the pyrolysis zone. 8+ The C4-C7 content or C4-C7 content is at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 70, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150% greater. 8+ Content. Figure 3 As shown, at least a portion of the heavy fraction may be sent to a cracking furnace 230 for cracking as an r-pyrolysis oil composition or as a portion of a pyrolysis oil composition to form an olefin-containing effluent 258, as discussed in further detail below.

[0305] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil is hydrotreated in the treatment zone, while in other embodiments, the pyrolysis oil is not hydrotreated before entering a downstream unit such as a cracking furnace. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil is not pretreated at all prior to 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.

[0306] In one embodiment or in combination with any embodiment described herein, the r-pyrolysis oil can be combined with a non-recovered cracker stream to minimize the amount of less desirable compounds present in the combined cracker feed. For example, when the r-pyrolysis oil has a certain concentration of less desirable compounds (e.g., impurities such as oxygenates, aromatics, or other compounds described herein), the r-pyrolysis oil can be combined with the cracker feed in an amount such that the total concentration of 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-recovered cracker feed to be combined with the r-pyrolysis oil stream can be determined by comparing the measured amount of one or more less desirable compounds present in the r-pyrolysis oil with target values for those compounds to determine the difference, and then determining the amount of non-recovered hydrocarbons to be added to the r-pyrolysis oil stream based on the difference. The amount of r-pyrolysis oil and non-recovered hydrocarbons can be within one or more ranges described herein.

[0307] At least a portion of the gamma-ethylene may be derived directly or indirectly from the cracking of the gamma-pyrolysis oil. The process for obtaining gamma-olefins from cracking (gamma-pyrolysis oil) may be as follows and as Figure 4 As described in.

[0308] Steering Figure 4 , which is a flow diagram of the steps associated with the cracking furnace 20 and separation zone 30 of a system for producing an r-composition obtained by cracking r-pyrolysis oil. Figure 4 As shown, a feed stream comprising r-pyrolysis oil (r-pyrolysis oil-containing feed stream) can be introduced into the cracking furnace 20 alone or in combination with a non-recovery cracker feed stream. The pyrolysis unit that produces the r-pyrolysis oil can be co-located with the production facility. In other embodiments, the r-pyrolysis oil can originate from a remote pyrolysis unit and be transported to the production facility.

[0309] In one embodiment or in combination with any embodiment mentioned herein, the feed stream containing r-pyrolysis oil can contain at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in an amount, in each case, of at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 98, or at least 99, or at least or 100 weight percent and / or no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20 of r-pyrolysis oil, based on the total weight of the feed stream containing r-pyrolysis oil.

[0310] In one embodiment or combination with any embodiment mentioned herein, at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 97, or at least 98, or at least 99, or 100 weight percent and / or no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10 weight percent of the r-pyrolysis oil is obtained from pyrolysis of a waste stream. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock containing plastic waste. Desirably, in each case, at least 90, or at least 95, or at least 97, or at least 98, or at least 99, or at least 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.

[0311] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have any one or combination of the compositional characteristics described above for the pyrolysis oil.

[0312] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can comprise at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent C4-C 30 Hydrocarbons, and as used herein, hydrocarbons include aliphatic, alicyclic, aromatic, and heterocyclic compounds. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may comprise primarily C5-C 25 、C5-C 22 or C5-C 20 hydrocarbons, or may contain at least 55, 60, 65, 70, 75, 80, 85, 90, or 95 weight percent C5-C 25 、C5-C 22 or C5-C 20 hydrocarbon.

[0313] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil composition may comprise C4-C 12 Aliphatic compounds (branched or unbranched alkanes and alkenes (including diolefins) and alicyclic hydrocarbons) and C 13 -C 22 aliphatic compounds in a weight ratio greater than 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on the weight of the r-pyrolysis oil.

[0314] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil composition may comprise C 13 -C 22 Aliphatic compounds (branched or unbranched alkanes and alkenes (including diolefins) and alicyclic hydrocarbons) and C4-C 12 aliphatic compounds in a weight ratio greater than 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on the weight of the r-pyrolysis oil.

[0315] In one embodiment, the two aliphatic hydrocarbons (branched or unbranched alkanes and alkenes, and alicyclic compounds) with the highest concentration in the r-pyrolysis oil are in the C5-C 18 , or C5-C 16 , or C5-C 14 , or C5-C 10 , or in the range of C5-C8 (inclusive).

[0316] The r-pyrolysis oil may include one or more of paraffinic, cycloparaffinic or cycloaliphatic hydrocarbons, aromatic hydrocarbons, aromatic-containing hydrocarbons, olefins, oxygen-containing compounds and polymers, heteroatom compounds or polymers, and other compounds or polymers.

[0317] For example, in one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can comprise at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, and / or no more than 99, or no more than 97, or no more than 9 ... More than 95, or not more than 93, or not more than 90, or not more than 87, or not more than 85, or not more than 83, or not more than 80, or not more than 78, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, not more than 25, not more than 30, or not more than 20, or not more than 15 of paraffins (either straight or branched), based on the total weight of the r-pyrolysis oil. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a paraffin content of 25 to 90, 35 to 90, or 40 to 80, or 40 to 70, or 40 to 65 weight percent, or 5 to 50, or 5 to 40, or 5 to 35, or 10 to 35, or 10 to 30, or 5 to 25, or 5 to 20, in each case as wt. % based on the weight of the r-pyrolysis oil composition.

[0318] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can include cycloalkanes or cycloaliphatic hydrocarbons in an amount of zero, or at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20, in each case by weight percent, and / or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 2, or no more than 1, or no more than 0.5, or in an undetectable amount, in each case by weight percent. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a cycloalkanes content of no more than 5, or no more than 2, or no more than 1 wt.%, or in an undetectable amount. Examples of ranges for the amount of cycloalkanes (or cycloaliphatic hydrocarbons) contained in the r-pyrolysis oil are 0-35, or 0-30, or 0-25, or 2-20, or 2-15, or 2-10, or 1-10, in each case wt. %, based on the weight of the r-pyrolysis oil composition.

[0319] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can have a paraffin to olefin weight ratio 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 of the embodiments mentioned herein, the r-pyrolysis oil can have a paraffin to olefin weight ratio of no more than 3: 1, or no more than 2.5: 1, or no more than 2: 1, or no more than 1.5: 1, or no more than 1.4: 1, or no more than 1.3: 1. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can have a paraffin to olefin weight ratio ranging from 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.

[0320] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of at least 0.001: 1, or at least 0.1: 1, or at least 0.2: 1, or at least 0.5: 1, or at least 1: 1, or at least 2: 1, or at least 3: 1, or at least 4: 1, or at least 5: 1, or at least 6: 1, or at least 7: 1, or at least 8: 1, or at least 9: 1, or at least 10: 1, or at least 15: 1, or at least 20: 1. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of no more than 100: 1, or no more than 50: 1, or no more than 40: 1, or no more than 30: 1. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have a normal to iso-paraffin weight ratio ranging from 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0321] In one embodiment, the r-pyrolysis oil contains no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 5, or no more than 2, or no more than 1 weight percent of aromatic hydrocarbons, in each case based on the total weight of the r-pyrolysis oil. As used herein, the term "aromatic hydrocarbons" refers to the total amount (by weight) of benzene, toluene, xylene, and styrene. The r-pyrolysis oil may include at least 1, or at least 2, or at least 5, or at least 8, or at least 10 weight percent of aromatic hydrocarbons, in each case based on the total weight of the r-pyrolysis oil.

[0322] In one embodiment or combination with any embodiment mentioned herein, the r-pyrolysis oil can include aromatic hydrocarbons in an amount of no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 5, or no more than 2, or no more than 1, by weight, in each instance, based on the total weight of the r-pyrolysis oil, or no detectable. Aromatic-containing compounds include the aromatic hydrocarbons described above and any compounds containing aromatic moieties, such as terephthalate residues and fused ring aromatic hydrocarbons, such as naphthalene and tetralin.

[0323] In one embodiment or in combination with any embodiment mentioned herein, the g-pyrolysis oil can include olefins in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20, or at least 30, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65 weight percent olefins in each case, and / or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10 weight percent olefins in each case, based on the weight of the g-pyrolysis oil. Olefins include mono-olefins and di-olefins. Examples of suitable ranges include wt. % ratios in which the amount of olefin present in each instance is from 5 to 45, or from 10 to 35, or from 15 to 30, or from 40 to 85, or from 45 to 85, or from 50 to 85, or from 55 to 85, or from 60 to 85, or from 65 to 85, or from 40 to 80, or from 45 to 80, or from 50 to 80, or from 55 to 80, or from 60 to 80, or from 65 to 80, 45 to 80, or from 50 to 80, or 55 to 80, or 60 to 80, or 65 to 80, or 40 to 75, or 45 to 75, or 50 to 75, or 55 to 75, or 60 to 75, or 65 to 75, or 40 to 70, or 45 to 70, or 50 to 70, or 55 to 70, or 60 to 70, or 65 to 70, or 40 to 65, or 45 to 65, or 50 to 65, or 55 to 65, based on the weight of the r-pyrolysis oil.

[0324] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can include an amount of zero or at least 0.01, or at least 0.1, or at least 1, or at least 2, or at least 5 weight percent of oxygenates or polymers in each case, and / or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 6, or no more than 5, or no more than 3, or no more than 2 weight percent of oxygenates or polymers in each case, based on the weight of the r-pyrolysis oil. Oxygenates and polymers are those that contain oxygen atoms. Examples of suitable ranges include oxygenates present in an amount in the range of 0-20, or 0-15, or 0-10, or 0.01-10, or 1-10, or 2-10, or 0.01-8, or 0.1-6, or 1-6, or 0.01-5 wt.%, based on the weight of the r-pyrolysis oil.

[0325] In one embodiment or in combination with any embodiment mentioned herein, the amount of oxygen atoms in the r-pyrolysis oil can be no more than 10, or no more than 8, or no more than 5, or no more than 4, or no more than 3, or no more than 2.75, or no more than 2.5, or no more than 2.25, or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.1, or no more than 0.05, in each case as wt. % based on the weight of the r-pyrolysis oil. Examples of amounts of oxygen in the r-pyrolysis oil may be 0-8, or 0-5, or 0-3, or 0-2.5 or 0-2, or 0.001-5, or 0.001-4, or 0.001-3, or 0.001-2.75, or 0.001-2.5, or 0.001-2, or 0.001-1.5, or 0.001-1, or 0.001-0.5, or 0.001-1, in each case in wt. %, based on the weight of the r-pyrolysis oil.

[0326] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can include a heteroatom compound or polymer in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20 weight percent, and / or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 6, or no more than 5, or no more than 3, or no more than 2 weight percent, based on the weight of the r-pyrolysis oil. A heteroatom compound or polymer is defined in this paragraph as any compound or polymer containing nitrogen, sulfur, or phosphorus. Any other atom is not considered a heteroatom for the purpose of determining the amount of heteroatoms, heterocompounds, or heteropolymers present in the r-pyrolysis oil. The r-pyrolysis oil may contain heteroatoms present in an amount of 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 0.075, or no more than 0.05, or no more than 0.03, or no more than 0.02, or no more than 0.01, or no more than 0.008, or no more than 0.006, or no more than 0.005, or no more than 0.003, or no more than 0.002, in each case wt. %, based on the weight of the r-pyrolysis oil.

[0327] In one embodiment or in combination with any embodiment mentioned herein, the solubility of water in r-pyrolysis oil at 1 atm and 25° C. is less than 2 wt.%, water, or no more than 1.5, or no more than 1, or no more than 0.5, or no more than 0.1, or no more than 0.075, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, in each case as wt.% water based on the weight of the r-pyrolysis oil. Desirably, the solubility of water in r-pyrolysis oil is no more than 0.1 wt.%, based on the weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil contains no more than 2 wt. % water, or no more than 1.5, or no more than 1, or no more than 0.5, desirably or no more than 0.1, or no more than 0.075, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, in each case as wt. % water based on the weight of the r-pyrolysis oil.

[0328] In one embodiment or in combination with any of the embodiments mentioned herein, the solids content of the r-pyrolysis oil is no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, or no more than 0.001, in each case as wt.% solids based on the weight of the r-pyrolysis oil.

[0329] In one embodiment or in combination with any embodiment mentioned herein, the sulfur content of the r-pyrolysis oil is no more than 2.5 wt.%, or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.1, or no more than 0.05, desirably 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.

[0330] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have the following component contents:

[0331] a carbon atom content of at least 75 wt.%, or at least 77, or at least 80, or at least 82, or at least 85, in each case wt.%, and / or at most 90, or at most 88, or at most 86, or at most 85, or at most 83, or at most 82, or at most 80, or at most 77, or at most 75, or at most 73, or at most 70, or at most 68, or at most 65, or at most 63, or at most 60, in each case wt.%, desirably at least 82% and at most 93%, and / or

[0332] The hydrogen atom content is at least 10 wt.%, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or not more than 19, or not more than 18, or not more than 17, or not more than 16, or not more than 15, or not more than 14, or not more than 13, or at most 11, in each case by wt.%,

[0333] The oxygen atom content is not more than 10, or not more than 8, or not more than 5, or not more than 4, or not more than 3, or not more than 2.75, or not more than 2.5, or not more than 2.25, or not more than 2, or not more than 1.75, or not more than 1.5, or not more than 1.25, or not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.1, or not more than 0.05, in each case by weight

[0334] In each case based on the weight of the r-pyrolysis oil.

[0335] In one embodiment or in combination with any embodiment mentioned herein, the amount of hydrogen atoms in the r-pyrolysis oil can be in the range of 10-20, or 10-18, or 11-17, or 12-16, or 13-16, or 13-15, or 12-15, in each case wt. % based on the weight of the r-pyrolysis oil.

[0336] In one embodiment or in combination with any embodiment mentioned herein, the metal content of the r-pyrolysis oil is desirably low, e.g., no more than 2 wt.%, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, in each case wt.% based on the weight of the r-pyrolysis oil.

[0337] In one embodiment or in combination with any embodiment mentioned herein, the alkali and alkaline earth metal or mineral content of the r-pyrolysis oil is desirably low, e.g., no more than 2 wt.%, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, in each case wt.% based on the weight of the r-pyrolysis oil.

[0338] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of paraffins to cycloalkanes in the r-pyrolysis oil can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.25:1, or at least 4.5:1, or at least 4.75:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 13:1, or at least 15:1, or at least 17:1, based on the weight of the r-pyrolysis oil.

[0339] In one embodiment or in combination with any embodiment mentioned herein, the weight ratio of the combination of paraffins and cycloalkanes to aromatic hydrocarbons can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.5:1, or at least 5:1, or at least 7:1, or at least 10:1, or at least 15:1, or at least 20:1, or at least 25:1, or at least 30:1, or at least 35:1, or at least 40:1, based on the weight of the r-pyrolysis oil. In one embodiment or combination with any of the embodiments mentioned herein, the ratio of the combination of paraffins and cycloalkanes to aromatics in the r-pyrolysis oil can be in the range of 50:1-1:1, or 40:1-1:1, or 30:1-1:1, or 20:1-1:1, or 30:1-3:1, or 20:1-1:1, or 20:1-5:1, or 50:1-5:1, or 30:1-5:1, or 1:1-7:1, or 1:1-5:1, 1:1-4:1, or 1:1-3:1.

[0340] In one embodiment or in combination with any of the embodiments described herein, the r-pyrolysis oil can have a boiling point curve defined by one or more of its 10%, 50%, and 90% boiling points, as defined below. As used herein, "boiling point" refers to the boiling point of a composition as determined by ASTM D2887 or according to the procedures described in the working examples. A boiling point having the stated value is satisfied if the value is obtained by either method. Additionally, as used herein, "x% boiling point" means that x weight percent of the composition boils at that boiling point according to any of these methods.

[0341] As used throughout, x% boiling at a stated temperature means that at least x% of the composition boils at that temperature. In one embodiment or combination with any embodiment described herein, the 90% boiling point of the cracker feed stream or composition can be no more than 350, or no more than 325, or no more than 300, or no more than 295, or no more than 290, or no more than 285, or no more than 280, or no more than 275, or no more than 270, or no more than 265, or no more than 260, or no more than 255, or no more than 250, or no more than 245, or no more than 240, or no more than 235, or no more than 230, or no more than 22 5, or no more than 220, or no more than 215, or no more than 200, or no more than 190, or no more than 180, or no more than 170, or no more than 160, or no more than 150, or no more than 140, in each case °C, and / or at least 200, or at least 205, or at least 210, or at least 215, or at least 220, or at least 225, or at least 230, in each case °C, and / or no more than 25, 20, 15, 10, 5, or 2 weight percent of the r-pyrolysis oil may have a boiling point of 300°C or higher.

[0342] Reference again Figure 3%, or r-pyrolysis oil can be introduced into the cracking furnace or coils or tubes alone (e.g., in a mixture comprising at least 85, or at least 90, or at least 95, or at least 99, or 100, in each case by weight % pyrolysis oil based on the weight of the cracker feed stream) or in combination with one or more non-recycled cracker feed streams. When introduced into the cracker furnace, coils or tubes with the non-recycled cracker feed streams, the r-pyrolysis oil can be present in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 12, or at least 15, or at least 20, or at least 25, or at least 30, in each case by weight %, and / or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 5, or no more than 2, in each case by weight percent based on the total weight of the combined streams. Thus, the non-recovery cracker feed stream or composition can be present in the combined stream in an amount of at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, in each case as weight percent, and / or no more than 99, or no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, in each case as weight percent based on the total weight of the combined stream. Unless otherwise indicated herein, the properties of the cracker feed stream described below apply to the non-recycled cracker feed stream before (or in the absence of) combination with a stream comprising r-pyrolysis oil, as well as to a combined cracker stream comprising both non-recycled cracker feed and r-pyrolysis oil feed.

[0343] In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed stream can comprise a composition comprising primarily C2-C4 hydrocarbons, or a composition comprising primarily C5-C 22As used herein, the term "primarily C2-C4 hydrocarbons" refers to a stream or composition containing at least 50 weight percent C2-C4 hydrocarbon components. Examples of specific types of C2-C4 hydrocarbon streams or compositions include propane, ethane, butane, and LPG. In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed can contain at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.%, based on the total weight of the feed, and / or no more than 100, or no more than 99, or no more than 95, or no more than 92, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, in each case weight percent C2-C4 hydrocarbons or linear alkanes, based on the total weight of the feed. The cracker feed may comprise primarily propane, primarily ethane, primarily butane, or a combination of two or more of these components. These components may be non-recycled components. The cracker feed may comprise primarily propane, or at least 50 mol% propane, or at least 80 mol% propane, or at least 90 mol% propane, or at least 93 mol% propane, or at least 95 mol% propane (including any recycled streams mixed with fresh feed). The cracker feed may comprise HD5 quality propane as raw or fresh feed. The cracker may contain greater than 50 mol% ethane, or at least 80 mol% ethane, or at least 90 mol% ethane, or at least 95 mol% ethane. These components may be non-recycled components.

[0344] In one embodiment or in combination with any embodiment described herein, the cracker feed stream may comprise a primarily C5-C 22 As used herein, "primarily C5-C 22 "Hydrocarbon" refers to hydrocarbons containing at least 50 weight percent of C5-C 22 %, or at least 99, or at least 95, or at least 92, or at least 90, or at least 85, or at least 80, or at least 75, or at least 70, or at least 85, or at least 90, or at least 95, in each case wt.%, and / or no more than 100, or no more than 99, or no more than 95, or no more than 92, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, in each case C5-C 22 , or C5-C20 The hydrocarbon weight percentage is based on the total weight of the stream or composition. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed can have at least 0.5, or at least 1, or at least 2, or at least 5 C 15 and heavier (C 15+ ) content, in each case in percent by weight, and / or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 18, or not more than 15, or not more than 12, or not more than 10, or not more than 5, or not more than 3, in each case in percent by weight, based on the total weight of the feed.

[0345] The cracker feed can have a boiling point curve defined by one or more of its 10%, its 50%, and its 90% boiling points, said boiling points being obtained by the above method. Additionally, as used herein, "x% boiling point" means the boiling point at which x weight percent of the composition boils according to the above method. In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feed stream or composition 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 more than 270, or not more than 265, or not more than 260, or not more than 255, or not more than 250, or not more than 245, or not more than 240, or not more than 235, or not more than 230, or not more than 225, or not more than 220, or not more than 215, in each case °C, and / or at least 200, or at least 205, or at least 210, or at least 215, or at least 220, or at least 225, or at least 230°C, in each case °C.

[0346] In one embodiment or in combination with any of the embodiments mentioned herein, the 10% boiling point of the cracker feed stream or composition can be at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, or at least 155, in each case °C, and / or no more than 250, no more than 240, no more than 230, no more than 220, no more than 210, no more than 200, no more than 190, no more than 180, or no more than 170, in each case °C.

[0347] In one embodiment or in combination with any of the embodiments mentioned herein, the 50% boiling point of the cracker feed stream or composition can be at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, or at least 230, in each case °C, and / or no more than 300, no more than 290, no more than 280, no more than 270, no more than 260, no more than 250, no more than 240, no more than 230, no more than 220, no more than 210, no more than 200, no more than 190, no more than 180, no more than 170, no more than 160, no more than 150, or no more than 145 °C. The 50% boiling point of the cracker feed stream or composition may be in the range of 65 to 160, 70 to 150, 80 to 145, 85 to 140, 85 to 230, 90 to 220, 95 to 200, 100 to 190, 110 to 180, 200 to 300, 210 to 290, 220 to 280, 230 to 270, in each case °C.

[0348] In one embodiment or in combination with any embodiment mentioned herein, the cracker feed or stream or composition may have a 90% boiling point of at least 350°C, a 10% boiling point of at least 60°C, and a 50% boiling point in the range of 95°C to 200°C. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed or stream or composition may have a 90% boiling point of at least 150°C, a 10% boiling point of at least 60°C, and a 50% boiling point in the range of 80°C to 145°C. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed or stream has a 90% boiling point of at least 350°C, a 10% boiling point of at least 150°C, and a 50% boiling point in the range of 220 to 280°C.

[0349] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil is cracked in a gas furnace. A gas furnace is a furnace having at least one coil that receives (or is operated to receive) a feed that is primarily in the gas phase (more than 50% of the feed weight is vapor) at the coil inlet at the convection zone inlet ("gas coil"). In one embodiment or in combination with any embodiment mentioned herein, the gas coil can receive a primarily C2-C4 feedstock or a primarily C2-C3 feedstock to the inlet of the coil in the convection section, or alternatively, have at least one coil that receives more than 50 wt.% ethane and / or more than 50% propane and / or more than 50% LPG, or in any of these cases, at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, based on the weight of the cracker feed to the coil, or alternatively, based on the weight of the cracker feed to the convection zone. A gas furnace may have more than one gas coil. In one embodiment or in combination with any embodiment mentioned herein, 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 in 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, of which at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is vapor.

[0350] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil is cracked in a cracking furnace. The cracking furnace is a gas furnace. The cracking furnace comprises at least one gas coil and at least one liquid coil in the same furnace, in the same convection zone, or in the same convection box. The liquid coil is a coil that receives a feed that is primarily in liquid phase (greater than 50% of the feed weight is liquid) at the coil inlet at the inlet of the convection zone ("liquid coil"). In one embodiment or in combination with any embodiment mentioned herein, the liquid coil may receive a feed that is primarily in liquid phase (greater than 50% of the feed weight is liquid) at the inlet of the convection section ("liquid coil"). 5+ In one embodiment or in combination with any embodiment mentioned herein, the liquid coil may receive a liquid comprising primarily C6-C 22 The raw materials are mainly C7-C 16or alternatively, having at least one coil receiving more than 50 wt.% naphtha, and / or more than 50% 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 in any of these cases at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 98 wt.%, or at least 99 wt.%, based on the weight of the cracker feed to the liquid coils, or alternatively based on the weight of the cracker feed to the convection zone. In one embodiment or combination with any embodiment mentioned herein, at least one coil 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 in the convection zone or in the convection box of the furnace are liquid coils. In one embodiment or in combination with any embodiment mentioned herein, the liquid coil receives a vapor phase feed at the coil inlet at the inlet of the convection zone, wherein at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is liquid.

[0351] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil is cracked in a thermal gas cracker. In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil is cracked in a hot steam gas cracker in the presence of steam. Steam cracking refers to the high-temperature cracking (decomposition) of hydrocarbons in the presence of steam. In one embodiment or in combination with any of the embodiments mentioned herein, the r-composition is derived directly or indirectly from cracking the r-pyrolysis oil in a gas furnace. The coils in the gas furnace can consist entirely of gas coils, or the gas furnace can be a cracking furnace.

[0352] When the feed stream containing r-pyrolysis oil is combined with the non-recovery cracker feed, this combination can occur upstream of the cracking furnace or within the cracking furnace or within a single coil or tube. Alternatively, the feed stream containing r-pyrolysis oil and the non-recovery cracker feed can be introduced into the furnace separately and can pass through a portion or all of the furnaces simultaneously while being isolated from each other by feeding into separate tubes within the same furnace (e.g., a cracking furnace). According to one embodiment or in combination with any embodiment mentioned herein, the manner in which the feed stream containing r-pyrolysis oil and the non-recovery cracker feed are introduced into the cracking furnace is described in further detail below.

[0353] Now turn Figure 5 , shows a schematic diagram of a cracking furnace suitable for use in the embodiments or in combination with any of the embodiments mentioned herein.

[0354] In one embodiment or combination of any of the mentioned embodiments, there is provided a method for preparing one or more olefins comprising:

[0355] (a) feeding a first cracker feed comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to a cracker furnace;

[0356] (b) feeding a second cracker feed to the cracking furnace, wherein the second cracker feed does not contain the r-pyrolysis oil or contains less (by weight) of the r-pyrolysis oil than the first cracker feed stream; and

[0357] (c) cracking said first and said second cracker feeds in respective first and second tubes to form olefin-containing effluent streams.

[0358] The r-pyrolysis oil can be combined with the cracker stream to produce a combined cracker stream, or as described above, a first cracker stream. The first cracker stream can be 100% r-pyrolysis oil or a combination of a non-recovery cracker stream and r-pyrolysis oil. The feeding of steps (a) and / or (b) can be carried out upstream of the convection zone or within the convection zone. The r-pyrolysis oil can be combined with the non-recovery cracker stream to form a combined or first cracker stream and fed to the inlet of the convection zone, or alternatively, the r-pyrolysis oil can be fed separately to the inlet of a coil or distributor along with the non-recovery cracker stream to form the first cracker stream at the inlet of the convection zone, or the r-pyrolysis oil can be fed into a tube containing the non-recovery cracker feed downstream of the inlet of the convection zone, but before crossing, to produce the 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.

[0359] The amount of r-pyrolysis oil added to the non-recycled cracker stream to prepare the first cracker stream or the combined cracker stream can be as described above; for example, in an amount of at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95, in each case as weight percent, and / or no more than 95, 90, 85, 80, 75, 70, 65, 60, 55, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 or 1, in each case as weight percent, based on the total weight of the first cracker feed or the combined cracker feed (introduced into or within the tube as described above). Other examples include 5-50, 5-40, 5-35, 5-30, 5-25, 5-20 or 5-15 wt.%.

[0360] The first cracker stream is cracked in a first coil or tube. The second cracker stream is cracked in a second coil or tube. The first and second cracker streams and the first and second coils or tubes may be within the same cracker furnace.

[0361] The second cracker stream may contain no r-pyrolysis oil or contain less r-pyrolysis oil (by weight) than the first cracker feed stream. In addition, the second cracker stream may contain only non-recycled cracker feed in the second coil or tube. The second cracker feed stream may be primarily C2 to C4, or hydrocarbons (e.g., non-recycled components), or ethane, propane, or butane, in each case in an amount of at least 55, 60, 65, 70, 75, 80, 85, or at least 90 weight percent based on the second cracker feed in the second coil or tube. If r-pyrolysis oil is included in the second cracker feed, the amount of such r-pyrolysis oil by weight may be at least 10%, 20, 30, 40, 50, 60, 70, 80, 90, 95, 97, or 99% less than the amount of r-pyrolysis oil in the first cracker feed.

[0362] In one embodiment or in combination with any embodiment described herein, although not shown, an evaporator may be provided to evaporate the condensed feed of C2-C5 hydrocarbons 350 to ensure that the feed to the coil inlet in the convection box 312 or the inlet of the convection zone 310 is primarily a vapor phase feed.

[0363] Figure 5 The cracking furnace shown in FIG3 includes a convection section or zone 310, a radiant section or zone 320, and a cross section or zone 330 located between the convection section and the radiant sections 310 and 320. The convection section 310 is the portion of the furnace 300 that receives heat from the hot flue gases and includes a row of tubes or coils 324 through which the cracker stream 350 passes. In the convection section 310, the cracker stream 350 is heated by convection from the hot flue gases passing therethrough. The radiant section 320 is the section of the furnace 300 that primarily transfers heat to the heater tubes by radiation from the hot gases. The radiant section 320 also includes a plurality of burners 326 for introducing heat into the lower portion of the furnace. The furnace includes a combustion chamber 322 that surrounds and houses the tubes within the radiant section 320, and the burners are oriented into the combustion chamber. The crossover section 330 includes piping for connecting the convection section 310 and the radiant section 320 and can transfer the heated cracker stream from inside or outside one section to another within the furnace 300 .

[0364] As the hot combustion gases rise upward through the furnace, the gases may pass through a convection section 310 where at least a portion of the waste heat may be recovered and used to heat the cracker stream passing through the convection section 310. In one embodiment or in combination with any of the embodiments mentioned herein, the cracking furnace 300 may have a single convection (preheat) section 310 and a single radiant section 320, while in other embodiments, the furnace may include two or more radiant sections that share a common convection section. At least one induced draft (ID) fan 316 near the furnace may control the flow of the hot flue gases and the distribution of heat through the furnace, and one or more heat exchangers 340 may be used to cool the furnace effluent 370. In one embodiment or in combination with any of the embodiments mentioned herein (not shown), in addition to or in lieu of Figure 5 The exchanger shown in FIG. 5 (eg, a transfer line heat exchanger or TLE) may use a liquid quench to cool the cracked olefin-containing effluent.

[0365] The furnace 300 also includes at least one furnace coil 324 through which the cracker stream passes through the furnace. The furnace coil 324 can be formed from any material that is inert to the cracker stream and suitable for withstanding the high temperatures and thermal stresses within the furnace. The coil can have any suitable shape and can, for example, have a circular or oval cross-sectional shape.

[0366] The diameter of the coils or tubes within the coils in the convection section 310 can be at least 1, or at least 1.5, or at least 2, or at least 2.5, or at least 3, or at least 3.5, or at least 4, or at least 4.5, or at least 5, or at least 5.5, or at least 6, or at least 6.5, or at least 7, or at least 7.5, or at least 8, or at least 8.5, or at least 9, or at least 9.5, or at least 10, or at least 10.5, in each case cm, and / or no more than 12, or no more than 11.5, or no more than 11, 1, or no more than 0.5, or no more than 10, or no more than 9.5, or no more than 9, or no more than 8.5, or no more than 8, or no more than 7.5, or no more than 7, or no more than 6.5, in each case cm. All or a portion of one or more coils can be substantially straight, or one or more coils can include spirals, twists, or spiral segments. One or more coils can also have a U-tube or split U-tube design. In one embodiment or in combination with any embodiment mentioned herein, the interior of the tube can be smooth or substantially smooth, or a portion (or all) can be roughened to minimize coking. Alternatively, or in addition, the interior of the tube can include inserts or fins and / or surface metal additives to prevent coke buildup.

[0367] In one embodiment or in combination with any of the embodiments described herein, all or a portion of one or more furnace coils 324 passing through the convection section 310 may be oriented horizontally, while all or at least a portion of the furnace coils passing through the radiant section 322 may be oriented vertically. In one embodiment or in combination with any of the embodiments described herein, a single furnace coil may extend through both the convection and radiant sections. Alternatively, at least one coil may be split into two or more tubes at one or more points within the furnace, allowing the cracker stream to pass in parallel along multiple paths. For example, the cracker stream (including r-pyrolysis oil) 350 may be introduced into multiple coil inlets in the convection section 310, or into multiple tube inlets in the radiant section 320 or the crossover section 330. When multiple coils or tube inlets are introduced simultaneously or nearly simultaneously, the amount of r-pyrolysis oil introduced into each coil or tube may not be adjusted. In one embodiment or in combination with any of the embodiments described herein, the r-pyrolysis oil and / or cracker stream may be introduced into a common header, which then directs the r-pyrolysis oil to the multiple coils or tube inlets.

[0368] A single furnace can have at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8 or more, in each case a coil. Each coil can be 5 to 100, 10 to 75, or 20 to 50 meters long and can include at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 10, or at least 12, or at least 14 or more tubes. The tubes of a single coil can be arranged in many configurations and, in one embodiment or in combination with any of the embodiments mentioned herein, can be connected by one or more 180° ("U" shaped) bends. Figure 6 One example of a furnace coil 410 having a plurality of tubes 420 is shown in FIG.

[0369] The olefins plant can have a single cracking furnace, or it can have at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8 or more cracking furnaces operating in parallel. Any one or each furnace can be a gas cracker or a liquid cracker or a cracking furnace. In one embodiment or in combination with any 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, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, or at least 90 wt.% ethane, propane, LPG, or a combination thereof, based on the weight of all cracker feeds to the furnace. In one embodiment or in combination with any embodiment mentioned herein, the furnace is a liquid or naphtha cracker that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.% of C5-C 22 In one embodiment or in combination with any embodiment mentioned herein, the cracker is a cracking furnace that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, or at least 90 wt.% ethane, propane, LPG, or a combination thereof, and receives a cracker feed stream containing at least 0.5 wt.%, or at least 0.1 wt.%, or at least 1 wt.%, or at least 2 wt.%, or at least 5 wt.%, or at least 7 wt.%, or at least 10 wt.%, or at least 13 wt.%, or at least 15 wt.%, or at least 20 wt.% liquids and / or r-pyrolysis oil (when measured at 25°C and 1 atm), each based on the weight of all cracker feeds to the furnace.

[0370] Now turn Figure 7 , showing several possible locations for introducing the feed stream containing r-pyrolysis oil and the non-recovery cracker feed stream into the cracking furnace.

[0371] In one embodiment or in combination with any embodiment described herein, the feed stream 550 containing r-pyrolysis oil can be combined with the non-recovered cracker feed 552 upstream of the convection section to form a combined cracker feed stream 554, which can then be introduced into the convection section 510 of the furnace. Alternatively or additionally, the feed 550 containing r-pyrolysis oil can be introduced into a first furnace coil, while the non-recovered cracker feed 552 can be introduced into a separate or second furnace coil, within the same furnace or within the same convection zone. The two streams can then travel parallel to each other through the convection section 510 within the convection box 512, the crossover 530, and the radiant section 520 within the radiant box 522, such that each stream is substantially fluidly isolated from the other stream for most or all of its path from the inlet to the outlet of the furnace. The pyrolysis stream introduced into any heating zone within the convection section 510 can flow through the convection section 510 and into the radiant box 522 as the vaporized stream 514b. In other embodiments, the feed stream 550 containing r-pyrolysis oil may also be introduced into the non-recovery cracker stream 552 as it flows through the furnace coils in the convection section 510 into the cross section 530 of the furnace to form the combined cracker stream 514a, also as shown. Figure 7 As shown in .

[0372] In one embodiment or in combination with any of the embodiments mentioned herein, the Figure 7 The first or second heating zone shown introduces r-pyrolysis oil 550 into the first furnace coil, or an additional amount into the second furnace coil. The r-pyrolysis oil 550 may be introduced into the furnace coil at these locations via nozzles. A convenient method of introducing the r-pyrolysis oil feed is via one or more dilution steam feed nozzles which are used to feed steam into the coils in the convection zone. The services of one or more dilution steam nozzles may be used to inject r-pyrolysis oil, or new nozzles may be fastened to the coils specifically for the injection of r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, both steam and r-pyrolysis oil may be fed together into the furnace coil via nozzles downstream of the coil inlet and upstream of the crossover, optionally in the first or second heating zone within the convection zone, as Figure 7 shown.

[0373] When introduced into the furnace and / or when combined with a feed containing r-pyrolysis oil, the non-recovery cracker feed stream may be primarily liquid and have a vapor fraction of less than 0.25 (by volume) or less than 0.25 (by weight), or it may be primarily vapor and have a vapor fraction of at least 0.75 (by volume) or at least 0.75 (by weight). Similarly, the feed containing r-pyrolysis oil may be primarily vapor or primarily liquid when introduced into the furnace and / or combined with the non-recovery cracker stream.

[0374] In one embodiment or in combination with any of the embodiments mentioned herein, at least a portion or all of the r-pyrolysis oil stream or cracker feed stream may be preheated prior to introduction into the furnace. Figure 8 As shown, preheating can be performed with an indirect heat exchanger 618 heated by a heat transfer medium (e.g., steam, hot condensate, or a portion of the olefin-containing effluent) or via a directly fired heat exchanger 618. The preheating step can vaporize all or a portion of the stream comprising r-pyrolysis oil, and can, for example, vaporize at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 weight percent of the stream comprising r-pyrolysis oil.

[0375] When preheating is performed, the temperature of the stream containing r-pyrolysis oil can be increased to a temperature within about 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 2° C. of the bubble point temperature of the stream containing r-pyrolysis oil. Additionally or alternatively, preheating can increase the temperature of the stream containing r-pyrolysis oil to a temperature that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 100° C. below the coking temperature of the stream. In one embodiment or in combination with any embodiment mentioned herein, the preheated r-pyrolysis oil stream can have a temperature of at least 200, 225, 240, 250, or 260° C., and / or no more than 375, 350, 340, 330, 325, 320, or 315° C., or at least 275, 300, 325, 350, 375, or 400° C., and / or no more than 600, 575, 550, 525, 500, or 475° C. When an atomized liquid (as described below) is injected into the vapor-phase heated cracker stream, the liquid can evaporate rapidly such that, for example, the entire combined cracker stream is vapor (e.g., 100% vapor) within 5, 4, 3, 2, or 1 second of injection.

[0376] In one embodiment or in combination with any embodiment mentioned herein, the heated r-pyrolysis oil stream (or cracker stream comprising r-pyrolysis oil and non-recovery cracker stream) can optionally be passed through a vapor liquid separator to remove any residual heavy components or liquid components (when present). The resulting light fraction can then be introduced into the cracking furnace alone or in combination with one or more other cracker streams described in various embodiments herein. For example, in one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil stream can comprise at least 1, 2, 5, 8, 10, or 12 weight percent C 15 The separation can remove at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 weight percent of the heavier components from the r-pyrolysis oil stream.

[0377] Back to Figure 7, the cracker feed stream (alone or when combined with the r-pyrolysis oil feed stream) can be introduced into the furnace coils at or near the inlet of the convection section. The cracker stream can then pass through at least a portion of the furnace coils in the convection section 510, and dilution steam can be added at some points to control the temperature and cracking severity in the furnace. In one embodiment or in combination with any 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 stream containing r-pyrolysis oil and a non-recovered cracker stream (alone or in combination with steam) can also be introduced into the convection section or upstream of or at the inlet of the convection section, or downstream of the inlet of the convection section - in the convection section, at the cross section, or at the inlet of the radiant section. Steam may be combined with the r-pyrolysis oil stream and / or the cracker stream, and the combined stream may be introduced at one or more of these locations, or steam and r-pyrolysis oil and / or non-recovery cracker stream may be added separately.

[0378] 70, 760, 750, 740, 730, 720, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, or 650°C when combined with steam and fed into or near the crossover section of the furnace. The resulting steam and r-pyrolysis oil stream may have a vapor fraction of at least 0.75, 0.80, 0.85, 0.90, or at least 0.95 by weight, or at least 0.75, 0.80, 0.85, 0.90, and 0.95 by volume.

[0379] When combined with steam and fed into or near the inlet of convection section 510, the r-pyrolysis oil and / or cracker stream may have a temperature of at least 30, 35, 40, 45, 50, 55, 60, or 65, and / or no more than 100, 90, 80, 70, 60, 50, or 45°C.

[0380] The amount of steam added may depend on the operating conditions, including the feed type and the desired product, but may be added to achieve a steam to hydrocarbon ratio of at least 0.10:1, 0.15:1, 0.20:1, 0.25:1, 0.27:1, 0.30:1, 0.32:1, 0.35:1, 0.37:1, 0.40:1, 0.42:1, 0.45:1, 0.47:1, 0.50:1, 0.52:1, 0.55:1, 0.57:1, 0.60:1, 0.62:1, 0.65:1, and / or : 1, or it may be in the range of 0.1:1 to 1.0:1, 0.15:1 to 0.9:1, 0.2:1 to 0.8:1, 0.3:1 to 0.75:1, or 0.4:1 to 0.6:1. When determining the "steam to hydrocarbon" ratio, all hydrocarbon components are included and the ratio is by weight. In one embodiment or in combination with any embodiment described herein, steam may be used in the same furnace ( Figure 7 Steam may be added to the cracker feed (or any intermediate cracker stream within the furnace) when the cracker stream has a vapor fraction of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90.

[0381] When the feed stream containing r-pyrolysis oil is introduced into the cracking furnace separately from the non-recycled feed stream, the molar flow rate of the r-pyrolysis oil and / or the stream containing r-pyrolysis oil can be different from the molar flow rate of the non-recycled feed stream. In one embodiment or in combination with any of the other mentioned embodiments, there is provided a process for producing one or more olefins by:

[0382] (a) feeding a first cracker stream having r-pyrolysis oil to a first tube inlet in a cracker furnace;

[0383] (b) feeding a second cracker stream containing or consisting essentially of C2-C4 hydrocarbons to a second tube inlet in the cracking furnace, wherein the second tube is separate from the first tube and the total molar flow rate of the first cracker stream fed at the first tube inlet is less than the total molar flow rate of the second cracker stream to the second tube inlet calculated in the absence of the influence of steam. The feeds to steps (a) and (b) may be to separate coil inlets.

[0384] For example, when the r-pyrolysis oil or the first cracker stream passes through the tubes in the cracking furnace, its molar flow rate can be higher than the hydrocarbon components (e.g., C2-C4 or C5-C6) in the non-recycled feed stream or the second cracker stream. 22 ) component through the other or second tube is at least 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55, or 60 percent lower. When steam is present in the g-pyrolysis oil-containing stream or the first cracker stream and in the second cracker stream or the non-recycled feed stream, the total molar flow rate of the g-pyrolysis oil-containing stream or the first cracker stream (including the g-pyrolysis oil and the dilution steam) may be at least 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55, or 60 percent higher than the total molar flow rate (including hydrocarbons and dilution steam) of the non-recycled cracker feed or the second cracker stream (wherein the percentage is calculated as the difference between the two molar flow rates divided by the flow rate of the non-recycled stream).

[0385] In one embodiment or in combination with any embodiment mentioned herein, the molar flow rate of the r-pyrolysis oil in the feed stream containing r-pyrolysis oil to the furnace tubes (the first cracker stream) can be greater than the molar flow rate of the hydrocarbons (e.g., C2-C4 or C5-C6) in the non-recovery cracker stream (the second cracker stream). 22) is at least 0.01, 0.02, 0.025, 0.03, 0.035, and / or no more than 0.06, 0.055, 0.05, 0.045 kmol lb / hr lower. In one embodiment or combination with any embodiment mentioned herein, the molar flow rates of the g-pyrolysis oil and the cracker feed stream can be substantially similar such that the two molar flow rates are within 0.005, 0.001, or 0.0005 kmol lb / hr of each other. The molar flow rate of the r-pyrolysis oil in the furnace tubes may be at least 0.0005, 0.001, 0.0025, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15 kmol-lb / hr, and / or no more than 0.25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15 kmol-lb / hr. 25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, and / or no more than 0.25, 0.01, or 0.008 kmol lb / hr, while the molar flow rate of the hydrocarbon component in the other one or more 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 no more than 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 kmol lb / hr.

[0386] In one embodiment or in combination with any embodiment mentioned herein, the total molar flow rate of the stream containing r-pyrolysis oil (the first cracker stream) can be at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 less than the total molar flow rate of the non-recycled feed stream (the second cracker stream), and / or no more than 0.30, 0.25, 0.20, 0.15, 0.13, 0.10, 0.09, 0.08, 0.07, or 0.06 kilomol pounds per hour, or the same as the total molar flow rate of the non-recycled feed stream (the second cracker stream). The total molar flow rate of the gamma-pyrolysis oil-containing stream (the first cracker stream) may be at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, and / or no more than 0.10, 0.09, 0.08, 0.07, or 0.06 kmol lb / hr greater than the total molar flow rate of the second cracker stream, while the total molar flow rate of the non-recycled feed stream (the second cracker stream) may be at least 44, 0.43, 0.42, 0.41, 0.40 kmol lb / hr.

[0387] In one embodiment or in combination with any of the embodiments mentioned herein, the stream containing r-pyrolysis oil or the first cracker stream has a steam to hydrocarbon ratio that differs from the steam to hydrocarbon ratio of the non-recycled feed stream or the second cracker stream by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80%. The steam to hydrocarbon ratio can be higher or lower. For example, the steam to hydrocarbon ratio of the stream containing r-pyrolysis oil or the first cracker stream can differ from the steam to hydrocarbon ratio of the non-recycled feed stream or the second cracker stream by at least 0.01, 0.025, 0.05, 0.075, 0.10, 0.125, 0.15, 0.175, or 0.20 and / or no more than 0.3, 0.27, 0.25, 0.22, or 0.20. The steam to hydrocarbon ratio of the gamma-pyrolysis oil containing stream or the first cracker stream can be at least 0.3, 0.32, 0.35, 0.37, 0.4, 0.42, 0.45, 0.47, 0.5, and / or no more than 0.7, 0.67, 0.65, 0.62, 0.6, 0.57, 0.55, 0.52 or 0.5 and the steam to hydrocarbon ratio of the non-recycled cracker feed or the second cracker stream can be at least 0.02, 0.05, 0.07, 0.10, 0.12, 0.15, 0.17, 0.20, 0.25 and / or no more than 0.45, 0.42, 0.40, 0.37, 0.35, 0.32 or 0.30.

[0388] In one embodiment or in combination with any of the embodiments mentioned herein, the temperature of the stream containing r-pyrolysis oil as it passes through the crossover section in the cracking furnace can be different from the temperature of the non-recovery cracker feed as it passes through the crossover section when the streams are introduced separately through the furnace. For example, the temperature of the r-pyrolysis oil stream as it passes through the crossover section can differ from the temperature of the non-recovery hydrocarbon stream (e.g., C2-C4 or C5-C22) as it passes through the crossover section in another coil by at least 0.01, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75%. This percentage can be calculated based on the temperature of the non-recovery stream according to the following formula:

[0389] [(r - temperature of pyrolysis oil stream - temperature of non-recovery cracker stream)] / (temperature of non-recovery cracker steam), expressed as a percentage.

[0390] The difference may be higher or lower. The average temperature of the stream containing r-pyrolysis oil at the cross section may be at least 400, 425, 450, 475, 500, 525, 550, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620 or 625°C and / or not more than 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525 or 500°C, instead of recycling The average temperature of the cracker feed may be at least 401, 426, 451, 476, 501, 526, 551, 560, 565, 570, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620 or 625°C and / or no more than 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525 or 500°C.

[0391] The heated cracker stream typically has a temperature of at least 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670 or 680°C and / or no more than 850, 840, 830, 820, 810, 800, 790, 780, 770, 760 , 750, 740, 730, 720, 710, 705, 700, 695, 690, 685, 680, 675, 670, 665, 660, 655 or 650°C, or a temperature in the range of 500 to 710°C, 620 to 740°C, 560 to 670°C or 510 to 650°C, can then be transferred from the convection section to the radiant section of the furnace via a cross section.

[0392] In one embodiment or in combination with any of the embodiments mentioned herein, a feed stream containing r-pyrolysis oil can be added to the cracker stream at a crossover section. When introduced into the furnace in the crossover section, the r-pyrolysis oil can be at least partially vaporized, for example, by preheating the stream in a direct or indirect heat exchanger. When evaporated or partially vaporized, the stream containing r-pyrolysis oil has a vapor fraction of at least 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 0.99 by weight, or in one embodiment or in combination with any of the embodiments mentioned, by volume.

[0393] When the stream containing r-pyrolysis oil is atomized before entering the intersection section, one or more atomizing nozzles can be used for atomization. Atomization can be carried out in the furnace or outside the furnace. In one embodiment or in combination with any embodiment mentioned herein, an atomizing agent can be added to the stream containing r-pyrolysis oil during or before the atomization of the stream containing r-pyrolysis oil. The atomizing agent can include steam, or it can mainly include ethane, propane or its combination. When used, the atomizing agent can be at least 1, 2, 4, 5, 8, 10, 12, 15, 10, 25 or 30 weight percent, and / or be no more than 50, 45, 40, 35, 30, 25, 20, 15 or 10 weight percent in the amount of the stream to be atomized (for example, the composition containing r-pyrolysis oil).

[0394] The atomized or gasified 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 stream containing r-pyrolysis oil can be injected into the cracker feed stream using at least one nozzle, and the nozzle can be oriented to discharge the atomized stream at an angle of about 45, 50, 35, 30, 25, 20, 15, 10, 5, or 0° from vertical. The nozzle or nozzles can also be oriented to discharge the atomized stream into the coils in the furnace at an angle of about 30, 25, 20, 15, 10, 8, 5, 2, or 1° parallel to the axial centerline of the coils at the introduction point. In the cross and / or convection section of the furnace, at least two, three, four, five, six, or more nozzles can be used to perform the step of spraying the atomized r-pyrolysis oil.

[0395] In one embodiment or in combination with any embodiment mentioned herein, atomized r-pyrolysis oil, alone or in combination with at least a portion of the non-recovery cracker stream, can be fed into the inlet of one or more coils in the convection section of the furnace. The temperature of such atomization can be at least 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80°C, and / or no more than 120, 110, 100, 90, 95, 80, 85, 70, 65, 60, or 55°C.

[0396] In one embodiment or in combination with any embodiment mentioned herein, the temperature of the atomized or vaporized stream can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350°C cooler than the temperature of the cracker stream to which it is added, and / or no more than 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 75, 70, 60, 55, 50, 45, 40, 30, or 25°C cooler than the temperature of the cracker stream to which it is added. The resulting combined cracker stream comprises a continuous gas phase and a discontinuous liquid phase (or droplets or particles) dispersed therein. The atomized liquid phase may comprise r-pyrolysis oil, while the gas phase may comprise primarily C2-C4 components, ethane, propane, or 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, in one embodiment or combination with any of the embodiments mentioned, by volume.

[0397] The temperature of the cracker stream passing through the crossover section may be at least 500, 510, 520, 530, 540, 550, 555, 560, 565, 570, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620, 625, 630, 635, 640, 645, 650, 660, 670 or 680°C, and / or no more than 850, 840, 830, 820, 810, 800, 890, 900, 910, 920, 930, 940, 950, 960, 970 or 980°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, 510 to 630°C.

[0398] The resulting cracker feed stream then enters the radiant section. In one embodiment or in combination with any of the embodiments mentioned herein, the cracker stream from the convection section (with or without r-pyrolysis oil) can be passed through a vapor liquid separator to separate the stream into heavy and light fractions before further cracking the light fractions in the radiant section of the furnace. Figure 8 An example of this is shown in .

[0399] In one embodiment or in combination with any of the embodiments mentioned herein, the vapor liquid separator 640 can include a flash tank, while in other embodiments, it can include a fractionation column. As the stream 614 passes through the vapor liquid separator 640, the gas stream impinges on and flows through the trays, while the liquid from the trays falls to the bottom stream 642. The vapor liquid separator can also include a demister or chevron or other device located near the vapor outlet to prevent liquid from being carried over from the vapor liquid separator 640 into the gas outlet.

[0400] Within the convection section 610, the temperature of the cracker stream can be increased by at least 50, 75, 100, 150, 175, 200, 225, 250, 275, or 300°C, and / or no more than about 650, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, or 275°C so that the passage of the heated cracker stream exiting the convection section 610 through the vapor liquid separator 640 can be carried out at a temperature of at least 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650°C, and / or no more than 800, 775, 750, 725, 700, 675, 650, 625°C. When heavier components are present, at least a portion or substantially all of the heavier components may be removed in the heavy components as bottom stream 642. At least a portion of the light fraction 644 from separator 640 may be removed alone or with one or more other cracker streams, such as primarily C5-C 22 The hydrocarbon stream or the combination of C2-C4 hydrocarbon streams is introduced into the cross section or radiation zone pipe 624 after separation.

[0401] refer to Figure 5 and 6 , the cracker feed stream (non-recycled cracker feed stream or when combined with the r-pyrolysis oil feed stream) 350 and 650 can be introduced into the furnace coils at or near the inlet of the convection section. The cracker feed stream can then pass through at least a portion of the furnace coils in the convection sections 310 and 610, and dilution steam 360 and 660 can be added at some points to control the temperature and cracking severity in the radiant sections 320 and 620. The amount of steam added can depend on the furnace operating conditions, including the feed type and the desired product distribution, but can be added to achieve a steam to hydrocarbon ratio in the range of 0.1 to 1.0, 0.15 to 0.9, 0.2 to 0.8, 0.3 to 0.75, or 0.4 to 0.6 by weight. In one embodiment or in combination with any embodiment described herein, steam can be used in the same furnace ( Figure 5 Steam 360 and 660 may be added to the cracker feed (or any intermediate cracker feed stream within the furnace) when the cracker feed stream has a vapor fraction by weight of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90, or by volume in one embodiment or combination of any of the mentioned embodiments.

[0402] The heated cracker stream typically has a temperature of at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case °C, and / or no more than 850, or no more than 840, or no more than 830, or no more than 820, or no more than 810, or no more than 800, or no more than 790, or no more than 780, or no more than 770 , or not more than 760, or not more than 750, or not more than 740, or not more than 730, or not more than 720, or not more than 710, or not more than 705, or not more than 700, or not more than 695, or not more than 690, or not more than 685, or not more than 680, or not more than 675, or not more than 670, or not more than 665, or not more than 660, or not more than 655°C, or not more than 650°C, in each case °C, or in the range of 500 to 710°C, 620 to 740°C, 560 to 670°C, or 510 to 650°C, and then may pass from the convection section 610 of the furnace to the radiant section 620 via the crossover section 630. In one embodiment or in combination with any embodiment mentioned herein, the feed stream 550 containing r-pyrolysis oil may be added to the cracker stream at the crossover section 530, such as Figure 6When introduced into the furnace at the intersection, the r-pyrolysis oil may be at least partially vaporized or atomized before being combined with the cracker stream at the intersection. The temperature of the cracker stream passing through the intersection 530 or 630 may be at least 400, 425, 450, 475, or at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case ° C, and / or no more than 850, or no more than 840, or no more than 830, or no more than 820, or no more than 8 ℃ or less, or in the range of 620 to 740 ℃, 550 to 680 ℃ or 510 to 630 ℃.

[0403] The resulting cracker feed stream is then passed through a radiant section, wherein the feed stream containing the gamma-pyrolysis oil is thermally cracked to form lighter hydrocarbons, including olefins such as ethylene, propylene, and / or butadiene. The residence time of the cracker feed stream in the radiant section may be at least 0.1, or at least 0.15, or at least 0.2, or at least 0.25, or at least 0.3, or at least 0.35, or at least 0.4, or at least 0.45, in each case seconds, and / or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.9, or no more than 0.8, or no more than 0.75, or no more than 0.7, or no more than 0.65, or no more than 0.6, or no more than 0.5, in each case seconds. The temperature at the inlet of the furnace coil is at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case °C, and / or not more than 850, or not more than 840, or not more than 830, or not more than 820, or not more than 810, or not more than 800, or not more than 790, or not more than 780, or not more than 790 or not more than 770, or not more than 760, or not more than 750, or not more than 740, or not more than 730, or not more than 720, or not more than 710, or not more than 705, or not more than 700, or not more than 695, or not more than 690, or not more than 685, or not more than 680, or not more than 675, or not more than 670, or not more than 665, or not more than 660, or not more than 655°C, or not more than 650°C, in each case in °C, or in the range of 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.

[0404] The coil outlet temperature may be at least 640, or at least 650, or at least 660, or at least 670, or at least 680, or at least 690, or at least 700, or at least 720, or at least 730, or at least 740, or at least 750, or at least 760, or at least 770, or at least 780, or at least 790, or at least 800, or at least 810, or at least 820, in each case °C, and / or no more than 1000, or no more than 990, or no more than 980, or not more than 970, or not more than 960, or not more than 950, or not more than 940, or not more than 930, or not more than 920, or not more than 910, or not more than 900, or not more than 890, or not more than 880, or not more than 875, or not more than 870, or not more than 860, or not more than 850, or not more than 840, or not more than 830, in each case °C, in the range of 730 to 900°C, 750 to 875°C, or 750 to 850°C.

[0405] The cracking performed in the furnace coils can include cracking the cracker feed stream under a set of process conditions that include a target value for at least one operating parameter. Examples of suitable operating parameters include, but are not limited to, maximum cracking temperature, average cracking temperature, average tube outlet temperature, maximum tube outlet temperature, and average residence time. When the cracker stream further includes steam, the operating parameters can include hydrocarbon molar flow rate and total molar flow rate. When two or more cracker streams pass through separate coils in the furnace, one of the coils can operate under a first set of process conditions, and at least one of the other coils can operate under a second set of process conditions. At least one target value for an operating parameter from a first set of processing conditions can differ from the target value for the same parameter in a second set of conditions by at least 0.01, 0.03, 0.05, 0.1, 0.25, 0.5, 1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95%, and / or no more than about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15%. Examples include 0.01 to 30, 0.01 to 20, 0.01 to 15, 0.03 to 15%. The percentage is calculated according to the following formula:

[0406] [(Measured value of the operating parameter) - (Target value of the operating parameter)] / [(Target value of the operating parameter)], expressed as a percentage.

[0407] As used herein, the term "different" means higher or lower.

[0408] The coil outlet temperature may be at least 640, 650, 660, 670, 680, 690, 700, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820°C and / or no more than 1000, 990, 980, 970, 960, 950, 940, 930, 920, 910, 900, 890, 880, 875, 870, 860, 850, 840, 830°C, within the range of 730 to 900°C, 760 to 875°C or 780 to 850°C.

[0409] In one embodiment or in combination with any embodiment mentioned herein, the addition of r-pyrolysis oil to the cracker feed stream can result in a change in one or more of the aforementioned operating parameters compared to the value of the operating parameter when the same cracker feed stream is processed in the absence of r-pyrolysis oil. For example, the value of one or more of the aforementioned parameters can differ (e.g., be higher or lower) by at least 0.01, 0.03, 0.05, 0.1, 0.25, 0.5, 1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% compared to the value of the same parameter when the same feed stream is processed without r-pyrolysis oil. The percentage is calculated according to the following formula:

[0410] [(Measured value of the operating parameter) - (Target value of the operating parameter)] / [(Target value of the operating parameter)], expressed as a percentage.

[0411] 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 example, in one embodiment or in combination with any of the embodiments described herein, when a cracker stream without r-pyrolysis oil is present, the cracker can be operated to achieve a first coil outlet temperature (COT1). Next, r-pyrolysis oil can be added to the cracker stream via any of the methods described herein, and the combined stream can be cracked to achieve a second coil outlet temperature (COT2) that is different from COT1.

[0412] In some cases, when the r-pyrolysis oil is heavier than the cracker stream, COT2 may be less than COT1, while in other cases, when the r-pyrolysis oil is lighter than the cracker stream, COT2 may be greater than or equal to COT1. When the r-pyrolysis oil is lighter than the cracker stream, it may have a 50% boiling point that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% higher than the 50% boiling point of the cracker stream, and / or no more than 80, 75, 70, 65, 60, 55, or 50%. The percentages are calculated according to the following formula:

[0413] [(r-50% boiling point of pyrolysis oil in °R)-(50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0414] Alternatively or additionally, the 50% boiling point of the r-pyrolysis oil may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100° C. lower than the 50% boiling point of the cracker stream, and / or not more than 300, 275, 250, 225, or 200° C. The heavier cracker stream may include, for example, vacuum gas oil (VGO), atmospheric gas oil (AGO), or even coker gas oil (CGO), or combinations thereof.

[0415] When the r-pyrolysis oil is lighter than the cracker stream, it may have a 50% boiling point that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% lower than the 50% boiling point of the cracker stream, and / or no more than 80, 75, 70, 65, 60, 55, or 50%. The percentages are calculated according to the following formula:

[0416] [(r - 50% boiling point of pyrolysis oil) - (50% boiling point of cracker stream)] / [(50% boiling point of cracker stream)], expressed as a percentage.

[0417] Additionally or alternatively, the 50% boiling point of the r-pyrolysis oil may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100° C. higher than the 50% boiling point of the cracker stream, and / or not more than 300, 275, 250, 225, or 200° C. The lighter cracker stream may include, for example, LPG, naphtha, kerosene, natural gasoline, straight-run gasoline, and combinations thereof.

[0418] In some cases, COT1 may differ from COT2 (either above or below) by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50°C, and / or by no more than about 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70, or 65°C, or COT1 may differ from COT2 by at least 0.3, 0.6, 1, 2, 5, 10, 15, 20, or 25, and / or by no more than 80, 75, 70, 65, 60, 50, 45, or 40% (wherein a percentage 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 may be at least 730, 750, 77, 800, 825, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, and / or no more than 1200, 1175, 1150, 1140, 1130, 1120, 1110, 1100, 1090, 1080, 1070, 1060, 1050, 1040, 1030, 1020, 1010, 1000, 990, 980, 970, 960950, 940, 930, 920, 910 or 900°C.

[0419] In one embodiment or combination with any embodiment mentioned herein, the mass velocity of the cracker feed stream through at least one or at least two radiant coils (for clarity, as determined across the entire coil as opposed to tubes within the coil) is between 60 and 165 kilograms per second (kg / s) per square meter (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 When steam is present, the mass velocity is based on the total flow rate of hydrocarbons and steam.

[0420] In one embodiment or in combination with any of the mentioned embodiments, there is provided a process for preparing one or more olefins by:

[0421] (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit;

[0422] (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and

[0423] (c) cracking the combined cracker stream 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.

[0424] The reason or cause for the temperature drop of the second coil outlet temperature (COT2) is not limited, as long as COT2 is lower than the first coil outlet temperature (COT1). In one embodiment or in combination with any of the aforementioned embodiments, in one embodiment or in combination with any of the other aforementioned embodiments, the COT2 temperature on the coil of the r-pyrolysis oil feed can be set to a temperature lower than COT1 ("set" mode), or at least 1, 2, 3, 4, or at least 5°C lower than COT1, or can be allowed to change or float without setting the temperature on the coil of the r-pyrolysis oil feed ("free floating" mode).

[0425] In the set mode, COT2 can be set to at least 5°C lower than COT1. All coils in the furnace can be fed with a feed stream containing r-pyrolysis oil, or at least one, or at least two coils can be fed with a feed stream containing r-pyrolysis oil. In either case, at least one of the coils containing r-pyrolysis oil can be in the set mode. By reducing the cracking severity of the combined cracking stream, the lower thermal energy required to crack the r-pyrolysis oil can be utilized when its average number average molecular weight is higher than that of the cracker feed stream, such as a gaseous C2-C4 feed. Although the cracking severity of the cracker feed (e.g., C2-C4) can be reduced, thereby increasing the amount of unconverted C2-C4 feed in a single pass, a higher amount of unconverted feed (e.g., C2-C4 feed) is required to increase the final yield of olefins, such as ethylene and / or propylene, in multiple passes by recycling the unconverted C2-C4 feed through the furnace. Alternatively, other cracker products, such as aromatics and diene content, can be reduced.

[0426] In one embodiment or in combination with any of the above embodiments, when the hydrocarbon mass flow rate of the combined cracker stream in at least one coil is equal to or less than the hydrocarbon mass flow rate of the cracker stream in step (a) in said coil, the COT2 in the coil can be fixed in the set mode to be lower than COT1, or at least 1, 2, 3, 4, or at least 5°C lower. 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. Fixed 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 the pyrolysis oil because higher molecular weight molecules require less thermal energy to crack. If it is desired to avoid over-cracking of the pyrolysis oil, a reduced COT2 temperature can help reduce by-product formation, and while the single-pass olefin yield is also reduced, the final yield of olefins can be satisfactory or increased by recycling unconverted cracker feed through the furnace.

[0427] In set mode, the temperature can be fixed or set by adjusting the furnace to burner fuel ratio.

[0428] In one embodiment or in combination with any of the other mentioned embodiments, COT2 is in free floating mode and is the result of feeding pyrolysis oil and allowing COT2 to rise or fall without fixing the temperature of the coils containing the pyrolysis oil feed. In this embodiment, not all of the coils contain r-pyrolysis oil. The heat energy provided to the coils containing r-pyrolysis oil can be provided by maintaining a constant temperature or fuel feed rate to the burners on the coils containing the non-recycled cracker feed. Without fixing or setting COT2, when pyrolysis oil is fed to the cracker stream to form a combined cracker stream having a higher hydrocarbon mass flow rate than the hydrocarbon mass flow rate of the cracker stream in step (a), COT2 can be lower than COT1. Adding pyrolysis oil to the cracker feed to increase the hydrocarbon mass flow rate of the combined cracker feed reduces COT2 and can exceed the warming effect of using a higher average molecular weight pyrolysis oil. These effects can be seen while other cracker conditions are kept constant, such as the dilution steam ratio, feed location, composition of the cracker feed and pyrolysis oil, and the fuel feed rate to the combustor burners in the furnace on tubes containing only cracker feed and no r-pyrolysis oil feed.

[0429] COT2 may be lower than COT1, or at least 1, 2, 3, 4, 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, 50°C lower, and / or no more than about 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70, or 65°C lower than COT1.

[0430] Regardless of the cause or origin of the temperature drop in COT2, the time period for engaging step (a) is flexible, but ideally, step (a) reaches steady state before engaging step (b). In one embodiment or in combination with any of the aforementioned embodiments, step (a) operates for at least 1 week, or at least 2 weeks, or at least 1 month, or at least 3 months, or at least 6 months, or at least 1 year, or at least 1.5 years, or at least 2 years. Step (a) can be represented by a cracking furnace that has never been operated to receive a pyrolysis oil feed or a combination of a pyrolysis oil feed and a pyrolysis oil feed. Step (b) can be the first time the furnace has received a pyrolysis oil feed or a combination cracker feed containing pyrolysis oil. In one embodiment or in combination with any of the other mentioned embodiments, steps (a) and (b) can be repeated 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 feed of pyrolysis oil is adjusted to represent multiple cycles of steps (a) and (b). When the feed supply of pyrolysis oil is depleted or shut off, COT1 is allowed to reach a steady-state temperature before engaging step (b).

[0431] Alternatively, the feeding of pyrolysis oil to the cracker feed may be continuous throughout the course of at least 1 calendar year or at least 2 calendar years.

[0432] In one embodiment or in combination with any of the other mentioned embodiments, the composition of the cracker feed used in steps (a) and (b) remains constant, allowing for regular compositional changes to be observed over the course of a calendar year. In one embodiment or in combination with any of the other mentioned embodiments, the flow of cracker feed in step (a) is continuous and remains continuous as the pyrolysis oil enters the cracker feed to prepare the combined cracker feed. The cracker feeds in steps (a) and (b) may be taken from the same source, such as the same stockpile or pipeline.

[0433] In one embodiment or combination with any of the mentioned embodiments, COT2 is lower or at least 1, 2, 3, 4, or at least 5°C lower for at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 85%, or at least 90%, or at least 95% of the time that the pyrolysis oil is fed to the cracker stream to form the combined cracker stream, measured when all conditions other than COT are held constant, such as cracking furnace and pyrolysis oil feed rates, steam ratio, feed location, composition of the cracking furnace feed and pyrolysis oil, etc.

[0434] In one embodiment or in combination with any of the embodiments mentioned, the hydrocarbon mass flow rate of the combined cracker feed can be increased. A method for producing one or more olefins by the following steps is now provided:

[0435] (a) cracking a cracker stream at a first hydrocarbon mass flow rate (MF1) in a cracking unit;

[0436] (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream, the combined cracker stream having a second hydrocarbon mass flow rate (MF2) greater than MF1; and

[0437] (c) cracking the combined cracker stream in the cracking unit at MF2 to obtain an olefin-containing effluent having a combined yield of ethylene and propylene that is the same as or higher than that obtained by cracking only the cracker stream at MF1.

[0438] Yield refers to the production of the target compound per unit time, expressed as weight, e.g., kg / hr. Increasing the mass flow rate of the cracker stream by adding r-pyrolysis oil can increase the combined ethylene and propylene production, thereby increasing the furnace throughput. Without being bound by theory, it is believed that this is possible because the total energy of the reaction with the added pyrolysis oil is not endothermic relative to the total energy of the reaction with lighter cracker feeds, such as propane or ethane. Because the heat flux to the furnace is limited and the total heat of reaction with the pyrolysis oil is less endothermic, more limited heat energy is available per unit time 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 the coils fed with r-pyrolysis oil, or can be increased by at least 1, 2, 3, 5, 7, 10, 10, 13, 15, 18, or 20%, as measured by furnace throughput, provided that at least one coil is processing r-pyrolysis oil. Alternatively, the increase in combined ethylene and propylene production can be achieved without changing the heat flux in the furnace, or the r-pyrolysis oil feed coil outlet temperature, or the fuel feed rate to the burners used to heat the coils containing only non-recycled cracker feed, or the fuel feed rate to any burners in the furnace. The higher hydrocarbon mass flow rate of MF2 in the coils containing r-pyrolysis oil can be passed through one or at least one coil in the furnace, or through two or at least two, or 50% or at least 50%, or 75% or at least 75%, or through all coils in the furnace.

[0439] The olefin-containing effluent stream may have a total yield of propylene and ethylene from the combined cracker streams at MF2 that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% greater than the yield of propylene and ethylene of the effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, as determined by:

[0440]

[0441] Among them O mf1 is the combined yield of propylene and ethylene content in the cracker effluent without the use of MF1 made with r-pyrolysis oil; mf2 is the combined yield of propylene and ethylene content in the cracker effluent under MF2 made using r-pyrolysis oil.

[0442] The total production of propylene and ethylene in the combined cracker stream at MF2 in the olefin-containing effluent stream is, as a percentage, at least 1, 5, 10, 15, 20%, and / or at most 80, 70, 65% of the increase in mass flow rate between MF2 and MF1. Examples of suitable ranges include 1 to 80, or 1 to 70, or 1 to 65, or 5 to 80, or 5 to 70, or 5 to 65, or 10 to 80, or 10 to 70, or 10 to 65, or 15 to 80, or 15 to 70, or 15 to 65, or 20 to 80, or 20 to 70, or 20 to 65, or 25 to 80, or 25 to 70, or 26 to 65, or 35 to 80, or 35 to 70, or 35 to 65, or 40 to 80, or 40 to 70, or 40 to 65, each expressed as a percentage. For example, if the percentage difference between MF2 and MF1 is 5%, and the total production of propylene and ethylene increases by 2.5%, then the increase in olefins as a function of the increase in mass flow rate is 50% (2.5% / 5% x 100). This can be determined as:

[0443]

[0444] where ΔO% is the percentage increase (using the above formula) between the combined production of propylene and ethylene content in the cracker effluent for MF1 produced without r-pyrolysis oil and MF2 produced with r-pyrolysis oil; and

[0445] ΔMF% is the percentage of increase in MF2 compared to MF1.

[0446] Alternatively, the olefin-containing effluent stream may have a total wt.% of propylene and ethylene from the combined cracker stream at MF2 that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% higher than the wt.% of propylene and ethylene of the effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, as determined by:

[0447]

[0448] Among them E mf1 is the combined wt.% of propylene and ethylene content in the cracker effluent without using r-pyrolysis oil; E mf2 is the combined wt.% of propylene and ethylene content in the cracker effluent at MF2 made using r-pyrolysis oil.

[0449] Also provided is a process for preparing one or more olefins, the process comprising:

[0450] (a) cracking a cracker stream in a cracking furnace to provide a first olefin-containing effluent exiting the cracking furnace at a first coil outlet temperature (COT1);

[0451] (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and

[0452] (c) cracking the combined cracker stream in the cracking unit to provide a second olefin-containing effluent exiting the cracking furnace at a second coil outlet temperature (COT2),

[0453] wherein, when the r-pyrolysis oil is heavier than the cracker stream, COT2 is equal to or less than COT1,

[0454] Wherein, when the r-pyrolysis oil is lighter than the cracker stream, COT2 is greater than or equal to COT1.

[0455] In this method, the above embodiments are applicable for COT2 being lower than COT1. COT2 can be in set mode or free-floating mode. In one embodiment or in combination with any of the other mentioned embodiments, COT2 is in free-floating mode, and the hydrocarbon mass flow rate of the combined cracker stream in step (b) is higher than the hydrocarbon mass flow rate of the cracker stream in step (a). In one embodiment or in combination with any of the mentioned embodiments, COT2 is in set mode.

[0456] In one embodiment or in combination with any of the mentioned embodiments, there is provided a process for preparing one or more olefins by:

[0457] (a) cracking a cracker stream at a first coil outlet temperature (COT1) in a cracking unit;

[0458] (b) after step (a), adding a stream comprising a recycled component pyrolysis oil composition (r-pyrolysis oil) to the cracker stream to form a combined cracker stream; and

[0459] (c) cracking the combined cracker stream in the cracking unit at a second coil outlet temperature (COT2), wherein the second coil outlet temperature is higher than the first coil outlet temperature.

[0460] COT2 may be at least 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, 50°C higher than COT1, and / or no more than about 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70, or 65°C higher.

[0461] In one embodiment or in combination with any of the other mentioned embodiments, r-pyrolysis oil is added to the inlet of at least one coil, or at least two coils, or at least 50%, or at least 75%, or all of the 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 number of coils receiving r-pyrolysis oil feed. At least one, at least two, or at least all of the coils fed with r-pyrolysis oil may have a COT2 greater than their respective COT1. In one embodiment or in combination with any of the mentioned embodiments, at least one, at least two, or at least 50%, or at least 75% of the coils within the cracking furnace contain only non-recycled cracker feed, wherein at least one coil in the cracking furnace is fed with r-pyrolysis oil, and at least some of the coils or coils fed with r-pyrolysis oil have a COT2 greater than their respective COT1.

[0462] In one embodiment or in combination with any of the mentioned embodiments, the hydrocarbon mass flow rate of the combined stream in step (b) is substantially equal to or lower than the hydrocarbon mass flow rate of the cracker stream in step (a). Substantially the same means no more than 2% difference, or no more than 1% difference, or no more than 0.25% difference. When the hydrocarbon mass flow rate of the combined cracker stream in step (b) is substantially equal to or lower than the hydrocarbon mass flow rate of cracker stream (a), and COT2 is allowed to operate in a free-floating mode (wherein at least 1 tube contains a non-recycled cracker stream), COT2 on the coil containing r-pyrolysis oil can be increased relative to COT1. This is true even if the pyrolysis oil, having a larger number average molecular weight than the cracker stream, requires less energy to crack. Without being bound by theory, it is believed that one factor or combination of factors contributes to the temperature rise, including the following:

[0463] (i) requiring less thermal energy to crack the pyrolysis oil in the combined stream; or

[0464] (ii) Exothermic reactions such as Diels-Alder reactions occur in the cracking products of the pyrolysis oil.

[0465] This effect is seen when other process variables are constant, such as combustor fuel rate, dilution steam ratio, feed location, and cracker feed composition.

[0466] In one embodiment or in combination with any of the embodiments mentioned, COT2 can be set or fixed to a higher temperature than COT1 (set mode). This is particularly applicable when the hydrocarbon mass flow rate of the combined cracker stream is higher than the hydrocarbon mass flow rate of the cracker stream, which would otherwise reduce COT2. A higher second coil outlet temperature (COT2) can help increase the severity and reduce the yield of unconverted lighter cracker feeds (e.g., C2-C4 feeds), which can help with downstream capacity-constrained fractionators.

[0467] In one embodiment or in combination with any of the embodiments mentioned, regardless of whether COT2 is higher or lower than COT1, when comparing between COT2 and COT1, the cracker feed composition is the same. Desirably, the cracker feed composition in step (a) is the same cracker composition as the cracker composition used to prepare the combined cracker stream in step (b). Alternatively, the cracker composition feed in step (a) is fed continuously to the cracker unit, and the pyrolysis oil in step (b) is added to the continuous cracker feed in step (a). Alternatively, the pyrolysis oil is fed to the cracker feed continuously 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.

[0468] In any of the mentioned embodiments, the amount of the cracker feed increased or decreased in step (b) can be at least 2%, or at least 5%, or at least 8%, or at least 10%. In one embodiment or combination with any of the mentioned embodiments, the amount of the cracker feed decreased in step (b) can be an amount corresponding to the addition of pyrolysis oil by weight. In one embodiment or combination with any of the mentioned embodiments, the mass flow rate of the combined cracker feed is at least 1%, or at least 5%, or at least 8%, or at least 10% higher than the hydrocarbon mass flow rate of the cracker feed in step (a).

[0469] In any or all of the mentioned embodiments, the cracker feed or combined cracker feed mass flow rate and COT relationship and measurement is satisfied if any one coil in the furnace satisfies the relationship, but may exist in multiple tubes depending on how the pyrolysis oil is fed and distributed.

[0470] In one embodiment or combination with any embodiment mentioned herein, the burners in the radiant zone provide an average heat flux into the coil of 60 to 160 kW / m 2 , or 70 to 145kW / m 2 , or 75 to 130kW / m 2 The maximum (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 (bara), or 2.5 to 7 bar, and the outlet pressure of the furnace coil in the radiant section is in the range of 1.03 to 2.75 bar, or 1.03 to 2.06 bar. The pressure drop across the furnace coil in the radiant section 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.

[0471] In one embodiment or in combination with any embodiment mentioned herein, the yield of olefins-ethylene, propylene, butadiene or a combination thereof can be at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, in each case as a percentage. As used herein, the term "yield" refers to mass of product / mass of feedstock × 100%. The olefin-containing effluent stream comprises at least about 30, or at least 40, or at least 50, or at least 60, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case as a weight percent of ethylene, propylene, or ethylene and propylene, based on the total weight of the effluent stream.

[0472] In one embodiment or in combination with one or more embodiments described herein, the olefin-containing effluent stream 670 can comprise C2-C4 olefins, or propylene, or ethylene, or C4 olefins in an amount of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 weight percent, based on the weight of the olefin-containing effluent. The stream can comprise primarily ethylene, primarily propylene, or primarily ethylene and propylene, based on the weight of the olefins in the olefin-containing effluent, based on the weight of the C1-C5 hydrocarbons in the olefin-containing effluent, or based on the weight of the olefin-containing effluent stream. The weight ratio of ethylene to propylene in the olefin-containing effluent stream may be at least about 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1, and / or no more than 3:1, 2.9:1, 2.8:1, 2.7:1, 2.5:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.7:1, 1.5:1, or 1.25:1. In one embodiment or in combination with one or more embodiments mentioned herein, the olefin-containing effluent stream can have a propylene:ethylene ratio that is higher than the propylene:ethylene ratio of the effluent stream obtained by cracking the same cracker feed but without r-pyrolysis oil at the same dilution steam ratio, feed location, cracker feed composition (other than r-pyrolysis oil), and floating the coils fed with r-pyrolysis oil, or at the same temperature before feeding r-pyrolysis oil if all coils in the furnace are fed with r-pyrolysis oil. As described above, this is possible when the mass flow rate of the cracker feed remains substantially the same when r-pyrolysis oil is added relative to the original feed to the cracker stream, resulting in a higher hydrocarbon mass flow rate of the combined cracker stream.

[0473] The olefin-containing effluent stream may have a propylene:ethylene ratio that is at least 1% higher, or at least 2% higher, or at least 3% higher, or at least 4% higher, or at least 5% higher, or at least 7% higher, or at least 10% higher, or at least 12% higher, or at least 15% higher, or at least 17% higher, or at least 20% higher than the propylene:ethylene ratio of an effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil. Alternatively, in addition, the olefin-containing effluent stream may have a propylene:ethylene ratio that is up to 50% higher, or up to 45% higher, or up to 40% higher, or up to 35% higher, or up to 25% higher, or up to 20% higher than the propylene:ethylene ratio of an effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, in each case determined as:

[0474]

[0475] where E is the propylene:ethylene ratio in the cracker effluent produced without the use of r-pyrolysis oil, in wt.%; E r is the propylene:ethylene ratio in the cracker effluent prepared using r-pyrolysis oil, in wt.%.

[0476] In one embodiment or in combination with any embodiment mentioned herein, relative to the effluent stream not containing r-pyrolysis oil, the amount of ethylene and propylene in the olefin-containing effluent stream of cracking can keep substantially unchanged or increase. Surprisingly, liquid r-pyrolysis oil can be fed to a gas feed furnace, which accepts and cracks mainly C2-C4 compositions and obtains an olefin-containing effluent stream, which can keep substantially unchanged or improve relative to the C2-C4 cracker feed not containing r-pyrolysis oil in some cases. The high molecular weight of r-pyrolysis oil can mainly contribute to the formation of aromatic hydrocarbons, and only participates in the formation of olefins (particularly ethylene and propylene) on a small scale. However, we find that, under identical hydrocarbon mass flow rates, relative to the cracker feed not containing r-pyrolysis oil, when r-pyrolysis oil is added to the cracker feed to form a combined cracker feed, the combined weight percent of ethylene and propylene, even output, does not significantly decline, and in many cases, keeps the same or may increase. The olefin-containing effluent stream may have a combined wt.% of propylene and ethylene that is equal to or at least 0.5%, or at least 1%, or at least 2%, or at least 2.5% greater than the propylene and ethylene content of an effluent stream obtained by cracking the same cracker feed but without the r-pyrolysis oil, as determined by:

[0477]

[0478] Where E is the combined wt.% of propylene and ethylene in the cracker effluent produced without using r-pyrolysis oil; E r is the combined wt.% of propylene and ethylene content in the cracker effluent produced using r-pyrolysis oil, which.

[0479] In one embodiment or in combination with one or more embodiments mentioned herein, the wt.% of propylene in the olefin-containing effluent stream can be increased when the dilution steam ratio (weight ratio of steam: hydrocarbons) is greater than 0.3, or greater than 0.35, or at least 0.4. When the dilution steam ratio is at least 0.3, or at least 0.35, or at least 0.4, the increase in propylene wt.% can 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 the increase is measured as the simple difference in propylene wt.% between an olefin-containing effluent stream prepared with an r-pyrolysis oil having a dilution steam ratio of 0.2 and an olefin-containing effluent stream prepared with an r-pyrolysis oil having a dilution steam ratio of at least 0.3, all other conditions being equal.

[0480] When the dilution steam ratio is increased as described above, the propylene:ethylene ratio may also increase, or may be at least 1% higher, or at least 2% higher, or at least 3% higher, or at least 4% higher, or at least 5% higher, or at least 7% higher, or at least 10% higher, or at least 12% higher, or at least 15% higher, or at least 17% higher, or at least 20% higher than the propylene:ethylene ratio of an olefin-containing effluent stream produced using r-pyrolysis oil having a dilution steam ratio of 0.2.

[0481] In one embodiment or in combination with one or more embodiments described herein, the olefin-containing effluent stream can have a reduced wt.% of methane as the dilution steam ratio increases, when measured relative to the olefin-containing effluent stream at a dilution steam ratio of 0.2. The wt.% of methane in the olefin-containing effluent stream can be reduced by at least 0.25 wt.%, or at least 0.5 wt.%, or at least 0.75 wt.%, or at least 1 wt.%, or at least 1.25 wt.%, or at least 1.5 wt.%, measured as the absolute difference in wt.% between the olefin-containing effluent stream at a dilution steam ratio of 0.2 and a higher dilution steam ratio.

[0482] In one embodiment or in combination with one or more embodiments mentioned herein, when measuring relative to the cracker feed that does not contain r-pyrolysis oil and all other conditions identical (comprising hydrocarbon mass flow rate), the amount of unconverted products in the olefins effluent is reduced.For example, the amount of propane and / or ethane can be reduced by adding r-pyrolysis oil.This can help reduce the mass flow rate of recovery loop, thereby (a) reduces low-temperature energy cost and / or (b) if equipment is capacity-limited, then increase the capacity of equipment potentially. In addition, if propylene fractionator has reached its capacity limit, then it can eliminate the bottleneck of propylene fractionator.The amount of unconverted products in the olefins effluent can reduce 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%.

[0483] In one embodiment or in combination with one or more embodiments mentioned herein, when measured relative to a cracker feed not containing r-pyrolysis oil, the amount of unconverted products in the olefin-containing effluent (e.g., propane and ethane amounts combined) decreases, while the combined and output of ethylene and propylene does not decline and even improves. Alternatively, all other conditions are identical, including hydrocarbon mass flow rate and temperature, wherein the fuel feed rate of the heating burner to the non-recovery cracker feed coil remains unchanged, or alternatively when the fuel feed rate to all coils in the furnace remains unchanged. Alternatively, the same relationship can be established on a wt.% basis rather than on a yield basis.

[0484] For example, the total amount (either yield or wt. %) of propane and ethane in the olefin-containing effluent can be reduced by at least 2%, or at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15%, or at least 18%, or at least 20%, and in each case up to 40%, or up to 35%, or up to 30%, in each case without a reduction in the total amount of ethylene and propylene, and can even be accompanied by an increase in the total amount of ethylene and propylene. For example, the amount of propane in the olefin-containing effluent can be reduced by at least 2%, or at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15%, or at least 18%, or at least 20%, and in each case up to 40%, or up to 35%, or up to 30%, in each case without a reduction in the total amount of ethylene and propylene, and can even be accompanied by an increase in the total amount of ethylene and propylene. In any of these embodiments, the cracker feed (other than r-pyrolysis oil and as fed to the inlet of the convection zone) can be primarily propane, or at least 90 mol% propane, or at least 95 mol% propane, or at least 96 mol% propane, or at least 98 mol% propane on a molar basis; or the fresh supply of cracker feed can be at least HD5 quality propane.

[0485] 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, when 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 can be no more than 0.50:1, or less than 0.50:1, or no more than 0.48:1, or no more than 0.46:1, or no more than 0.43:1, or no more than 0.40:1, or no more than 0.38:1, or no more than 0.35:1, or no more than 0.33:1, or no more than 0.30:1. A low ratio means that high amounts of ethylene+propylene can be achieved or maintained while correspondingly reducing unconverted products such as propane.

[0486] In one embodiment or in combination with one or more embodiments mentioned herein, when the r-pyrolysis oil and steam are fed downstream of the inlet of the convection box, or when one or both of the r-pyrolysis oil and steam are fed at a crossover position, the C 6+ The amount of product can be increased if such product is desired, for example for a BTX stream to prepare its derivatives. When r-pyrolysis oil and steam are fed downstream of the convection box inlet, the C in the olefin-containing effluent is about 100% when measured relative to feeding r-pyrolysis oil at the convection box inlet. 6+ The amount of product may be increased by 5%, or 10%, or 15%, or 20%, or 30%, all other conditions being the same. The % increase may be calculated as:

[0487]

[0488] Among them E i The C in the olefin-containing cracker effluent prepared by introducing r-pyrolysis oil at the inlet of the convection box 6+ content; and

[0489] E d The C in the olefin-containing cracker effluent is obtained by introducing pyrolysis oil and steam downstream of the convection box inlet. 6+ content.

[0490] In one embodiment or in combination with any embodiment described herein, the cracked olefin-containing effluent stream can contain relatively small amounts of aromatic hydrocarbons and other heavy components. For example, the olefin-containing effluent stream can contain at least 0.5, 1, 2, or 2.5 weight percent, and / or no more than about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 weight percent aromatic hydrocarbons, based on the total weight of the stream. We have found that C 6+ The level of the substance 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, and all paraffins and cyclic compounds having 6 or more carbon atoms. As used throughout the text, the amount of aromatic hydrocarbons referred to can be determined by C 6+ The amount of substance is expressed because the amount of aromatic hydrocarbons will not exceed C 6+ The amount of substance.

[0491] The olefin-containing effluent may have a ratio of at least 2:1, 3.1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1 1, 7: 1, 8: 1, 9: 1, 10: 1, 15: 1, or 5: 1. As used herein, "olefins to aromatics" is the ratio of the total weight of C2 and C3 olefins to the total weight of aromatics, as defined above. In one embodiment or in combination with any embodiment mentioned herein, the effluent stream can have at least 2.5:1, 2.75:1, 3.5:1, 4.5:1, 5.5:1, 6.5:1, 7.5:1, 8.5:1, 9.5:1, 10.5:1, 11.5:1, 12.5:1, or 13:5:1 olefins to aromatics.

[0492] The olefin-containing effluent may have olefins: C 6+ The olefin-containing effluent may have an olefin:C ratio (by weight) of at least 8.5:1, or at least 9.5:1, or at least 10:1, or at least 10.5:1, or at least 12:1, or at least 13:1, or at least 15:1, or at least 17:1, or at least 19:1, or at least 20:1, or at least 25:1, or at least 28:1, or at least 30:1. Additionally or alternatively, the olefin-containing effluent may have an olefin:C ratio of at least 8.5:1, or at least 9.5:1, or at least 10:1, or at least 10.5:1, or at least 12:1, or at least 13:1, or at least 15:1, or at least 17:1, or at least 19:1, or at least 20:1, or at least 25:1, or at least 28:1, or at least 30:1. 6+ The ratio is at most 40: 1, or at most 35: 1, or at most 30: 1, or at most 25: 1, or at most 23: 1. As used herein, "olefins to aromatics" is the ratio of the total weight of C2 and C3 olefins to the total weight of aromatics as defined above.

[0493] Additionally or alternatively, the olefin-containing effluent stream may have olefins and C 6+The ratio is at least about 1.5:1, 1.75:1, 2:1, 2.25:1, 2.5:1, 2.75:1, 3:1, 3.25:1, 3.5:1, 3.75:1, 4:1, 4.25:1, 4.5:1, 4.75:1, 5:1, 5.25:1, 5.5:1, 5.75:1, 6:1, 6.25:1, 6 .5:1, 6.75:1, 7:1, 7.25:1, 7.5:1, 7.75:1, 8:1, 8.25:1, 8.5:1, 8.75:1, 9:1, 9.5:1, 10:1, 10.5:1, 12:1, 13:1, 15:1, 17:1, 19:1, 20:1, 25:1, 28:1 or 30:1.

[0494] In one embodiment or combination with any of the embodiments described herein, the olefin:aromatic ratio decreases as the amount of r-pyrolysis oil added to the cracker feed increases. Because r-pyrolysis oil cracks at a lower temperature, it will crack earlier than propane or ethane and therefore has more time to react to produce other products, such as aromatics. Although the aromatic content of the olefin-containing effluent increases with increasing pyrolysis oil content, as described above, the amount of aromatics produced is significantly low.

[0495] Olefin composition can also comprise trace aromatic hydrocarbons.For example, composition can have at least 0.25,0.3,0.4,0.5 weight percent, and / or be no more than about 2,1.7,1.6,1.5 weight percent of benzene content.Additionally or alternatively, composition can have at least 0.005,0.010,0.015 or 0.020 and / or be no more than 0.5,0.4,0.3 or 0.2 weight percent of toluene content.Two percentages are all based on the gross weight of composition.Alternatively or additionally, the benzene content of effluent can be at least 0.2,0.3,0.4,0.5 or 0.55 weight percent, and / or be no more than about 2,1.9,1.8,1.7 or 1.6 weight percent, and / or toluene content can be at least 0.01,0.05 or 0.10 weight percent, and / or be no more than 0.5,0.4,0.3 or 0.2 weight percent.

[0496] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent taken out from the cracking furnace of the composition comprising r-pyrolysis oil can include an increased amount of one or more compounds or by-products not present in the olefin-containing effluent stream formed by processing conventional cracker feed. For example, the cracker effluent formed by cracking r-pyrolysis oil (r-olefin) can include an increased amount of 1,3-butadiene, 1,3-cyclopentadiene, dicyclopentadiene or a combination of these components. In one embodiment or in combination with any embodiment mentioned herein, the total amount (by weight) of these components can be higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without r-pyrolysis oil treatment by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85%. The total amount of 1,3-butadiene (by weight) can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without the r-pyrolysis oil treatment. The total amount of 1,3-cyclopentadiene (by weight) can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without the r-pyrolysis oil treatment. The total amount of dicyclopentadiene (by weight) can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% higher than the same cracker feed stream under the same conditions and at the same mass feed rate but without the r-pyrolysis oil treatment. The percentage difference is calculated by dividing the difference in weight percentage of one or more of the above components in the r-pyrolysis oil and the conventional stream by the amount of the component in the conventional stream (by weight percentage), or:

[0497]

[0498] wherein E is the wt.% of the components in the cracker effluent produced without using r-pyrolysis oil; and

[0499] E r is the wt.% of the components in the cracker effluent made with r-pyrolysis oil.

[0500] In one embodiment or in combination with any of the embodiments described herein, the olefin-containing effluent stream can include acetylene. The amount of acetylene can 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 stream from the furnace. It can 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.

[0501] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream can include methylacetylene and propadiene (MAPD). The amount of MAPD can be at least 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 gross weight of the effluent stream. It can also be no more than 50,000 ppm, no more than 40,000 ppm, or no more than 30,000 ppm, or no more than 10,000 ppm, or no more than 6,000 ppm, or no more than 5,000 ppm.

[0502] In one embodiment or in combination with any embodiment mentioned herein, the olefin-containing effluent stream can contain little or no carbon dioxide. The olefin-containing effluent stream can have an amount of carbon dioxide, measured in wt.%, that is no more than the amount of carbon dioxide in an effluent stream obtained by cracking the same cracker feed under equivalent conditions but without r-pyrolysis oil, or an amount that is no more than 5%, or no more than 2%, of the amount of carbon dioxide, measured in wt.%, or the same amount as a comparative effluent stream without r-pyrolysis oil. Alternatively or additionally, the olefin-containing effluent stream can have an amount of carbon dioxide that is no more than 1000 ppm, or no more than 500 ppm, or no more than 100 ppm, or no more than 80 ppm, or no more than 50 ppm, or no more than 25 ppm, or no more than 10 ppm, or no more than 5 ppm.

[0503] Now go to Figure 9 , a block diagram illustrating the main elements of the furnace effluent processing section is shown.

[0504] like Figure 9 As shown, the olefin-containing effluent stream from the cracking furnace 700, which includes the recovered components, is rapidly cooled (e.g., quenched) in a transfer line exchange ("TLE") 680, as shown. Figure 8As shown, to prevent the production of large amounts of undesirable by-products and to minimize fouling in downstream equipment, as well as to generate steam. In one embodiment or in combination with any embodiment mentioned herein, the temperature of the effluent containing the r-composition from the furnace can be reduced by 35 to 485°C, 35 to 375°C, or 90 to 550°C to a temperature of 500 to 760°C. The cooling step is performed immediately after the effluent stream leaves the furnace, for example, within 1 to 30, 5 to 20, or 5 to 15 milliseconds. In one embodiment or in combination with any embodiment mentioned herein, the quenching step is performed in the quench zone 710 by heating the effluent in a heat exchanger (sometimes referred to as a transfer line exchanger, such as Figure 5 TLE 340 is shown and Figure 8 In some embodiments, the quenching step is performed by indirect heat exchange with high pressure water or steam in a quenching liquid 712 (shown as TLE 680 in FIG. 1 ), while in other embodiments, the quenching step is performed by direct contact of the effluent with a quenching liquid 712 (shown as Figure 9 ). The temperature of the quench liquid can be at least 65, or at least 80, or at least 90, or at least 100, in each case, and / or no more than 210, or no more than 180, or no more than 165, or no more than 150, or no more than 135, in each case, °C. When a quench liquid is used, contacting can be carried out in a quench tower, and a liquid stream comprising 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 vapor.

[0505] The resulting cooled effluent stream is then subjected to vapor-liquid separation, and the vapor is compressed in a compression zone 720, such as in a gas compressor having, for example, 1 to 5 compression stages, with optional interstage cooling and liquid removal. The gas stream pressure at the outlet of the first set of compression stages is in the range of 7 to 20 bar gauge (barg), 8.5-18 psig (0.6 to 1.3 barg), or 9.5 to 14 barg.

[0506] The resulting compressed stream is then treated in acid gas removal zone 722 to remove acid gases, including CO, CO2, and H2S, by contacting it with an acid gas removal agent. Examples of acid gas removal agents may include, but are not limited to, caustic amines and various types of amines. In one embodiment or in combination with any of the embodiments described herein, a single contactor may be used, while in other embodiments, a dual-tower absorber-stripper configuration may be employed.

[0507] The treated compressed olefin-containing stream can then be further compressed in another compression zone 724 via a compressor, 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.

[0508] Now go to Figure 10 , provides a schematic diagram of the main steps of the fractionation section. In one embodiment or in combination with any of the embodiments described herein, the initial column of the fractionation system may not be a demethanizer 810, but may be a deethanizer 820, a depropanizer 840, or any other type of column. As used herein, the term "demethanizer" refers to a column whose light bonds are methane. Similarly, "deethanizer" and "depropanizer" refer to columns having ethane and propane as light bond components, respectively.

[0509] like Figure 10As shown, the feed stream 870 from the quench section can be introduced into a demethanizer (or other) 810, wherein methane and lighter (CO, CO2, H2) components 812 are separated from ethane and heavier components 814. The demethanizer is operated at a temperature of at least -145, or at least -142, or at least -140, or at least -135, in each case, and / or no more than -120, -125, -130, -135°C. The bottoms stream 814 from the demethanizer is then introduced into a deethanizer 820 where the C2 and lighter components 816 are separated from the C3 and heavier components 818 by fractionation, said bottoms stream comprising at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%, in each case as a percentage, of the total amount of ethane and heavier components introduced into the column. The deethanizer 820 can be operated at an overhead temperature of at least -35, or at least -30, or at least -25, or at least -20, in each case, and / or no more than -5, -10, -10, -20°C, and an overhead pressure of at least 3, or at least 5, or at least 7, or at least 8, or at least 10, in each case, barg, and / or no more than 20, or no more than 18, or no more than 17, or no more than 15, or no more than 14, or no more than 13, in each case, barg. The deethanizer 820 recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case, a 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 embodiment mentioned herein, the overhead stream 816 removed from the deethanizer comprises at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case weight percent ethane and ethylene, based on the total weight of the overhead stream.

[0510] like Figure 10As shown, the C2 and lighter overhead stream 816 from the deethanizer 820 is further separated in an ethane-ethylene fractionator (ethylene fractionator) 830. In the ethane-ethylene fractionator 830, an ethylene and lighter components stream 822 can be withdrawn from the overhead of the column 830 or as a side stream from the overhead, while ethane and any remaining heavier components are removed in a bottoms stream 824. The ethylene fractionator 830 can be operated at an overhead temperature of at least -45, or at least -40, or at least -35, or at least -30, or at least -25, or at least -20, in each case, and / or no more than -15, or no more than -20, or no more than -25, in each case, and an overhead pressure of at least 10, or at least 12, or at least 15, in each case, barg, and / or no more than 25, 22, or 20 barg. The ethylene-rich overhead stream 822 can contain at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 98, or at least 99, in each case weight percent ethylene, based on the total weight of the stream, and can be sent to downstream processing units for further processing, storage, or sale. The overhead ethylene stream 822 produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-ethylene composition or stream. In one embodiment or in combination with any of the embodiments mentioned herein, the r-ethylene stream can be used to produce one or more petrochemical products.

[0511] The bottoms stream from the ethane-ethylene fractionator 824 can include at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98 weight percent ethane, in each case based on the total weight of the bottoms stream. As previously described, all or a portion of the recovered ethane can be recycled to the cracking furnace as additional feedstock, either alone or in combination with a feed stream containing r-pyrolysis oil.

[0512] The liquid bottoms stream 818 exiting the deethanizer may be enriched in C3 and heavier components and may be separated in the depropanizer 840, such as Figure 10In the depropanizer 840, C3 and lighter components are removed as an overhead vapor stream 826, while C4 and heavier components can exit the column in a liquid bottoms stream 828. The depropanizer 840 can be operated at an overhead temperature of at least 20, or at least 35, or at least 40, in each case, and / or no more than 70, 65, 60, or 55°C, and an overhead pressure of at least 10, or at least 12, or at least 15, in each case, barg, and / or no more than 20, or no more than 17, or no more than 15, in each case, barg. The depropanizer 840 recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case, a percentage of the total amount of C3 and lighter components introduced into the column in the overhead stream 826. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 826 removed from the depropanizer 840 comprises at least or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98, in each case weight percent of propane and propylene based on the total weight of the overhead stream 826.

[0513] The overhead stream 826 from the depropanizer 840 is introduced into a propane-propylene fractionator (propylene fractionator) 860, wherein propylene and any lighter components are removed in an overhead stream 832, while propane and any heavier components exit the column in a bottoms stream 834. The propylene fractionator 860 can be operated at an overhead temperature of at least 20, or at least 25, or at least 30, or at least 35, in each case, and / or no more than 55, 50, 45, or 40° C., and an overhead pressure of at least 12, or at least 15, or at least 17, or at least 20, in each case, barg, and / or no more than 20, or no more than 17, or no more than 15, or no more than 12, in each case, barg. The overhead stream 860 rich in propylene can contain at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 98, or at least 99, in each case, propylene weight percent, based on the gross weight of the stream, and can be sent to downstream processing units for further processing, storage, or sale. The overhead propylene stream produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-propylene composition or stream. In one embodiment or in combination with any of the embodiments mentioned herein, this stream can be used to prepare one or more petrochemical products.

[0514] The bottoms stream 834 from the propane-propylene fractionator 860 can include at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98 weight percent propane, in each case based on the total weight of the bottoms stream 834. As previously described, all or a portion of the recovered propane can be recycled to the cracking furnace as additional feedstock, either alone or in combination with the r-pyrolysis oil.

[0515] Refer again Figure 10 The bottom stream 828 from the depropanizer 840 can be fed to a debutanizer 850 for separating the C4 components, including butenes, butanes and butadiene, from the C 5+ Component separation. The debutanizer can be operated at a top temperature of at least 20, or at least 25, or at least 30, or at least 35, or at least 40, in each case, ° C., and / or no more than 60, or no more than 65, or no more than 60, or no more than 55, or no more than 50, in each case, ° C., and a top pressure of at least 2, or at least 3, or at least 4, or at least 5, in each case, barg, and / or no more than 8, or no more than 6, or no more than 4, or no more than 2, in each case, barg. The debutanizer recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case, a percentage of the total amount of C4 and lighter components introduced into the column in overhead 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 weight percent butadiene, based on the total weight of the overhead stream. The overhead stream 836 produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-butadiene composition or stream. The bottoms stream 838 from the debutanizer primarily contains C5 and heavier components in an amount of at least 50, or at least 60, or at least 70, or at least 80, or at least 90, or at least 95 weight percent, based on the total weight of the stream. The debutanizer bottoms stream 838 can be sent for further separation, processing, storage, sale, or use.

[0516] The overhead stream 836 or C4 from the debutanizer may be subjected to any conventional separation method such as extraction or distillation processes to recover a more concentrated butadiene stream.

[0517] Dehalogenation systems and processes

[0518] In one aspect, a method of producing pyrolysis oil and / or pyrolysis gas from a waste (eg, containing waste plastic) feed containing some halogen content is provided.

[0519] In one embodiment or in combination with any embodiment mentioned herein, reference Figure 2 , the waste plastic feed fed to the pretreatment unit 114 and / or the pyrolysis reactor 118 may contain at least 1, at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95 or at least 99, in each case by weight percent, of halogen-containing plastic, such as polyvinyl chloride.

[0520] In an embodiment, in the raw material pretreatment unit 114, the introduced waste plastics can undergo a pretreatment including dehalogenation, optionally in addition to other pretreatments described herein, such as washing, mechanical stirring, flotation, diameter reduction, separation. In one embodiment or in combination with any embodiment mentioned herein, the pretreatment unit 114 may include one or more systems or components that can at least partially dehalogenate the plastic raw material introduced into the unit 114. More particularly, the pretreatment unit 114 can remove at least a portion of halogen-containing (e.g., chlorine-containing) compounds from the raw material introduced into the unit 114, thereby forming a dehalogenated raw material. The removed halogen waste comprising the removed halogen-containing compound (e.g., chlorine-containing compound such as HCl) can be discarded from the pyrolysis system.

[0521] In one embodiment or in combination with any embodiment mentioned herein, the dehalogenation process within the pretreatment unit 114 can include one or more of the following steps: (i) physically separating solid halogen-containing waste plastic from at least one other type of waste plastic upstream (e.g., by using a flotation tank); (ii) melting and physically separating molten halogen-containing waste plastic from at least one other type of molten waste plastic; and (iii) heating the halogen-containing waste plastic to a temperature sufficient to crack at least a portion of the halogen-containing waste plastic to release a halogen-containing gas, such as gaseous hydrogen chloride, and then discharging the halogen-containing gas. The heating of step (iii) can be performed at a temperature of at least 150°C, at least 175°C, at least 200°C, at least 225°C, at least 250°C, at least 275°C, or at least 300°C and / or no more than 400°C, no more than 375°C, or no more than 350°C. The heating of step (iii) can be performed at a temperature in the range of 150°C to 400°C, 175°C to 375°C, or 250°C to 375°C. Discharge can be performed using a column with a discharge system, a piping system, a polycondensation reactor, a wiped film reactor, a stirred reactor, a vacuum, or a separator capable of removing at least a portion of the gaseous halogen-containing byproducts such as gaseous HCl.

[0522] In one embodiment or in combination with any embodiment mentioned herein, the dehalogenation process within the pretreatment unit 114 may include: (i) physically separating the solid halogen-containing waste plastic from at least one other type of waste plastic upstream (e.g., by using a flotation tank); and then (ii) heating the halogen-containing waste plastic to a temperature sufficient to crack at least a portion of the halogen-containing waste plastic to release a halogen-containing gas, such as gaseous hydrogen chloride, and then discharging the halogen-containing gas. The heating of step (ii) may be at least 150°C, at least 175°C, at least 200°C, at least 225°C, at least 250°C, at least 275°C, or at least 300°C and / or no more than 400°C, no more than 375°C, or no more than 350°C. The heating of step (ii) may be carried out at a temperature in the range of 150°C to 400°C, 175°C to 375°C, or 250°C to 375°C.

[0523] Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the dehalogenation process within the pretreatment unit 114 can include one or more of the following steps: (i) physically separating solid halogen-containing waste plast...

Claims

1. A method for preparing pyrolysis oil, the method comprising: (a) providing a plastic-containing feed comprising at least one halogen-containing waste plastic; (b) dehalogenating at least a portion of the plastic-containing feed, thereby forming a halogen waste stream and a dehalogenated feed; and (c) pyrolyzing at least a portion of the dehalogenated feed to form a pyrolysis effluent comprising pyrolysis oil, wherein the pyrolysis oil- (i) contains less than 25% by weight of aromatic hydrocarbons; (ii) contains an alkane content of at least 25% by weight; (iii) contains at least 90% of the boiling points of at least 350°C; and (iv) exhibiting a strength of less than 0.9 g / cm at 15°C 3 density, wherein the dehalogenation of step (b) comprises pre-treating the plastic-containing feed by heating to a temperature of at least 150° C. and not more than 325° C. for a time sufficient to remove at least 5% of the halogens initially present in the plastic-containing feed, thereby releasing a halogen-containing waste stream and forming a dehalogenated feed having a halogen content of not more than 1000 ppm, wherein the pyrolysis in step (c) is carried out at a temperature of at least 450° C. and not more than 1100° C.; and Wherein, the pyrolysis oil has not been hydrogenated.

2. The method of claim 1, wherein the dehalogenation comprises: (i) physically separating the halogen-containing waste plastics from at least one other type of waste plastics upstream of the pyrolysis unit, (ii) melting and physically separating the molten halogen-containing waste plastic from at least one other type of molten waste plastic, (iii) heating the halogen-containing waste plastics to a temperature of at least 150° C. and not more than 325° C. for a time sufficient to crack at least a portion of the halogen-containing waste plastics to remove at least 5% of the halogen initially present in the plastics-containing feed, thereby releasing a halogen-containing gas; subsequently discharging the halogen-containing gas to form a dehalogenated feed having a halogen content of not more than 1000 ppm; and absorbing the halogen-containing gas into a halogen scavenger.

3. The method of claim 1, wherein the dehalogenation comprises melting and physically separating the molten halogen-containing waste plastic from at least one other type of molten waste plastic. The method of claim 1 , wherein the dehalogenating comprises venting the halogen-containing gas.

5. The method of claim 1, wherein the dehalogenating comprises absorbing the halogen-containing gas into a halogen scavenger. 6 . The method of claim 5 , wherein the halogen scavenger comprises a metal oxide, a metal hydroxide, a carbon composite, or a combination thereof.

7. The method of claim 5, wherein the halogen scavenger comprises slaked lime, calcium carbonate, or a combination thereof.

8. The method of claim 1, wherein the dehalogenation removes at least 50% of the halogens initially present in the plastic-containing feed.

9. The method of claim 1, wherein the plastic-containing feed comprises at least 5 weight percent of at least one halogen-containing waste plastic.

10. The process of claim 1, wherein the dehalogenation feed comprises a halogen content of less than 1,000 ppm.

11. The method of claim 1 , wherein the pyrolysis oil comprises less than 5 weight percent aromatic hydrocarbon content.

12. The method of claim 1, wherein the pyrolysis oil exhibits a viscosity of at least 0.65 g / cm2 at 15°C. 3 and less than 0.9g / cm 3 density.

13. The method of claim 1, wherein the pyrolysis oil comprises a combined paraffin and olefin content of at least 55 weight percent and no more than 99 weight percent.

14. The method of claim 1, wherein the pyrolysis oil comprises a C6-C12 hydrocarbon content of at least 10 weight percent and less than 95 weight percent.

15. The method of claim 1 , wherein the pyrolysis oil comprises at least 1 weight percent and no more than 80 weight percent C13-C23 hydrocarbon content; and wherein the pyrolysis oil comprises at least 1 weight percent and less than 15 weight percent C24+ hydrocarbon content.

16. The method of claim 1, wherein the pyrolysis occurs at a temperature of at least 775°C and no more than 1,100°C.

17. The method of claim 1, wherein the pyrolysis occurs in the presence of a pyrolysis catalyst.

18. The method of claim 1, wherein the pyrolysis occurs in the absence of a pyrolysis catalyst.

19. The method of claim 1, wherein the pyrolysis oil comprises a C8+ hydrocarbon content of at least 35 wt. %, based on the total weight of the pyrolysis oil.

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