Recovery of component polyvinyl acetal

Abstract

A polyvinyl acetal composition, such as a polyvinyl butyral composition or a polyvinyl butyral resin, containing a recovered component can be prepared by preparing PVA using a recovered component aldehyde composition as a raw material, or by applying a recovery quota (e.g., a dispensing amount or a credit) to the aldehyde composition or the PVA composition. The recovered component is obtained by cracking the recovered component pyrolysis oil to produce various olefins such as propylene or ethylene.

Description

[0001] This application is a divisional application of the Chinese invention patent application with application number 202080077286.7, application date November 6, 2020, and invention name “Recycled component polyvinyl alcohol acetal”. Technical Field

[0002] The present invention relates to a recycled component in polyvinyl acetal, and in particular to a recycled component in polyvinyl acetal such as polyvinyl butyral, wherein the recycled component is directly or indirectly obtained from cracked recycled component pyrolysis oil. Background Art

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

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

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

[0006] Some recycling efforts involve complex and detailed separation of waste streams, which results in increased costs to obtain recycled waste components. For example, conventional methanolysis technology requires a high purity PET stream. Some downstream products are also very sensitive to dyes and inks present on the waste product, and their pre-treatment and removal also increase the cost of the raw materials manufactured from these wastes. It is desirable to establish recycled components that do not need to be classified as a single type of plastic or waste material, or that can tolerate multiple impurities in the waste stream flowing through the raw material.

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

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

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

[0010] It is also desirable to continue to purchase raw materials for the preparation of polyvinyl acetals from aldehydes prepared from olefins obtained from cracking facilities that are struggling due to the lack of economic attractiveness of production from natural gas fields or petroleum.

[0011] Furthermore, it is desirable that the polyvinyl acetal not rely solely on credits to establish recycled content in the polyvinyl acetal, thereby providing polyvinyl acetal manufacturers with multiple options for determining recycled content.

[0012] It is also desirable that the polyvinyl acetal manufacturer can determine the amount and timing of establishing recycled content. The polyvinyl acetal manufacturer may wish to establish more or less recycled content or no recycled content at certain times or for different batches. This method is desirable with flexibility and without the need for adding a large amount of investment. Summary of the invention

[0013] A method for obtaining recycled content polyvinyl acetal, recycled content aldehydes that can be used to prepare polyvinyl acetal, and articles made from or with recycled content polyvinyl acetal or containing recycled content polyvinyl acetal, its use, its composition, and its system are now provided, each of which is further described in the claims and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] 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).

[0015] 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.

[0016] Figure 3 is a schematic diagram of a pyrolysis process to produce an olefin-containing product.

[0017] Figure 4 is a block flow diagram showing the steps associated with the cracking furnace and separation zone of a system for producing an r-composition obtained from cracking r-pyrolysis oil and non-recovered cracker feed.

[0018] Figure 5 is a schematic diagram of a cracking furnace suitable for receiving r-pyrolysis oil.

[0019] Figure 6A furnace coil configuration with multiple tubes is shown.

[0020] Figure 7 Various feed positions of r-pyrolysis oil into the cracking furnace are shown.

[0021] Figure 8 A cracking furnace with a vapor liquid separator is shown.

[0022] Fig. 9 is a block diagram showing the process of recovering constituent furnace effluent.

[0023] Fig.10 A fractionation scheme is shown for separating and isolating the separation sections of the main r-compositions, including a demethanizer, a deethanizer, a depropanizer and a fractionation column, the main r-compositions including r-propylene, r-ethylene, r-butene, etc.

[0024] Fig.11 A laboratory scale cracking unit design is shown.

[0025] Fig.12 Design features for a plant-based experimental feeding of r-pyrolysis oil to a gas-fed cracking furnace are described.

[0026] Fig.13 is a boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis with 74.86% C8+, 28.17% C15+, 5.91% aromatics, 59.72% paraffins and 13.73% unidentified components.

[0027] Fig.14 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0028] Fig.15 The boiling point curve of r-pyrolysis oil obtained by gas chromatography analysis.

[0029] Fig.16 The boiling point curve of r-pyrolysis oil obtained by distillation in the laboratory and chromatography analysis.

[0030] Fig.17 is a boiling point graph of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350°C, 50% boils between 95°C and 200°C, and at least 10% boils at 60°C.

[0031] Fig.18 is a boiling point graph of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 150°C, 50% boils between 80°C and 145°C, and at least 10% boils at 60°C.

[0032] Fig.19is a boiling point graph of r-pyrolysis oil distilled in the laboratory, where at least 90% boils at 350°C, at least 10% boils at 150°C, and 50% boils between 220°C and 280°C.

[0033] Fig. 20 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with 90% boiling points between 250-300°C.

[0034] Fig.21 is a graph of the boiling point of r-pyrolysis oil distilled in the laboratory with 50% boiling point between 60-80°C.

[0035] Fig. 22 is a boiling point graph of r-pyrolysis oil distilled in the laboratory with 34.7% aromatic content.

[0036] Fig.23 This is a boiling point curve of the r-pyrolysis oil used in the factory trial experiment.

[0037] Fig.24 is a graph of the carbon distribution of the pyrolysis oil used in the plant experiments.

[0038] Fig.25 is a plot of the cumulative weight percent carbon distribution of the pyrolysis oil used in the plant experiments. DETAILED DESCRIPTION

[0039] As used herein, "containing" and "including" are open ended and synonymous with "comprising."

[0040] 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.

[0041] As used herein, "recycled content composition," "recycled composition," and "r-composition" refer to a composition having recycled content.

[0042] The term "pyrolysis recovery component" is used herein as a noun, i) to refer to a physical component (e.g., a compound, molecule, or atom) at least a portion of which is derived directly or indirectly from the pyrolysis of recovery waste, or ii) as an adjective modifying a specific composition (e.g., a feedstock, a product, or a stream) at least a portion of which is derived directly or indirectly from the pyrolysis of recovery waste. For example, the pyrolysis recovery component can be derived directly or indirectly from the cracking of the recovery component pyrolysis oil, the recovery component pyrolysis gas, or the recovery component pyrolysis oil, such as by a thermal steam cracker or a fluid catalytic cracker.

[0043] As used herein, "pyrolysis recycled content composition", "pyrolysis recycled composition" and "pr-composition" refer to a composition (e.g., compound, polymer, feedstock, product or stream) having pyrolysis recycled content. The pr-composition is a subset of the r-composition, wherein at least a portion of the recycled content of the r-composition is derived directly or indirectly from the pyrolysis of recycled waste.

[0044] As used herein, a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "directly derived" or "derived directly" from recycled waste has at least one physical component traceable to recycled waste, while a composition (e.g., a compound, polymer, feedstock, product, or stream) that is "indirectly derived" or "derived indirectly" from recycled waste has a recycled component quota associated with it and may or may not contain physical components traceable to recycled waste.

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

[0046] 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.

[0047] As used herein, "recovered content pyrolysis oil," "recovered pyrolysis oil," "pyrolysis recovered content pyrolysis oil," and "r-pyrolysis oil" refer to a pyrolysis oil at least a portion of which is obtained from pyrolysis and has a recovered content.

[0048] As used herein, "pyrolysis gas" and "pyrolysis gas" refer to a composition of matter that is a gas when measured at 25°C and 1 atm and at least a portion of which is obtained from pyrolysis.

[0049] 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.

[0050] As used herein, "Et" is the ethylene component (eg, feedstock, product, or stream), and "Pr" is the propylene component (eg, feedstock, product, or stream).

[0051] As used herein, "recycled content ethylene", "r-ethylene" and "r-Et" refer to Et with recycled content; "recycled content propylene", "r-propylene" and "r-Pr" refer to Pr with recycled content.

[0052] As used herein, "AD" is an aldehyde resin, product, feedstock, stream or composition. Optionally, the aldehyde has 2-10 carbon atoms, or 2-5 carbon atoms, or 2-4 carbon atoms, and can be linear or branched, alicyclic or aliphatic, substituted or unsubstituted, saturated or unsaturated, or an anhydride in which the carbon number is doubled, ideally an unsubstituted aliphatic linear aldehyde having 2-5 or 2-4 carbon atoms, or an anhydride thereof having 4-10 or 4-8 carbon atoms.

[0053] As used herein, "recovered component aldehyde" and "rA" refer to AD having a recovered component.

[0054] As used herein, "pyrolysis-recovered component aldehyde" and "pr-A" refer to rA having a pyrolysis-recovered component.

[0055] As used herein, "PVA" is a polyvinyl acetal polymer, resin, product, stream or composition.

[0056] As used herein, "recycled content polyvinyl acetal" and "r-PVA" refer to PVA having recycled content.

[0057] As used herein, "pyrolyzed content polyvinyl acetal" and "pr-PVA" refer to r-PVA having a pyrolyzed recycled content.

[0058] As used herein, "PVOH" is a PVOH polymer, resin, product, feedstock, stream or composition.

[0059] As used herein, "PVAc" is a polyvinyl acetate polymer, resin, product, feedstock, stream or composition.

[0060] As used throughout, the general description of a compound, composition, or logistics does not require the presence of its substance, but does not exclude and may include its substance. For example, "PVA" or "any PVA" may include polyvinyl acetal prepared by any method, and may contain or not contain recycled components, and may be prepared by or not by non-recycled component raw materials or by recycled component raw materials, and may include or not include r-PVA or pr-PVA. Similarly, r-PVA may include or not include pr-PVA, although it is mentioned that r-PVA does require it to have recycled components. In another example, "AD" or "any AD" may include aldehydes prepared by any method, and may have or not have recycled components, and may include or not include rA or pr-A. Similarly, rA may include or not include pr-A, although it is mentioned that rA does require it to have recycled components.

[0061] "Pyrolytic recycled content" is a specific subset / type (kind) of "recycled content" (genus). Wherever "recycled content" and "r-" are used herein, such use should be interpreted as explicitly disclosing and providing claim support for "pyrolytic recycled content" and "pr-", even if not explicitly stated as such. For example, whenever the term "recycled content polyvinyl acetal" or "r-PVA" is used herein, it should be interpreted as also explicitly disclosing and providing claim support for "pyrolytic recycled content polyvinyl acetal" and "pr-PVA".

[0062] Similarly, whenever the terms "olefins" and "r-olefins" are used herein, they should be interpreted as also explicitly disclosing and providing claim support for "pyrolysis recovered component olefins" and "pr-olefins". When the terms "aldehydes" or "r-aldehydes" are used herein, they should be interpreted as also explicitly disclosing and providing claim support for "pyrolysis recovered component aldehydes" and "pr-aldehydes".

[0063] As used throughout, whenever the cracking of r-pyrolysis oil is mentioned, such cracking can be carried out in a liquid feed furnace or in a gas feed furnace or in any cracking process by a thermal cracker or a hot steam cracker. 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. As used throughout, whenever the pyrolysis of recycled waste or r-pyrolysis oil is mentioned, all embodiments also include the option of (i) cracking the pyrolysis recycled waste or cracking the effluent of r-pyrolysis oil and / or (ii) the option of the feed of the cracked effluent or r-pyrolysis oil as a gas feed furnace or the tubes of a gas furnace / cracker.

[0064] As used throughout, a "family of entities" means at least one person or entity that directly or indirectly controls, is controlled by, or is under common control with another person or entity, where control means ownership of at least 50% of the voting stock, or shared management, common use of facilities, equipment, and employees, or family interests. As used throughout, references to persons or entities provide claim support to, and include, any person or entity in the family of entities.

[0065] In one embodiment or in combination with any other mentioned embodiment, reference to rA also includes pr-A, or pr-A obtained directly or indirectly from the cracking of r-pyrolysis oil or from r-pyrolysis gas; and r-PVA also includes pr-PVA or pr-PVA obtained directly or indirectly from the cracking of r-pyrolysis oil or from r-pyrolysis gas.

[0066] A method for preparing an r-PVA composition ("r-PVA") by reacting AD with PVA is provided. AD can be rA or pr-A. In one embodiment, the method for making r-PVA begins by feeding AD into a reactor for making PVA, and optionally AD is rA or pr-A, and optionally pr-A is obtained directly or indirectly from r-pyrolysis gas or cracked r-pyrolysis oil.

[0067] Figure 1 The present invention is a schematic diagram illustrating an embodiment of a process for preparing one or more recycled component compositions (e.g., ethylene, propylene, butadiene, hydrogen and / or pyrolysis gasoline) (r-composition) using a recycled component pyrolysis oil composition (r-pyrolysis oil) (or recycled waste) or in combination with any embodiment mentioned herein. One or more products from the separation zone can then be used to form a variety of end products, including, for example, for the preparation of oxo alcohols and / or oxo plasticizers.

[0068] like Figure 1As shown in , the recycled waste can be subjected to pyrolysis in a pyrolysis unit 10 to produce a pyrolysis product / effluent containing a recycled component pyrolysis oil composition (r-pyrolysis oil). The r-pyrolysis oil can be fed to a cracker 20 together with a non-recycled cracker feed (e.g., propane, ethane and / or natural gasoline). A recycled component cracking effluent (r-cracked effluent) can be produced from the cracker and then separated in a separation train 30. In one embodiment or in combination with any embodiment mentioned herein, or in combination with any of the mentioned embodiments, the r-composition can be separated and recovered from the r-cracked effluent. The r-propylene stream can contain primarily propylene, while the r-ethylene stream can contain primarily ethylene.

[0069] As used herein, a furnace includes a convection zone and a radiant zone. The convection zone includes tubes and / or coils inside the convection box, which may also continue outside the convection box downstream of the coil inlet at the inlet of the convection box. For example, Figure 5 As shown, the convection zone 310 includes coils and ducts within the convection box 312, and may optionally extend outside the convection box 312 and return to or interconnect with ducts 314 within the convection box 312. The radiant zone 320 includes radiant coils / tubes 324 and burners 326. The convection zone 310 and the radiant zone 320 may be contained in a single integral box, or in separate discrete boxes. The convection box 312 does not have to be a separate discrete box. As shown in FIG. Figure 5 As shown, the convection box 312 is integrated with the combustion chamber 322 .

[0070] Unless otherwise indicated, all component amounts provided herein (eg, for feeds, materials, streams, compositions, and products) are expressed on a dry basis.

[0071] As used herein, "r-pyoil" or "r-pyrolysis oil" are interchangeable and refer to a composition of matter that is liquid when measured at 25°C and 1 atmosphere, and at least a portion of which is obtained from pyrolysis, and has recycled content. In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the composition is obtained from pyrolysis of recycled waste (e.g., waste plastic or waste stream).

[0072] In one embodiment or in combination with any of the mentioned embodiments, "r-ethylene" can be a composition comprising: (a) ethylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) ethylene having a recovery content value attributable to at least a portion of the ethylene; and "r-propylene" can be a composition comprising (a) propylene obtained by cracking a cracker feed containing r-pyrolysis oil, or (b) propylene having a recovery content value attributable to at least a portion of the propylene.

[0073] 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).

[0074] As used herein, "site" means the largest contiguous geographic boundary owned by a polyvinyl acetal 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 polyvinyl acetal manufacturing facility.

[0075] As used herein, the term "predominantly" means greater than 50 weight percent, unless expressed in mole percent, in which case it means greater than 50 mol%. For example, a stream, composition, feedstock, or product that is primarily propane is a stream, composition, feedstock, or product that contains greater than 50 weight percent propane, or if expressed in mol%, refers to a product that contains greater than 50 mol% propane.

[0076] As used herein, a composition "directly derived from" cracked pyrolysis oil has at least one physical component traceable to an r-composition at least a portion of which was obtained by or in conjunction with cracking r-pyrolysis oil, while a composition "indirectly derived from" cracked r-pyrolysis oil has a recovered ingredient quota associated therewith and may or may not contain physical components traceable to an r-composition at least a portion of which was obtained by or in conjunction with cracking r-pyrolysis oil.

[0077] As used herein, "recycled content value" and "r-value" refer to a unit of measurement representing the amount of material that is derived from recycled waste. The r-value can be derived from any type of recycled waste processed in any type of process.

[0078] As used herein, the terms "pyrolysis recovery content value" and "pr value" refer to a unit of measurement representing the amount of material derived from the pyrolysis of recycled waste. The pr value is a specific subset / type of r-values ​​associated with the pyrolysis of recycled waste. Therefore, the term r-value includes but does not require a pr value.

[0079] Specific recovery component value (r-value or pr value) can be by mass or percentage or any other measurement unit, and can be determined according to the standard system for tracing back, allocating and / or depositing and lending the recovery component in various compositions. Recovery component value can be deducted from the recovery component inventory and applied to product or composition, to attribute the recovery component to product or composition. Unless otherwise stated, recovery component value is not necessarily derived from manufacturing or cracking r-pyrolysis oil. In one embodiment or in combination with any mentioned embodiment, at least a portion of the r-pyrolysis oil from which a quota is obtained is also cracked in the cracking furnace as described in one or more embodiments throughout this paper.

[0080] As used herein, "recycled content quota" or "quota" means a recycled content value of:

[0081] from a starting composition (e.g., a compound, polymer, feedstock, product or stream) at least a portion of which is obtained from recycled waste, or has at least a portion of recycled content value derived from recycled waste, optionally derived from r-pyrolysis oil, to a receiving composition (receiving a quota of the composition, e.g., a compound, polymer, feedstock, product or stream), the starting composition having at least a portion thereof obtained from recycled waste, or having at least a portion of recycled content value derived from recycled waste, optionally derived from r-pyrolysis oil, the receiving composition having or not having physical components traceable to a composition at least a portion of which is obtained from recycled waste; or

[0082] A starting composition (eg, a compound, polymer, feedstock, product, or stream) is deposited into a recycling stock, at least a portion of which is obtained from, or has at least a portion of which is derived from, a recycled content value or pr value derived from recycled waste.

[0083] As used herein, "pyrolysis recovery component quota" and "pyrolysis quota" or "pr-quota" means a recovery component value of:

[0084] (i) 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

[0085] (ii) deposited into a recycling stock 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, pyrolysis of recycling waste.

[0086] A pyrolysis recovery content quota is a specific type of recovery content quota associated with the pyrolysis of recovered waste. Thus, the term recovery content quota includes a pyrolysis recovery content quota.

[0087] In one embodiment or in combination with any of the mentioned embodiments, the pyrolysis recovery component quota or pyrolysis quota can have a recovery component value of:

[0088] from a starting composition (e.g., a compound, polymer, feedstock, product or stream) that was obtained at least in part from the cracking of an r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), or from recycled waste used to prepare cracked r-pyrolysis oil, or from cracked or to be cracked r-pyrolysis oil, or which has at least a portion of its recycled component value derived from the cracking of an 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 an r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), or from recycled waste used to prepare cracked r-pyrolysis oil, or from cracked or to be cracked r-pyrolysis oil, or which has at least a portion of its recycled component value derived from the cracking of an r-pyrolysis oil (e.g., liquid or gaseous thermal steam cracking), the receiving composition may or may not have physical components traceable to a composition at least in part of which was obtained from the cracking of an r-pyrolysis oil; or

[0089] Deposited into the recovery inventory and obtained from a composition (e.g., a compound, polymer, feedstock, product, or stream) at least a portion of which was obtained from, or has at least a portion of its recovery component value derived from, the cracking (e.g., liquid or gaseous thermal steam cracking) of an r-pyrolysis oil (regardless of whether the r-pyrolysis oil was cracked when the allowance was deposited into the recovery component inventory, provided that the r-pyrolysis oil from which the allowance was withdrawn was ultimately cracked).

[0090] A quota can be an allotment or a credit.

[0091] The recycled content quota may include a recycled content allocation or a recycled content credit obtained by diverting or using raw materials. In one embodiment or in combination with any of the mentioned embodiments, the composition receiving the recycled content quota may be a non-recycled composition, thereby converting the non-recycled composition into an r-composition.

[0092] 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.

[0093] As used herein, "non-recycled feed" in the context of a feed to a cracker or furnace refers to a feed that is not obtained from a recycled waste stream. Once the non-recycled feed obtains a recycled component quota (e.g., through a recycled component credit or recycled component allocation), the non-recycled feed becomes a recycled component feed, composition, or recycled PIA.

[0094] As used herein, term " reclaimed component allocation " refers to a type of reclaimed component quota, wherein the entity or individual of supplying composition sells or transfers composition to receiving individual or entity, and the individual or entity of preparing composition has quota, and at least a portion of this quota can be related to the composition that supplies individual or entity sells or transfers to receiving individual or entity. Supply entity or individual can be controlled by same entity or individual or entity family or different entity families. In one embodiment or with any embodiment combination mentioned, reclaimed component allocation is advanced together with composition and downstream derivative of said composition. In one embodiment or with any embodiment combination mentioned, allocation can be deposited in the reclaimed component stock, and is taken out from the reclaimed component stock as allocation, and is applied to composition to prepare r-composition or reclaim PIA.

[0095] As used herein, "recovered content credit" and "credit" means a recovered content quota wherein the quota is not limited to being associated with a composition made from cracked r-pyrolysis oil or downstream derivatives thereof, but rather has the flexibility to be derived from r-pyrolysis oil and is (i) applied to a composition or PIA made from a process other than cracking a feedstock in a furnace, or (ii) applied to downstream derivatives of compositions made from a process other than cracking a feedstock in a furnace through one or more intermediate feedstocks, or (iii) may be sold or transferred to a person or entity other than the owner of the quota, or (iv) may be sold or transferred by a person other than the supplier of the composition to which it is transferred. For example, a quota can be a credit when it is taken from r-pyrolysis oil and applied by the quota owner to a BTX composition or fraction thereof that is manufactured by the owner or within its family of entities and is obtained through the refining and fractionation of petroleum rather than through cracker effluent products; or it can be a credit if the quota owner sells the quota to a third party to allow the third party to resell the product or apply the credit to one or more components of the third party.

[0096] Credits may be available for sale, transfer or use, or may be sold, transferred or used, or:

[0097] does not sell the composition, or

[0098] sell or transfer the Composition, but the Quota does not relate to the sale or transfer of the Composition, or

[0099] 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 the recycled content raw materials, or that has such traceability but does not trace back to a specific quota applied to the composition.

[0100] In one embodiment or in combination with any of the embodiments mentioned, a quota can be deposited into a recycling component inventory, and a credit or allocation can be extracted from the inventory and applied to a composition. This will be the case where a first composition is prepared by pyrolysis of recycled waste, or by cracking of r-pyrolysis oil or r-pyrolysis oil, or by any other method of preparing the first composition from recycled waste, a quota is generated, and the allocation associated with the first component is deposited into a recycling component inventory, and the recycling component value is deducted from the recycling component inventory and applied to a second composition, which is not a derivative of the first composition or is not actually prepared as a raw material by the first composition. In this system, there is no need to track the source of the reactant to any atom contained in the cracking of the pyrolysis oil or the olefin-containing effluent, but any reactant made by any process can be used and a recycling component quota can be associated with such a reactant.

[0101] In one embodiment or in combination with any of the mentioned embodiments, the composition of the receiving quota is used as a feedstock to prepare a downstream derivative of the composition, and such composition is a product of a cracker feedstock cracked in a cracker furnace. In one embodiment or in combination with any of the mentioned embodiments, a process is provided, wherein:

[0102] a. Obtaining r-pyrolysis oil,

[0103] b. Obtaining recovery component value (or quota) from r-pyrolysis oil and

[0104] i. Deposit into recycled content stock, withdraw quota (or credit) from recycled content stock

[0105] and apply it to any composition to obtain an r-composition, or

[0106] ii. Direct application to any composition without depositing into the stock of recycled components to obtain

[0107] r-composition; and

[0108] 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

[0109] d. Optionally, at least a portion of the composition in step b originates from a cracker feed in a cracker furnace, optionally, the composition has been obtained by any of the feedstocks comprising r-pyrolysis oil and the methods described herein.

[0110] 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.

[0111] As used herein, "recycle content inventory" and "inventory" mean a group or collection of quotas (allotments or credits) from which the deposits and deductions of quotas under any unit can be traced. The inventory can be in any form (electronic or paper), using any one or more software programs, or using various modules or applications (which trace deposits and deductions together as a whole). Desirably, the total amount of recycled content removed (or applied to the composition) does not exceed the total amount of recycled content quotas or deposits in the recycled content inventory (from any source, not only from the cracking of r-pyrolysis oil). However, if a deficit in recycled content value is achieved, the recycled content inventory is rebalanced to achieve zero or positive available recycled content value. The timing of rebalancing can be determined and managed according to the rules of a specific certification system adopted by the olefin-containing effluent manufacturer or a member of its family of entities, or alternatively, rebalanced within one (1) year, six (6) months, three (3) months, or one (1) month of achieving a deficit. The timing of depositing the quota into the recycling component inventory, applying the quota (or credit) to the composition to prepare the r-composition and cracking the r-pyrolysis oil need not be simultaneous or in any particular order. In one embodiment or in combination with any of the mentioned embodiments, the step of cracking a specific volume of r-pyrolysis oil occurs after the recycling component value or quota from the volume of r-pyrolysis oil is deposited into the recycling component inventory. In addition, the quota or recycling component value taken from the recycling component inventory does not need to be traceable to r-pyrolysis oil or cracked r-pyrolysis oil, but can be obtained from any waste recycling stream and any method for processing recycling waste streams. Desirably, at least a portion of the recycling component value in the recycling component inventory is obtained from r-pyrolysis oil, optionally, at least a portion of the r-pyrolysis oil is processed in one or more cracking processes as described herein, optionally within one year of each other, optionally, at least a portion of the volume of r-pyrolysis oil (from which the recycling component value is deposited into the recycling component inventory) is also processed by any one or more of the cracking processes described herein.

[0112] 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 (such as olefins or aldehydes or oxo alcohols or oxo plasticizers) can be traced back to an r-composition prepared from recycled waste.

[0113] Determining whether a PR composition is derived directly or indirectly from the pyrolysis of recycled waste (e.g., derived from the cracking of r-pyrolysis oil or derived from r-pyrolysis gas) is not based on the presence or absence of intermediate steps or entities in the supply chain, but rather on whether at least a portion of the PR composition fed to the reactor used to prepare the final product (e.g., PVA) can be traced back to a PR composition prepared from the pyrolysis of recycled waste.

[0114] As described above, a final product is considered to be directly derived from recycled waste if at least a portion of the reactant feedstocks used to prepare the product can be traced back, optionally via one or more intermediate steps or entities, to at least a portion of an r-composition produced from recycled waste (e.g., during cracking of r-pyrolysis oil fed to a cracking furnace or as an effluent from a cracking furnace).

[0115] The r-composition as an effluent may be in the form of a crude product that requires refining to isolate a specific r-composition. The r-composition manufacturer may sell such r-composition to an intermediate entity, typically after refining and / or purifying and compressing to produce a desired grade of a specific r-composition, which then sells the r-composition or one or more derivatives thereof to another intermediate entity for the preparation of an intermediate product, or directly to a product manufacturer. Any number of intermediates and intermediate derivatives may be prepared before the final product is prepared.

[0116] The actual volume of r-composition, whether condensed as a liquid, supercritical or stored as a gas, may remain in the facility where it was prepared, or may be transported to a different location, or held in an off-site storage facility prior to use by an intermediate or product manufacturer. For tracking purposes, once an r-composition made by recycling waste (e.g., by cracking r-pyrolysis oil or from r-pyrolysis gas) is mixed with another volume of composition (e.g., r-propylene mixed with non-recycled propylene) in, for example, a storage tank, salt dome or cave, then the entire tank, dome or cave becomes the source of r-composition at that point, and for tracking purposes, withdrawals from such storage facilities are withdrawn from the source of r-composition until the entire volume or inventory of the storage facility is turned over or withdrawn and / or replaced with non-recycled composition after the feeding of r-composition to the tank has ceased. Likewise, this also applies to any downstream storage facilities for storing derivatives of r-composition, such as rA and pr-A compositions.

[0117] An R-composition is considered to be indirectly derived from recycled waste or pyrolysis or cracking of R-pyrolysis oils if the R-composition is associated with a recycled content quota and may or may not contain physical components that are traceable to cracked R-composition obtained from recycled waste or pyrolysis or cracking of R-pyrolysis oils from recycled waste. For example, (i) a product manufacturer may operate within a legal framework, or an association framework, or an industry-recognized framework to require recycled content through a system of credits, such as credits, that are transferred to the product manufacturer regardless of where or from whom the R-composition, or derivatives thereof, or reactant feedstocks for making the product are purchased or transferred, or (ii) a supplier of the R-composition or derivatives thereof ("supplier") operates within a quota framework that allows a recycled content value or PR value to be associated with or applied to a portion or all of the compounds in the olefin-containing effluent or derivatives thereof to prepare the R-composition and transfer that recycled content value or quota to the manufacturer of the product or any intermediary that obtains a supply of the R-composition or derivatives thereof from the supplier. In this system, there is no need to trace the source of the rA volume to make the r-composition from recycled waste / pyrolyzed recycled waste, but rather any aldehyde composition made by any process can be used and have a recycled component quota associated with such aldehyde composition.

[0118] Examples of how to obtain recycled content from AD compositions used to prepare PVA include (using propylene as an example, but other olefins are also applicable, such as ethylene):

[0119] (i) a cracker facility in which r-propylene is produced by cracking r-pyrolysis oil or obtained from r-pyrolysis gas, which may be in fluid communication with an AD forming facility (which may be a storage vessel to an AD facility or directly to an AD forming reactor) via interconnected pipelines, optionally via one or more storage vessels and valves or interlocks, either continuously or intermittently and via intermediate facilities (e.g., an AD facility), and the r-propylene feedstock is supplied via interconnected pipelines:

[0120] a. withdrawn from a cracker facility during r-propylene production or thereafter during the time r-propylene is piped to an AD formation facility; or

[0121] b. withdrawn from one or more storage tanks at any time, provided that at least one storage tank is fed with r-propylene, as long as the entire volume of the one or more storage tanks is replaced by feed containing no r-propylene; or

[0122] (ii) transporting from a storage vessel, vault or facility, or in an isotainer, by truck or rail or ship or by means other than pipeline, containing or having been fed with r-propylene until the entire volume of the vessel, vault or facility has been replaced by propylene gas feed that does not contain r-propylene; or

[0123] (iii) an AD manufacturer certifies, represents, or advertises to its customers or the public that its AD contains recycled content or is obtained from a feedstock containing recycled content or is obtained from recycled content, wherein such recycled content is claimed to be based in whole or in part on a propylene feedstock associated with an allocated amount of propylene produced from cracking r-pyrolysis oil or obtained from r-pyrolysis gas; or

[0124] (iv) The AD manufacturer has obtained:

[0125] a. Based on the volume of propylene produced from r-pyrolysis oil as certified, represented or advertised, or

[0126] b. has transferred credits or allocations of propylene supply to AD manufacturers to meet certification requirements or make representations or advertising thereof, or

[0127] c. Propylene to which a recovery component has been allocated, wherein this allocated amount is obtained via one or more intermediate entities from a cracked propylene volume at least part of which is obtained by cracking r-pyrolysis oil or from r-pyrolysis gas.

[0128] 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.

[0129] In one embodiment or in combination with any of the embodiments mentioned, the input or generation of the recovery component (recovery component raw material or quota) can be to or at the first site, and the recovery component value from the input is transferred to the second site and applied to one or more compositions prepared at the second site. The recovery component value can be applied to the composition symmetrically or asymmetrically at the second site. The recovery component value of "derived from cracked r-pyrolysis oil" or "obtained from cracked r-pyrolysis oil" or the recovery component value derived from cracked r-pyrolysis oil directly or indirectly does not imply the time when the recovery component value or quota is taken, captured, deposited in the recovery component inventory or transferred. The timing of depositing the quota or recovery component value in the recovery component inventory or realizing, identifying, capturing or transferring it is flexible, and can be carried out as early as receiving the r-pyrolysis oil at a site within the entity family that owns it or by an entity or individual that owns or operates a cracking facility to bring the r-pyrolysis oil into the inventory or within the entity family. Thus, a quota or recovered component value for a volume of r-pyrolysis oil may be obtained, captured, deposited into an inventory, or transferred to a product, without that volume having been fed to a cracking furnace and cracked. The quota may also be obtained during the feeding of r-pyrolysis oil to a cracker, during cracking, or when preparing an r-composition. The quota taken when r-pyrolysis oil is owned, possessed, or received and deposited into a recovered component inventory is a quota associated with, obtained from, or derived from cracked r-pyrolysis oil, even if the r-pyrolysis oil has not yet been cracked when the quota is taken or deposited, provided that the r-pyrolysis oil is cracked at some point in the future.

[0130] 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).

[0131] A recycled waste stream is a flow or accumulation of recycled waste from industrial and consumer sources that is at least partially recycled. A recycled waste stream includes materials, products, and articles (collectively referred to as "materials" when used alone). Recycled waste materials can be solid or liquid. Examples of solid recycled waste streams include plastics, rubber (including tires), textiles, wood, biowaste, modified cellulose, wet laid products, and any other material capable of pyrolysis. Examples of liquid waste streams include industrial sludge, oils (including those derived from plants and petroleum), recycled lubricating oils, or vegetable or animal oils, and any other chemical streams from industrial plants.

[0132] In one embodiment or in combination with any of the mentioned embodiments, the recycled waste stream that is pyrolyzed comprises a stream that contains at least in part post-industrial material, or post-consumer material, or both post-industrial material and post-consumer material. In one embodiment or in combination with any of the mentioned embodiments, post-consumer material is material that has been used at least once for its intended application for any duration regardless of wear and tear, or material that has been sold to an end-use consumer, or material that has been discarded into a recycling bin by any person or entity other than the manufacturer or business engaged in the manufacture or sale of the material.

[0133] In one embodiment or in combination with any of the mentioned embodiments, post-industrial materials are materials that have been manufactured and not used for their intended application, or not sold to an end-use customer, or discarded by the manufacturer or any other entity involved in the sale of the material. Examples of post-industrial materials include reprocessing, regrind, scrap, off-cuts, substandard materials, and finished materials that have been transferred from a manufacturer to any downstream customer (e.g., manufacturer to wholesaler to distributor) but have not yet been used or sold to an end-use customer.

[0134] The form of the recycled waste stream that can be fed to the pyrolysis unit is not limited and can include any form of article, product, material or part thereof. A portion of the article can take the form of a sheet, extruded profile, molded article, film, laminate, foam sheet, fragment, flake, granule, fiber, agglomerate, briquette, powder, fragment, strip, or any shaped piece having various shapes, or any other form other than the original form of the article, and suitable for feeding to the pyrolysis unit.

[0135] In one embodiment or in combination with any of the mentioned embodiments, the recycled waste is reduced in size. The reduction can be performed by any means including shredding, shredding, harrowing, grinding, pulverizing, cutting the stock, molding, compressing or dissolving in a solvent.

[0136] The recycled waste plastics can be separated as one type of polymer stream, or can be a stream of mixed recycled waste plastics. Plastics can be any organic synthetic polymer that is solid at 25°C and 1 atm. Plastics can be thermosetting, thermoplastic or elastomeric plastics. Examples of plastics include high density polyethylene and its copolymers, low density polyethylene and its copolymers, polypropylene and its copolymers, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyesters (including polyethylene terephthalate), copolyesters and terephthalate copolyesters (e.g., containing residues of TMCD, CHDM, propylene glycol or NPG monomers), polyethylene terephthalate, polyamides, poly(methyl methacrylate), polytetrafluoroethylene, acrylonitrile-butadiene-styrene (ABS), polyurethanes, cellulose and its derivatives, such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate; regenerated cellulose products such as viscose and rayon, epoxy resins, polyamides, phenolic resins, polyacetals, polycarbonates, polyphenyl alloys, polypropylene and its copolymers, polystyrene, styrene compounds, vinyl compounds, styrene-acrylonitrile, thermoplastic elastomers, urea-based polymers and melamine-containing polymers.

[0137] Suitable recycled waste plastics also include any of those with resin ID codes 1-7 within the chasing arrow triangle established by SPI. In one embodiment or in combination with any of the embodiments mentioned, r-pyrolysis oil is made from a recycled waste stream, at least a portion of which contains plastics that are not normally recycled. These include plastics with the numbers 3 (polyvinyl chloride), 5 (polypropylene), 6 (polystyrene), and 7 (others). In one embodiment or in combination with any of the embodiments mentioned, the recycled waste stream that is pyrolyzed contains less than 10 weight percent, or no more than 5 weight percent, or no more than 3 weight percent, or no more than 2 weight percent, or no more than 1 weight percent, or no more than 0.5 weight percent, or no more than 0.2 weight percent, or no more than 0.1 weight percent, or no more than 0.05 weight percent of No. 3 plastic (polyvinyl chloride), or alternatively No. 3 and No. 6 plastics, or alternatively No. 3, 6, and No. 7 plastics.

[0138] Examples of recycled rubber include natural and synthetic rubber. The form of the rubber is not limited, including tires.

[0139] 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.

[0140] Examples of recycled biorecyclable waste include household biorecyclable waste (eg food), green or garden biorecyclable waste, and biorecyclable waste from the industrial food processing industry.

[0141] The example of the textiles of recovery comprises natural and / or synthetic fiber, roving, yarn, nonwoven web, cloth, fabric and the product made by any of the above-mentioned articles or comprising any of the above-mentioned articles.Textiles can be woven, knitted, knotted, stitched, tufted, the fiber is pressed together, such as carried out in a felting operation, embroidered, lace, crocheted, braided or nonwoven web and material.Textiles include fabrics and fibers separated from textiles or other products comprising fibers, waste or substandard fibers or yarns or textiles, or any other loose fibers and yarn sources.Textiles also include staple fibers, continuous fibers, lines, tow bands, twisting and / or staple yarns, grey cloths made of yarn, finished textiles made by wet processing grey cloths, and clothing made by finished textiles or any other textiles.Textiles include clothing, interior furnishings and industrial textiles.

[0142] Examples of recycled textiles in the apparel category (things worn by humans or made for the body) include sport coats, suits, pants and casual or work pants, shirts, socks, sportswear, dresses, intimate apparel, outerwear such as raincoats, cold-weather jackets and coats, sweaters, protective clothing, uniforms and accessories such as scarves, hats and gloves. Examples of textiles in the furnishings category include furniture upholstery and furniture coverings, carpets and cushions, curtains, bedding such as sheets, pillowcases, duvets, quilts, mattress covers; linens, tablecloths, towels and blankets. Examples of industrial textiles include transportation (car, plane, train, bus) seats, floor mats, trunk liners and headliners; outdoor furniture and cushions, tents, backpacks, luggage, ropes, conveyor belts, calendar roller felts, polishing cloths, rags, soil erosion textiles and geotextiles, agricultural mats and screens, personal protective equipment, bulletproof vests, medical bandages, sutures, tapes, etc.

[0143] The nonwoven web of recovery can also be a dry-laid nonwoven web. The example of suitable products that can be formed by the dry-laid nonwoven web as described herein can include those for personal, consumer, industry, food service, medical and other types of end-uses. Specific examples can include but are not limited to baby wipes, flushable wipes, disposable diapers, training pants, feminine hygiene products such as sanitary towels and tampons, adult incontinence pads, underwear or underpants and pet training pads. Other examples include a variety of different dry or wet wipes, including those wipes used for consumers (such as personal care or family) and industry (such as food service, health care or professional). Nonwoven webs can also be used as pillows, mattresses and furniture decorations, for the cotton wool of bedding and quilt covers. In the medical and industrial fields, the nonwoven web of the present invention can be used for medical and industrial masks, protective clothing, hats and shoe covers, disposable sheets, surgical gowns, curtains, bandages and medical dressings. In addition, nonwoven webs can be used for environmental textiles, such as geotextiles and tarpaulins, oil pads and chemical absorbent pads, and building materials, such as sound insulation or heat insulation, tents, wood and soil coverings and sheets. Nonwoven webs can also be used for other consumer end uses, such as packaging, heat insulation or sound insulation and various types of clothing for carpet backing, consumer products, industrial products and agricultural products. Dry-laid nonwoven webs can also be used for a variety of filtering applications, including transportation (for example, automobile or aviation), business, residential, industrial or other professional applications. Example can include filter elements for consumer or industrial air or liquid filters (for example, gasoline, oil, water), including nanofiber webs for microfiltration and end uses such as tea bags, coffee filters and dryer sheets. In addition, nonwoven webs can be used to form a variety of components for automobiles, including but not limited to brake pads, trunk pads, carpet tufting and bottom fillers.

[0144] The recycled textiles may include a single type or multiple types of natural fibers and / or a single type or multiple types of synthetic fibers. Examples of textile fiber combinations include all natural, all synthetic, two or more types of natural fibers, two or more types of synthetic fibers, one type of natural fibers and one type of synthetic fibers, one type of natural fibers and two or more types of synthetic fibers, two or more types of natural fibers and one type of synthetic fibers, and two or more types of natural fibers and two or more types of synthetic fibers.

[0145] Examples of wet-laid products that are recycled include paperboard, office paper, newsprint and magazines, printing and writing paper, toilet paper, tissue / towel paper, packaging / containerboard, specialty papers, apparel, bleached paperboard, corrugated base, wet-laid molded products, unbleached kraft paper, decorative laminates, bond paper and currency, oversized graphics, specialty products, and food and beverage products.

[0146] Examples of modified cellulose include cellulose acetate, cellulose diacetate, cellulose triacetate, regenerated cellulose such as viscose, rayon and Lyocel TM Products in any form such as tow bands, staple fibers, continuous fibers, films, sheets, molded or stamped products, and contained in or on any articles such as cigarette filter rods, ophthalmic products, screwdriver handles, optical films and coatings.

[0147] Examples of recycled vegetable or animal oils include oils recycled from animal processing facilities and recycled waste from restaurants.

[0148] The sources of post-consumer or post-industrial recycled waste from which recycling is obtained are not limited and may include recycled waste present in and / or separated from a municipal solid recycled waste stream ("MSW"). For example, a MSW stream may be processed and sorted into a number of discrete components, including textiles, fibers, paper, wood, glass, metals, etc. Other sources of textiles include those obtained by collection agencies, or by or for or on behalf of textile brand owners or alliances or organizations, or by brokers, or from post-industrial sources, such as scraps from mills or commercial production facilities, unsold textiles from wholesalers or distributors, from mechanical and / or chemical sorting or separation facilities, from landfills, or stranded at docks or on ships.

[0149] In one embodiment or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit may contain at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99 weight percent of at least one, or at least two, or at least three, or at least four, or at least five, or at least six different kinds of recycled waste. Reference to "kind" is determined by resin ID code 1-7. In one embodiment or in combination with any of the embodiments mentioned, the feed to the pyrolysis unit contains less than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 1 weight percent of polyvinyl chloride and / or polyethylene terephthalate in each case. In one embodiment or in combination with any of the embodiments mentioned, the recycled waste stream contains at least one, two or three plasticized plastics.

[0150] Figure 2 An exemplary pyrolysis system 110 is described that can be used to at least partially convert one or more recycled wastes, particularly recycled plastic wastes, into various useful pyrolysis-derived products. It should be understood that Figure 2The pyrolysis system shown in is merely one example of a system in which the present disclosure may be implemented. The present invention may be applied to a variety of other systems in which it is desirable to effectively and efficiently pyrolyze recycled waste, particularly recycled plastic waste, into a variety of desired end products. Figure 2 An exemplary pyrolysis system is shown in FIG.

[0151] like Figure 2 As shown, the pyrolysis system 110 may include a waste plastic source 112 for supplying one or more waste plastics to the system 110. The plastic feedstock 112 may be, for example, a hopper, a storage bin, a rail car, a long-haul trailer, or any other device that can hold or store waste plastics. In one embodiment or in combination with any of the embodiments described herein, the waste plastics supplied by the plastic source 112 may be in the form of solid particles, such as chips, flakes, or powder. Although in Figure 2 Not depicted in the drawings, the pyrolysis system 110 may also include additional sources of other types of recycled waste, which may be used to provide other feed types to the system 110 .

[0152] In one embodiment or in combination with any of the embodiments mentioned herein, the waste plastics may include one or more post-consumer waste plastics, such as high-density polyethylene, low-density polyethylene, polypropylene, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyethylene terephthalate, polyamide, poly(methyl methacrylate), polytetrafluoroethylene, or a combination thereof. In one embodiment or in combination with any of the embodiments mentioned herein, the waste plastics may include high-density polyethylene, low-density polyethylene, polypropylene, or a combination thereof. As used herein, "post-consumer" refers to non-virgin plastics that have been previously introduced into the consumer market.

[0153] In one embodiment or in combination with any of the embodiments mentioned herein, a feed containing waste plastic can be supplied from a plastic source 112. In one embodiment or in combination with any of the embodiments mentioned herein, the feed containing waste plastic can comprise, consist essentially of, or consist of high-density polyethylene, low-density polyethylene, polypropylene, other polyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyethylene terephthalate, polyamide, poly(methyl methacrylate), polytetrafluoroethylene, or combinations thereof.

[0154] In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastics may contain at least one, two, three or four different types of waste plastics in each case at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99 weight percent. In one embodiment or in combination with any embodiment mentioned herein, the plastic waste may contain polyvinyl chloride and / or polyethylene terephthalate in each case at no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 1 weight percent. In one embodiment or in combination with any embodiment mentioned herein, the feed containing waste plastics may contain at least one, two or three plasticized plastics. Reference to "type" is determined by resin ID code 1-7.

[0155] like Figure 2 As shown, the solid waste plastic feed from the plastic source 112 can be supplied to the feedstock pretreatment unit 114. In the feedstock pretreatment unit 114, the introduced waste plastic can undergo a number of pretreatments to promote the subsequent pyrolysis reaction. Such pretreatments may include, for example, washing, mechanical agitation, flotation, diameter reduction, or any combination thereof. In one embodiment or in combination with any embodiment mentioned herein, the introduced plastic waste can be subjected to mechanical agitation or diameter reduction to reduce the particle size of the plastic waste. Such mechanical agitation can be provided by any mixing, shearing or grinding device known in the art, which can reduce the average particle size of the introduced plastic by at least 10%, or at least 25%, or at least 50%, or at least 75%.

[0156] Next, the pre-treated plastic feedstock can be introduced into the plastic feed system 116. The plastic feed system 116 can be configured to introduce the plastic feed into the pyrolysis reactor 118. The plastic feed system 116 can include any system known in the art capable of feeding solid plastic into the pyrolysis reactor 118. In one embodiment or in combination with any of the embodiments mentioned herein, the plastic feed system 116 can include a screw feeder, a hopper, a pneumatic conveying system, a mechanical metal bar or chain, or a combination thereof.

[0157] While in the pyrolysis reactor 118, at least a portion of the plastic feed can be subjected to a pyrolysis reaction that produces a pyrolysis effluent comprising a pyrolysis oil (e.g., r-pyrolysis oil) and a pyrolysis gas (e.g., r-pyrolysis gas). The pyrolysis reactor 118 can be, for example, an extruder, a tubular reactor, a tank, a stirred tank reactor, a riser reactor, a fixed bed reactor, a fluidized bed reactor, a rotary kiln, a vacuum reactor, a microwave reactor, an ultrasonic or supersonic reactor, or an autoclave, or a combination of these reactors.

[0158] Generally, pyrolysis is a process involving the chemical and thermal decomposition of an introduced feed. Although all pyrolysis processes can generally be characterized by a reaction environment that is substantially free of oxygen, the pyrolysis process can be further defined by, for example, the pyrolysis reaction temperature within the reactor, the residence time in the pyrolysis reactor, the type of reactor, the pressure within the pyrolysis reactor, and the presence or absence of a pyrolysis catalyst.

[0159] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction can include heating and converting the plastic feedstock in an atmosphere that is substantially free of oxygen or in an atmosphere that contains less oxygen relative to ambient air. In one embodiment or in combination with any of the embodiments mentioned herein, the atmosphere within the pyrolysis reactor 118 can contain oxygen in an amount not exceeding 5%, or not exceeding 4%, or not exceeding 3, or not exceeding 2, or not exceeding 1, or not exceeding 0.5 in each case.

[0160] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process can be carried out in the presence of an inert gas such as nitrogen, carbon dioxide and / or steam. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis process can be carried out in the presence of a reducing gas such as hydrogen and / or carbon monoxide.

[0161] In one embodiment or in combination with any of the embodiments mentioned herein, the temperature in the pyrolysis reactor 118 can be adjusted to promote the production of certain end products. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 can be at least 325°C, or at least 350°C, or at least 375°C, or at least 400°C, or at least 425°C, or at least 450°C, or at least 475°C, or at least 500°C, or at least 525°C, or at least 550°C, or at least 575°C, or at least 600°C, or at least 625°C, or at least 650°C, or at least 675°C, or at least 700°C, or at least 725°C, or at least 750°C, or at least 775°C, or at least 800°C, additionally or alternatively In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 can be no more than 1,100°C, or no more than 1,050°C, or no more than 1,000°C, or no more than 950°C, or no more than 900°C, or no more than 850°C, or no more than 800°C, or no more than 750°C, or no more than 700°C, or no more than 650°C, or no more than 600°C, or no more than 550°C, or no more than 525°C, or no more than 500°C, or no more than 475°C, or no more than 450°C, or no more than 425°C, or no more than 400°C. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis temperature in the pyrolysis reactor 118 can be in the range of 325 to 1,100°C, 350 to 900°C, 350 to 700°C, 350 to 550°C, 350 to 475°C, 500 to 1,100°C, 600 to 1,100°C, or 650 to 1,000°C.

[0162] 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.

[0163] 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.

[0164] In one embodiment or in combination with any of the embodiments mentioned herein, a pyrolysis catalyst can be introduced into the plastic feed prior to introduction into the pyrolysis reactor 118 and / or introduced directly into the pyrolysis reactor 118 to produce r-catalyzed pyrolysis oil or r-pyrolysis oil prepared by a catalytic pyrolysis process. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the catalyst may comprise: (i) a solid acid such as a zeolite (e.g., ZSM-5, mordenite, beta, ferrierite and / or zeolite-Y); (ii) a superacid such as sulfonated, phosphated or fluorinated forms of zirconium oxide, titania, alumina, silica-alumina, and / or clay; (iii) a solid base such as a metal oxide, mixed metal oxide, metal hydroxide and / or metal carbonate, particularly those of alkali metals, alkaline earth metals, transition metals and / or rare earth metals; (iv) hydrotalcites and other clays; (v) metal hydrides, particularly those of alkali metals, alkaline earth metals, transition metals and / or rare earth metals; (vi) alumina and / or silica-alumina; (vii) a homogeneous catalyst such as a Lewis acid, a metal tetrachloroaluminate or an organic ionic liquid; (viii) activated carbon; or (ix) combinations thereof.

[0165] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 occurs substantially in the absence of a catalyst, particularly the catalysts described above. In such an embodiment, non-catalytic, heat-retaining inert additives, such as sand, may still be introduced into the pyrolysis reactor 118 to facilitate heat transfer within the reactor 118.

[0166] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis reaction in the pyrolysis reactor 118 can occur at a temperature in the range of 350 to 550° C., at a pressure in the range of 0.1 to 60 bar, and at a residence time of 0.2 seconds to 4 hours or 0.5 hours to 3 hours in the substantial absence of a pyrolysis catalyst.

[0167] Reference again Figure 2 , the pyrolysis effluent 120 leaving the pyrolysis reactor 118 generally includes pyrolysis gases, pyrolysis vapors, and residual solids. As used herein, the vapors produced during the pyrolysis reaction may be interchangeably referred to as "pyrolysis oil," which refers to the vapors when condensed into their liquid state. In one embodiment or in combination with any of the embodiments mentioned herein, the solids in the pyrolysis effluent 20 may include particles of char, ash, unconverted plastic solids, other unconverted solids from the feedstock, and / or spent catalyst (if a catalyst is used).

[0168] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain at least 20, or at least 25, or at least 30, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80 weight percent of pyrolysis vapor in each case, which may subsequently be condensed into a resulting pyrolysis oil (e.g., r-pyrolysis oil). Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain no more than 99, or no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30 weight percent of pyrolysis vapor in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can comprise 20 to 99 weight percent, 40 to 90 weight percent, or 55 to 90 weight percent pyrolysis vapor.

[0169] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 may contain at least 1, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12 weight percent of pyrolysis gas (e.g., r-pyrolysis gas) in each case. As used herein, "pyrolysis gas" refers to a composition produced by pyrolysis, and is a gas at standard temperature and pressure (STP). Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 20 may contain no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15 weight percent of pyrolysis vapor in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can contain 1 to 90 weight percent, or 5 to 60 weight percent, or 10 to 60 weight percent, or 10 to 30 weight percent, or 5 to 30 weight percent pyrolysis gases.

[0170] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis effluent 120 can contain no more than 15, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6, or no more than 5, or no more than 4, or no more than 3 weight percent of residual solids, in each case.

[0171] like Figure 2 As shown, the conversion effluent 120 from the pyrolysis reactor 118 can be introduced into a solid separator 122. The solid separator 122 can be any conventional device capable of separating solids from gases and vapors, such as a cyclone separator or a gas filter or a combination thereof. In one embodiment or in combination with any embodiment mentioned herein, the solid separator 122 removes most of the solids from the conversion effluent 120. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the solid particles 24 recovered in the solid separator 122 can be introduced into an optional regenerator 126 for regeneration, typically by combustion. After regeneration, at least a portion of the hot regenerated solids 128 can be introduced directly into the pyrolysis reactor 118. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the solid particles 124 recovered in the solid separator 122 can be introduced directly back into the pyrolysis reactor 118, particularly if the solid particles 124 contain a significant amount of unconverted plastic waste. The solids can be removed from the regenerator 126 via a pipeline 145 and discharged from the system.

[0172] Back to Figure 2, the remaining gas and vapor conversion products 130 from the solid separator 122 can be introduced into a fractionation tower 132. In the fractionation tower 132, at least a portion of the pyrolysis oil vapor can be separated from the cracked gas to form a cracked gas product stream 134 and a pyrolysis oil vapor stream 136. Suitable systems for use as the fractionation tower 132 may include, for example, a distillation tower, a membrane separation unit, a quench tower, a condenser, or any other known separation unit known in the art. In one embodiment or in combination with any embodiment mentioned herein, any residual solids 146 accumulated in the fractionation tower 132 can be introduced into an optional regenerator 126 for additional processing.

[0173] In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the pyrolysis oil vapor stream 136 may be introduced into a quench unit 138 to at least partially quench the pyrolysis vapors into their liquid form (i.e., pyrolysis oil). The quench unit 138 may include any suitable quenching system known in the art, such as a quench tower. The resulting liquid pyrolysis oil stream 140 may be removed from the system 110 and used in other downstream applications described herein. In one embodiment or in combination with any embodiment mentioned herein, the liquid pyrolysis oil stream 140 may not be subjected to any additional treatment, such as hydroprocessing and / or hydrogenation, before being used in any downstream application described herein.

[0174] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, at least a portion of the pyrolysis oil vapor stream 136 can be introduced into a hydroprocessing unit 142 for further refining. The hydroprocessing unit 142 may include a hydrocracker, a catalytic cracker operated using a hydrogen feed stream, a hydroprocessing unit and / or a hydrogenation unit. In the hydroprocessing unit 142, the pyrolysis oil vapor stream 136 can be treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil and remove undesirable by-products from the pyrolysis oil. The resulting hydrotreated pyrolysis oil vapor stream 144 can be removed and introduced into a quenching unit 138. Alternatively, the pyrolysis oil vapor can be cooled, liquefied, and then treated with hydrogen and / or other reducing gases to further saturate the hydrocarbons in the pyrolysis oil. In this case, hydrogenation or hydroprocessing is performed in the liquid phase pyrolysis oil. In this embodiment, post-hydrogenation or post-hydroprocessing does not require a quenching step.

[0175] The pyrolysis system 110 described herein can produce pyrolysis oil (e.g., r-pyrolysis oil) and pyrolysis gas (e.g., r-pyrolysis gas), which can be directly used in various downstream applications based on their desired formulations. Various characteristics and properties of the pyrolysis oil and pyrolysis gas are described below. It should be noted that although all of the following characteristics and properties can be listed individually, it is contemplated that each of the following characteristics and / or properties of the pyrolysis oil or pyrolysis gas are not mutually exclusive and can be in any combination and exist.

[0176] The pyrolysis oil may mainly contain hydrocarbons having 4 to 30 carbon atoms per molecule (e.g., C4 to C 30 As used herein, the term "Cx" or "Cx hydrocarbons" refers to hydrocarbon compounds that include x total carbons per molecule, and includes all olefins, paraffins, aromatic hydrocarbons, and isomers having that number of carbon atoms. For example, each of normal, iso-, and tert-butane and butene and butadiene molecules would fall within the general description "C4".

[0177] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the cracking furnace may have a C4-C50 weight percent of at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent in each case. 30 Hydrocarbon content, based on the weight of the pyrolysis oil.

[0178] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil fed to the furnace may comprise primarily C5-C 25 , C5-C22 or C5-C20 hydrocarbons, or may contain at least about 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent of C5-C 25 、C5-C 22 or C5-C 20 Hydrocarbons, based on the weight of the pyrolysis oil.

[0179] The gas furnace can tolerate a variety of hydrocarbon numbers in the pyrolysis oil feedstock, thereby avoiding the necessity to subject the pyrolysis oil feedstock to separation techniques to deliver smaller or lighter hydrocarbon fractions to the cracking furnace. In one embodiment or in any of the mentioned embodiments, after delivery from the pyrolysis manufacturer, the pyrolysis oil does not undergo a separation process for separating the heavy hydrocarbon fraction from the lighter hydrocarbon fraction relative to each other before feeding the pyrolysis oil to the cracker furnace. Feeding the pyrolysis oil to the gas furnace allows the use of pyrolysis oil containing heavy tails or higher carbon numbers equal to or higher than 12. In one embodiment or in any of the mentioned embodiments, the pyrolysis oil fed to the cracking furnace is C5-C 25 A hydrocarbon stream containing at least 3 wt.%, or at least 5 wt.%, or at least 8 wt.%, or at least 10 wt.%, or at least 12 wt.%, or at least 15 wt.%, or at least 18 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%, or at least 45 wt.%, or at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.% of C 12 To C 25 (including the end value), or in the range of C14 To C 25 (including the end value), or in the range of C 16 To C 25 Hydrocarbons within the range of 20 Å to 50 Å (including the end value).

[0180] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55 weight percent C6-C 12 The hydrocarbon content is based on the weight of the pyrolysis oil. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a C6-C ... 12 In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have 10 to 95 weight percent, 20 to 80 weight percent, or 35 to 80 weight percent C6-C 12 Hydrocarbon content.

[0181] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a C 2+ content of at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, in each case by weight. 13 -C 23 Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a C content of no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, in each case by weight. 13 To C 23 In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have 1 to 80 weight percent, 5 to 65 weight percent, or 10 to 60 weight percent of C 13 To C 23 Hydrocarbon content.

[0182] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil or r-pyrolysis oil fed to the cracking furnace, or the r-pyrolysis oil fed to the cracking furnace that receives a predominantly C2-C4 feedstock prior to feeding the pyrolysis oil (and references to r-pyrolysis oil or pyrolysis oil throughout include any of these embodiments) may have at least 1, or at least 2, or at least 3, or at least 4, or at least 5 weight percent of C2-C4 in each case.24+ Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a C content of no more than 15, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6. 24+ In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have 1 to 15 weight percent, 3 to 15 weight percent, 2 to 5 weight percent, or 5 to 10 weight percent of C 24+ Hydrocarbon content.

[0183] The pyrolysis oil may also include various amounts of olefins, aromatics, and other compounds. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil contains at least 1, or at least 2, or at least 5, or at least 10, or at least 15, or at least 20 weight percent olefins and / or aromatics in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may contain no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 2, or no more than 1 weight percent olefins and / or aromatics in each case.

[0184] In one embodiment or in combination with any of the embodiments mentioned herein, the aromatic hydrocarbon content of the pyrolysis oil may be no more than 25, or no more than 20, or no more than 15, or no more than 14, or no more than 13, or no more than 12, or no more than 11, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6, or no more than 5, or no more than 4, or no more than 3, or no more than 2, or no more than 1, in each case by weight. In one embodiment or in combination with any of the embodiments mentioned, the aromatic hydrocarbon content of the pyrolysis oil is no more than 15, or no more than 10, or no more than 8, or no more than 6, in each case by weight.

[0185] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a cycloalkane content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a cycloalkane content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 10, or no more than 5, or no more than 2, or no more than 1, or no more than 0.5, or undetectable amounts in each case. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a cycloalkane content of no more than 5, or no more than 2, or no more than 1 wt.%, or undetectable amounts. Alternatively, the pyrolysis oil may contain 1 to 50 weight percent, 5 to 50 weight percent, or 10 to 45 weight percent cycloalkanes, especially if the r-pyrolysis oil is subjected to a hydrotreating process.

[0186] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a paraffin content of at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a paraffin content of no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have a paraffin content of 25 to 90 weight percent, 35 to 90 weight percent, or 40 to 80 weight percent, or 40 to 70 weight percent, or 40 to 65 weight percent.

[0187] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an n-paraffin content of at least 5, or at least 10, or at least 15, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an n-paraffin content of no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may have an n-paraffin content of 25 to 90 weight percent, 35 to 90 weight percent, or 40 to 70 weight percent, or 40 to 65 weight percent, or 50 to 80 weight percent.

[0188] 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.

[0189] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil can have a normal paraffin to isoparaffin weight ratio of no more than 100:1, 7, or no more than 5:1, or no more than 50:1, or no more than 40:1, or no more than 30:1. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a normal-to-isoparaffin weight ratio in the range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

[0190] It should be noted that all of the above hydrocarbon weight percentages can be determined using gas chromatography-mass spectrometry (GC-MS).

[0191] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may exhibit a temperature of at least 0.6 g / cm 3 , or at least 0.65g / cm 3 , or at least 0.7g / cm 3 Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may exhibit a density of no more than 1 g / cm at 15°C. 3 , or not more than 0.95g / cm 3 , or not more than 0.9g / cm 3 , or not more than 0.85g / cm 3 In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil exhibits a density of 0.6 to 1 g / cm at 15°C. 3 , 0.65 to 0.95 g / cm 3 or 0.7 to 0.9 g / cm 3 .

[0192] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may exhibit an API gravity of at least 28, or at least 29, or at least 30, or at least 31, or at least 32, or at least 33 at 15°C. Additionally, or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil may exhibit an API gravity of no more than 50, or no more than 49, or no more than 48, or no more than 47, or no more than 46, or no more than 45, or no more than 44 at 15°C. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis oil exhibits an API gravity of between 28 and 50, between 29 and 58, or between 30 and 44 at 15°C.

[0193] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a medium boiling point of at least 75°C, or at least 80°C, or at least 85°C, or at least 90°C, or at least 95°C, or at least 100°C, or at least 105°C, or at least 110°C, or at least 115°C. The value may be measured according to ASTM D-2887 or the procedure described in the working examples. If the value is obtained in any method, the medium boiling point having the value is satisfied. Additionally or alternatively, in one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a medium boiling point of no more than 250°C, or no more than 245°C, or no more than 240°C, or no more than 235°C, or no more than 230°C, or no more than 225°C, or no more than 220°C, or no more than 215°C, or no more than 210°C, or no more than 205°C, or no more than 200°C, or no more than 195°C, or no more than 190°C, or no more than 185°C, or no more than 180°C, or no more than 175°C, or no more than 170°C, or no more than 165°C, or no more than 160°C, 1°C, or no more than 55°C, or no more than 150°C, or no more than 145°C, or no more than 140°C, or no more than 135°C, or no more than 130°C, or no more than 125°C, or no more than 120°C. The values ​​can be measured according to ASTM D-2887 or the procedure described in the working examples. If this value is obtained in any method, the medium boiling point with the value is met. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may have a medium boiling point in the range of 75 to 250°C, 90 to 225°C, or 115 to 190°C. As used herein, "medium boiling point" refers to the median boiling point temperature of the pyrolysis oil when 50 weight percent of the pyrolysis oil boils above the medium boiling point and 50 weight percent of the pyrolysis oil boils below the medium boiling point.

[0194] In one embodiment or in combination with any embodiment mentioned herein, the boiling point range of the pyrolysis oil can be such that no more than 10% of the pyrolysis oil has a final boiling point (FBP) of 250°C, 280°C, 290°C, 300°C or 310°C. To determine the FBP, the procedure according to ASTM D-2887 or as described in the working examples can be used, and if the value is obtained under either method, the FBP having the stated value is satisfied.

[0195] Turning to the pyrolysis gases, the pyrolysis gases may have a methane content of at least 1, or at least 2, or at least 5, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20 weight percent. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gases may have a methane content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gases may have a methane content of 1 to 50 weight percent, 5 to 50 weight percent, or 15 to 45 weight percent.

[0196] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas may have a C3 hydrocarbon content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 15, or at least 20, or at least 25 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas may have a C3 hydrocarbon content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas may have a C3 hydrocarbon content of 1 to 50 weight percent, 5 to 50 weight percent, or 20 to 50 weight percent.

[0197] In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at least 11, or at least 12, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20 weight percent in each case. Additionally or alternatively, in one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25 weight percent in each case. In one embodiment or in combination with any of the embodiments mentioned herein, the pyrolysis gas may have a C4 hydrocarbon content of 1 to 50 weight percent, 5 to 50 weight percent, or 20 to 50 weight percent.

[0198] 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).

[0199] Various downstream applications that can utilize the pyrolysis oil and / or pyrolysis gas disclosed above are described in more detail below. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil may undergo one or more processing steps before being introduced into a downstream unit such as a cracking furnace. Examples of suitable processing steps may include, but are not limited to, separation of less desirable components (e.g., nitrogen-containing compounds, oxygen-containing compounds, and / or olefins and aromatics), distillation to provide a specific pyrolysis oil composition, and preheating.

[0200] Now turn to Figure 3 , showing a schematic diagram of a processing zone for pyrolysis oil, according to one embodiment or in combination with any embodiment mentioned herein.

[0201] like Figure 3 As shown in the processing zone 220 shown in , at least a portion of the r-pyrolysis oil 252 made from the recycled waste stream 250 in the pyrolysis system 210 can be passed through the processing zone 220, such as a separator, which can separate the r-pyrolysis oil into a light pyrolysis oil fraction 254 and a heavy pyrolysis oil fraction 256. The separator 220 used for this separation can be of any suitable type, including a single-stage vapor liquid separator or "flash" tower, or a multi-stage distillation tower. The vessel may or may not include internal components, and may or may not use reflux and / or boiling flow.

[0202] In one embodiment or in combination with any embodiment mentioned herein, the C4-C7 content or C8+ content of the heavy fraction can be at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 weight percent. The light fraction can include at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% C3 and lighter (C 3- ) or C7 and lighter (C 7- In some embodiments, the separator can concentrate the desired components into the heavy fraction, so that the heavy fraction can have a C4-C7 content or C7 content higher than the pyrolysis oil taken out from the pyrolysis zone. 8+ The C4-C7 content or C4-C7 content is at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 70, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150% greater. 8+ Content. Figure 3 As shown, at least a portion of the heavy fraction may be sent to a cracking furnace 230 to be cracked as an r-pyrolysis oil composition or as a portion of a pyrolysis oil composition to form an olefin-containing effluent 258, as discussed in further detail below.

[0203] In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil is hydrotreated in the treatment zone, while in other embodiments, the pyrolysis oil is not hydrotreated before entering a downstream unit such as a cracking furnace. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil is not pretreated at all before any downstream application and can be sent directly from the pyrolysis oil source. The temperature of the pyrolysis oil leaving the pretreatment zone can be in the range of 15 to 55°C, 30 to 55°C, 49 to 40°C, 15 to 50°C, 20 to 45°C, or 25 to 40°C.

[0204] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can be combined with a non-recovery cracker stream to minimize the amount of less desirable compounds present in the combined cracker feed. For example, when the r-pyrolysis oil has a concentration of less desirable compounds (e.g., impurities such as oxygenates, aromatic hydrocarbons, or other compounds described herein), the r-pyrolysis oil can be combined with the cracker feed so that the total concentration of the less desirable compounds in the combined stream is less than the original content of the compounds in the r-pyrolysis oil stream (calculated as the difference between the r-pyrolysis oil and the combined stream divided by the r-pyrolysis oil content, expressed as a percentage) by at least 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% combined. In some cases, the amount of non-recovery cracker feed to be combined with the r-pyrolysis oil stream can be determined by comparing the measured amount of one or more less desirable compounds present in the r-pyrolysis oil with the target value of these compounds to determine the difference, and then based on the difference, the amount of non-recovery hydrocarbons to be added to the r-pyrolysis oil stream is determined. The amount of r-pyrolysis oil and non-recovered hydrocarbons can be within one or more ranges described herein.

[0205] At least a portion of the r-olefins may be derived directly or indirectly from the cracking of the r-pyrolysis oil. The process for obtaining r-olefins by cracking (r-pyrolysis oil) may be as follows and as Figure 4 As described in.

[0206] Steering Figure 4 , which is a flow chart of the steps associated with the cracking furnace 20 and separation zone 30 of a system for producing an r-composition obtained by cracking r-pyrolysis oil. Figure 4 As shown, a feed stream containing r-pyrolysis oil (a feed stream containing r-pyrolysis oil) can be introduced into the cracking furnace 20 alone or in combination with a non-recovery cracker feed stream. The pyrolysis unit that produces r-pyrolysis oil can be located at the same location as the production facility. In other embodiments, the r-pyrolysis oil can originate from a remote pyrolysis unit and be transported to the production facility.

[0207] 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.

[0208] In one embodiment or combination with any embodiment mentioned herein, at least 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 97, or at least 98, or at least 99, or 100 weight percent of the r-pyrolysis oil and / or no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10 weight percent of the r-pyrolysis oil is obtained from pyrolysis of a waste stream. In one embodiment or in combination with any embodiment mentioned herein, at least a portion of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock containing plastic waste. Desirably, in each case, at least 90, or at least 95, or at least 97, or at least 98, or at least 99, or at least or 100 wt.% of the r-pyrolysis oil is obtained from the pyrolysis of a feedstock containing plastic waste, or a feedstock containing at least 50 wt.% plastic waste, or a feedstock containing at least 80 wt.% plastic waste, or a feedstock containing at least 90 wt.% plastic waste, or a feedstock containing at least 95 wt.% plastic waste.

[0209] 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.

[0210] In one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can contain at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 weight percent C4-C 30 Hydrocarbons, and as used herein, hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic compounds. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may mainly contain C5-C 25 、C5-C 22 or C5-C 20 hydrocarbons, or may contain at least 55, 60, 65, 70, 75, 80, 85, 90 or 95 weight percent C5-C 25 、C5-C 22 or C5-C 20 hydrocarbon.

[0211] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil composition can comprise C4-C 12 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and alicyclic hydrocarbons) and C 13 -C 22 aliphatic compounds in a weight ratio greater than 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on the weight of the r-pyrolysis oil.

[0212] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil composition can comprise C 13 -C 22 Aliphatic compounds (branched or unbranched alkanes and alkenes (including dienes) and alicyclic hydrocarbons) and 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.

[0213] In one embodiment, the two aliphatic hydrocarbons (branched or unbranched alkanes and alkenes, and alicyclic compounds) with the highest concentration in the r-pyrolysis oil are in the C5-C 18 , or C5-C 16 , or C5-C 14 , or C5-C 10, or in the range of C5-C8 (including the end values).

[0214] 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.

[0215] For example, in one embodiment or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil can contain at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, and / or no more than 99, or no more than 97, or no more than 98 weight percent in each case. More than 95, or not more than 93, or not more than 90, or not more than 87, or not more than 85, or not more than 83, or not more than 80, or not more than 78, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45, or not more than 40, or not more than 35, or not more than 30, not more than 25, not more than 30, or not more than 20, or not more than 15 of paraffins (either straight or branched) based on the total weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein, the pyrolysis oil can have a paraffin content of 25 to 90, 35 to 90, or 40 to 80, or 40 to 70, or 40 to 65 weight percent, or 5 to 50, or 5 to 40, or 5 to 35, or 10 to 35, or 10 to 30, or 5 to 25, or 5 to 20, in each case as wt. % based on the weight of the r-pyrolysis oil composition.

[0216] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include cycloalkanes or cycloaliphatic hydrocarbons in an amount of zero, or at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20, in each case by weight percent, and / or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 5, or no more than 2, or no more than 1, or no more than 0.5, or in an undetectable amount, in each case by weight percent. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have a cycloalkanes content of no more than 5, or no more than 2, or no more than 1 wt.%, or in an undetectable amount. Examples of ranges for the amount of cycloalkanes (or cycloaliphatic hydrocarbons) contained in the r-pyrolysis oil are 0-35, or 0-30, or 0-25, or 2-20, or 2-15, or 2-10, or 1-10, in each case wt. % based on the weight of the r-pyrolysis oil composition.

[0217] In one embodiment or in combination with any of the mentioned embodiments, the r-pyrolysis oil contains no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 5, or no more than 2, or no more than 1 weight percent of aromatic hydrocarbons, based on the total weight of the r-pyrolysis oil. As used herein, the term "aromatic hydrocarbons" refers to the total amount (by weight) of benzene, toluene, xylene, and styrene. The r-pyrolysis oil may include at least 1, or at least 2, or at least 5, or at least 8, or at least 10 weight percent of aromatic hydrocarbons, based on the total weight of the r-pyrolysis oil in each case.

[0218] In one embodiment or in combination with any of the embodiments mentioned or in combination with any of the embodiments mentioned herein, the r-pyrolysis oil may 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 case, based on the total weight of the r-pyrolysis oil, or undetectable. Aromatic compounds include the above aromatic hydrocarbons and any compounds containing aromatic moieties, such as terephthalate residues and fused ring aromatic hydrocarbons, such as naphthalene and tetralin.

[0219] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil can include olefins in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20, or at least 30, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65 olefins in each case by weight percent olefins, and / or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10 weight percent in each case, based on the weight of the r-pyrolysis oil. Olefins include mono-olefins and di-olefins. Examples of suitable ranges include wt. % ratios of 5 to 45, or 10 to 35, or 15 to 30, or 40 to 85, or 45 to 85, or 50 to 85, or 55 to 85, or 60 to 85, or 65 to 85, or 40 to 80, or 45 to 80, or 50 to 80, or 55 to 80, or 60 to 80, or 65 to 80, 45 to 80, or 50 to 80, or 55 to 80, or 60 to 80, or 65 to 80, or 40 to 75, or 45 to 75, or 50 to 75, or 55 to 75, or 60 to 75, or 65 to 75, or 40 to 70, or 45 to 70, or 50 to 70, or 55 to 70, or 60 to 70, or 65 to 70, or 40 to 65, or 45 to 65, or 50 to 65, or 55 to 65, based on the weight of the r-pyrolysis oil.

[0220] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include an amount of zero or at least 0.01, or at least 0.1, or at least 1, or at least 2, or at least 5 weight percent oxygenates or polymers in each case, and / or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 6, or no more than 5, or no more than 3, or no more than 2 weight percent oxygenates or polymers in each case, based on the weight of the r-pyrolysis oil. Oxygenates and polymers are those containing oxygen atoms. Examples of suitable ranges include oxygenates present in an amount in the range of 0-20, or 0-15, or 0-10, or 0.01-10, or 1-10, or 2-10, or 0.01-8, or 0.1-6, or 1-6, or 0.01-5wt.%, based on the weight of the r-pyrolysis oil.

[0221] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the amount of oxygen atoms in the r-pyrolysis oil may be no more than 10, or no more than 8, or no more than 5, or no more than 4, or no more than 3, or no more than 2.75, or no more than 2.5, or no more than 2.25, or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.1, or no more than 0.05, in each case wt. % based on the weight of the r-pyrolysis oil. Examples of amounts of oxygen in the r-pyrolysis oil may be 0-8, or 0-5, or 0-3, or 0-2.5 or 0-2, or 0.001-5, or 0.001-4, or 0.001-3, or 0.001-2.75, or 0.001-2.5, or 0.001-2, or 0.001-1.5, or 0.001-1, or 0.001-0.5, or 0.001-1, in each case in wt. %, based on the weight of the r-pyrolysis oil.

[0222] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may include heteroatom compounds or polymers in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 15, or at least 20 weight percent, and / or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 6, or no more than 5, or no more than 3, or no more than 2 weight percent, based on the weight of the r-pyrolysis oil. Heteroatom compounds or polymers are defined in this paragraph as any compound or polymer containing nitrogen, sulfur or phosphorus. Any other atom is not considered a heteroatom to determine the amount of heteroatoms, heterocompounds or heteropolymers present in the r-pyrolysis oil. The r-pyrolysis oil may contain heteroatoms present in an amount of not more than 5, or not more than 4, or not more than 3, or not more than 2.75, or not more than 2.5, or not more than 2.25, or not more than 2, or not more than 1.75, or not more than 1.5, or not more than 1.25, or not more than 1, or not more than 0.75, or not more than 0.5, or not more than 0.25, or not more than 0.1, or not more than 0.075, or not more than 0.05, or not more than 0.03, or not more than 0.02, or not more than 0.01, or not more than 0.008, or not more than 0.006, or not more than 0.005, or not more than 0.003, or not more than 0.002, in each case in wt. %, based on the weight of the r-pyrolysis oil.

[0223] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the solubility of water in r-pyrolysis oil at 1 atm and 25° C. is less than 2 wt.%, water, or no more than 1.5, or no more than 1, or no more than 0.5, or no more than 0.1, or no more than 0.075, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, in each case wt.% water based on the weight of the r-pyrolysis oil. Desirably, the solubility of water in r-pyrolysis oil is no more than 0.1 wt.%, based on the weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the r-pyrolysis oil contains no more than 2 wt.% water, or no more than 1.5, or no more than 1, or no more than 0.5, desirably or no more than 0.1, or no more than 0.075, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, in each case the wt.% water based on the weight of the r-pyrolysis oil.

[0224] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the solids content in the r-pyrolysis oil is no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, or no more than 0.025, or no more than 0.01, or no more than 0.005, or no more than 0.001, in each case as wt.% solids based on the weight of the r-pyrolysis oil.

[0225] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the sulfur content of the r-pyrolysis oil is no more than 2.5 wt.%, or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.1, or no more than 0.05, desirably or no more than 0.03, or no more than 0.02, or no more than 0.01, or no more than 0.008, or no more than 0.006, or no more than 0.004, or no more than 0.002, or no more than 0.001, in each case wt.% based on the weight of the r-pyrolysis oil.

[0226] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the r-pyrolysis oil can have the following component contents:

[0227] (i) 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 up to 90, or up to 88, or up to 86, or up to 85, or up to 83, or up to 82, or up to 80, or up to 77, or up to 75, or up to 73, or up to 70, or up to 68, or up to 65, or up to 63, or up to 60, in each case wt.%, desirably at least 82% and up to 93%, and / or

[0228] (ii) a hydrogen atom content of 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.%,

[0229] (iii) an oxygen atom content of 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.

[0230] In each case based on the weight of the r-pyrolysis oil.

[0231] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the amount of hydrogen atoms in the r-pyrolysis oil may be in the range of 10-20, or 10-18, or 11-17, or 12-16, or 13-16, or 13-15, or 12-15, in each case wt. % based on the weight of the r-pyrolysis oil.

[0232] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the metal content of the r-pyrolysis oil is desirably low, for example, no more than 2 wt.%, or no more than 1, or no more than 0.75, or no more than 0.5, or no more than 0.25, or no more than 0.2, or no more than 0.15, or no more than 0.1, or no more than 0.05, in each case wt.% based on the weight of the r-pyrolysis oil.

[0233] In one embodiment or in combination with any of the mentioned embodiments or in combination with any of the embodiments mentioned herein, the weight ratio of paraffins to cycloalkanes in the r-pyrolysis oil can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.25:1, or at least 4.5:1, or at least 4.75:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 13:1, or at least 15:1, or at least 17:1, based on the weight of the r-pyrolysis oil.

[0234] In one embodiment or in combination with any of the embodiments mentioned herein or in combination with any of the embodiments mentioned herein, the weight ratio of the combination of paraffins and cycloalkanes to aromatics can be at least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.5:1, or at least 5:1, or at least 7:1, or at least 10:1, or at least 15:1, or at least 20:1, or at least 25:1, or at least 30:1, or at least 35:1, or at least 40:1, based on the weight of the r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the ratio of the combination of paraffins and cycloalkanes to aromatics in the r-pyrolysis oil can be in the range of 50:1-1:1, or 40:1-1:1, or 30:1-1:1, or 20:1-1:1, or 30:1-3:1, or 20:1-1:1, or 20:1-5:1, or 50:1-5:1, or 30:1-5:1, or 1:1-7:1, or 1:1-5:1, 1:1-4:1, or 1:1-3:1.

[0235] In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil may have a boiling point curve defined by one or more of its 10%, its 50% and its 90% boiling points, as defined below. As used herein, "boiling point" refers to the boiling point of the composition measured by ASTM D2887 or according to the procedure described in the working examples. If the value is obtained in any method, the boiling point with the value is satisfied. In addition, as used herein, "x% boiling point" means that according to any of these methods, x weight percentages of the composition boil at the boiling point.

[0236] As used throughout, x% boiling at the temperature means that at least x% of the composition boils at the temperature. In one embodiment or combination with any embodiment described herein, the 90% boiling point of the cracker feed stream or composition can be no more than 350, or no more than 325, or no more than 300, or no more than 295, or no more than 290, or no more than 285, or no more than 280, or no more than 275, or no more than 270, or no more than 265, or no more than 260, or no more than 255, or no more than 250, or no more than 245, or no more than 240, or no more than 235, or no more than 230, or no more than 22 5, or no more than 220, or no more than 215, or no more than 200, or no more than 190, or no more than 180, or no more than 170, or no more than 160, or no more than 150, or no more than 140, in each case °C, and / or at least 200, or at least 205, or at least 210, or at least 215, or at least 220, or at least 225, or at least 230, in each case °C, and / or no more than 25, 20, 15, 10, 5, or 2 weight percent of the r-pyrolysis oil may have a boiling point of 300°C or higher.

[0237] Reference again Figure 3, r-pyrolysis oil may be introduced into a cracking furnace or coils or tubes alone (e.g., in an amount comprising at least 85, or at least 90, or at least 95, or at least 99, or 100, in each case wt.% pyrolysis oil based on the weight of the cracker feed stream) or in combination with one or more non-recovery cracker feed streams. When introduced into a cracker furnace, coils or tubes with a non-recovery cracker feed stream, the r-pyrolysis oil may be present in an amount of at least 1, or at least 2, or at least 5, or at least 8, or at least 10, or at least 12, or at least 15, or at least 20, or at least 25, or at least 30, in each case wt.%, and / or no more than 40, or no more than 35, or no more than 30, or no more than 25, or no more than 20, or no more than 15, or no more than 10, or no more than 8, or no more than 5, or no more than 2, in each case wt.% based on the total weight of the combined streams. Thus, the non-recovery cracker feed stream or composition can be present in the combined stream in an amount of at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, in each case by weight percent, and / or no more than 99, or no more than 95, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, or no more than 55, or no more than 50, or no more than 45, or no more than 40, in each case by weight percent based on the total weight of the combined stream. Unless otherwise indicated herein, the properties of the cracker feed stream described below apply to the non-recovered cracker feed stream before (or in the absence of) being combined with a stream comprising r-pyrolysis oil, as well as to a combined cracker stream comprising both a non-recovered cracker feed and an r-pyrolysis oil feed.

[0238] In one embodiment or in combination with any of the embodiments mentioned herein, the cracker feed stream may comprise a composition comprising primarily C2-C4 hydrocarbons, or a composition comprising primarily C5-C 22As used herein, the term "primarily C2-C4 hydrocarbons" refers to a stream or composition containing at least 50 weight percent of C2-C4 hydrocarbon components. Examples of specific types of C2-C4 hydrocarbon streams or compositions include propane, ethane, butane, and LPG. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed may contain at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.%, based on the total weight of the feed, and / or no more than 100, or no more than 99, or no more than 95, or no more than 92, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, in each case C2-C4 hydrocarbons or linear alkanes weight percent, based on the total weight of the feed. The cracker feed may comprise mainly propane, mainly ethane, mainly butane or a combination of two or more of these components. These components may be non-recovery components. The cracker feed may comprise mainly propane, or at least 50 mol% propane, or at least 80 mol% propane, or at least 90 mol% propane, or at least 93 mol% propane, or at least 95 mol% propane (including any recovery stream mixed with fresh feed). The cracker feed may comprise HD5 quality propane as raw or fresh feed. The cracker may comprise greater than 50 mol% ethane, or at least 80 mol% ethane, or at least 90 mol% ethane, or at least 95 mol% ethane. These components may be non-recovery components.

[0239] In one embodiment or in combination with any embodiment described herein, the cracker feed stream may comprise a predominantly C5-C 22 As used herein, "primarily C5-C 22 "Hydrocarbon" refers to hydrocarbons containing at least 50 weight percent of C5-C 22 %, or at least 90, or at least 95, or at least 92, or at least 90, or at least 85, or at least 80, or at least 85, or at least 90, or at least 95, in each case wt.%, and / or no more than 100, or no more than 99, or no more than 95, or no more than 92, or no more than 90, or no more than 85, or no more than 80, or no more than 75, or no more than 70, or no more than 65, or no more than 60, in each case C5-C 22 , or C5-C20 The hydrocarbon weight percentage is based on the total weight of the stream or composition. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed can have at least 0.5, or at least 1, or at least 2, or at least 5 C 15 and heavier (C 15+ ) content, in each case as weight percent, and / or not more than 40, or not more than 35, or not more than 30, or not more than 25, or not more than 20, or not more than 18, or not more than 15, or not more than 12, or not more than 10, or not more than 5, or not more than 3, in each case as weight percent, based on the total weight of the feed.

[0240] The cracker feed may have a boiling point curve defined by one or more of its 10%, its 50% and its 90% boiling points, the boiling points being obtained by the above method, and further, as used herein, "x% boiling point" means the boiling point at which x weight percent of the composition boils according to the above method. In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feed stream or composition may be no more than 360, or no more than 355, or no more than 350, or no more than 345, or no more than 340, or no more than 335, or no more than 330, or no more than 325, or no more than 320, or no more than 315, or no more than 300, or no more than 295, or no more than 290, or no more than 285, or no more than 280, or no more than 275 , or not more than 270, or not more than 265, or not more than 260, or not more than 255, or not more than 250, or not more than 245, or not more than 240, or not more than 235, or not more than 230, or not more than 225, or not more than 220, or not more than 215, in each case °C, and / or at least 200, or at least 205, or at least 210, or at least 215, or at least 220, or at least 225, or at least 230 °C, in each case °C.

[0241] 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.

[0242] 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.

[0243] In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feed or stream or composition may be at least 350°C, the 10% boiling point may be at least 60°C; and the 50% boiling point may be in the range of 95°C to 200°C. In one embodiment or in combination with any embodiment mentioned herein, the 90% boiling point of the cracker feed or stream or composition may be at least 150°C, the 10% boiling point may be at least 60°C, and the 50% boiling point may be in the range of 80°C to 145°C. In one embodiment or in combination with any embodiment mentioned herein, the cracker feed or stream has a 90% boiling point of at least 350°C, a 10% boiling point of at least 150°C, and a 50% boiling point in the range of 220 to 280°C.

[0244] In one embodiment or in combination with any embodiment mentioned herein or in combination with any embodiment mentioned herein, the r-pyrolysis oil is cracked in a gas furnace. A gas furnace is a furnace having at least one coil that receives (or is operated to receive) a feed that is primarily in the gas phase (more than 50% of the feed weight is vapor) at the coil inlet at the convection zone inlet ("gas coil"). In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the gas coil 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, receives at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, based on the weight of the cracker feed to the coil, or alternatively based on the weight of the cracker feed to the convection zone. The gas furnace may have more than one gas coil. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, 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 or in combination with any mentioned embodiment, the gas coil receives a vapor-phase feed at the coil inlet at the inlet of the convection zone, in which at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is vapor.

[0245] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil is cracked in a cracking furnace. The cracking furnace is a gas furnace. The cracking furnace comprises at least one gas coil and at least one liquid coil in the same furnace, or in the same convection section, or in the same convection box. The liquid coil is a coil that receives a feed that is mainly in liquid phase (more than 50% of the feed weight is liquid) at the coil inlet at the inlet of the convection section ("liquid coil"). In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the liquid coil may receive a feed that is mainly in liquid phase (more than 50% of the feed weight is liquid) at the inlet of the convection section ("liquid coil"). 5+ In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the liquid coil can receive a liquid feedstock of mainly C6-C 22 The raw materials are mainly C7-C 16or alternatively, having at least one coil receiving more than 50 wt. % naphtha, and / or more than 50 wt. % natural gasoline, and / or more than 50 wt. % diesel, and / or more than JP-4, and / or more than 50 wt. % dry cleaning solvent, and / or more than 50 wt. % kerosene, and / or more than 50 wt. % fresh creosote, and / or more than 50 wt. % JP-8 or Jet-A, and / or more than 50 wt. % heating oil, and / or More than 50% heavy fuel oil, and / or more than 50% marine grade C, and / or more than 50% lubricating oil, or in any of these cases at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 98 wt.%, or at least 99 wt.%, based on the weight of the cracker feed to the liquid coils, or alternatively based on the weight of the cracker feed to the convection zone. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, at least one coil in the convection zone or in the convection box of the furnace and not more than 75% of the coils, or not more than 50% of the coils, or not more than at least 40% of the coils are liquid coils. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the liquid coil receives a vapor phase feed at the coil inlet at the inlet of the convection zone, in which liquid phase feed at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 98 wt.%, or at least 99 wt.%, or at least 99.5 wt.%, or at least 99.9 wt.% of the feed is liquid.

[0246] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil is cracked in a thermal gas cracker.

[0247] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-pyrolysis oil is cracked in the presence of steam in a hot steam gas cracker. Steam cracking refers to the high temperature cracking (decomposition) of hydrocarbons in the presence of steam.

[0248] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the r-composition is derived directly or indirectly from cracking r-pyrolysis oil in a gas furnace. The coils in the gas furnace can consist entirely of gas coils, or the gas furnace can be a cracking furnace.

[0249] When the feed stream containing r-pyrolysis oil is combined with the non-recovery cracker feed, this combination can occur upstream of the cracking furnace or inside the cracking furnace or in a single coil or tube. Alternatively, the feed stream containing r-pyrolysis oil and the non-recovery cracker feed can be introduced into the furnace separately, and can pass through a portion or all of the furnaces at the same time, while being isolated from each other by feeding into separate tubes in the same furnace (e.g., a cracking furnace). According to one embodiment or in combination with any embodiment mentioned herein, the manner in which the feed stream containing r-pyrolysis oil and the non-recovery cracker feed are introduced into the cracking furnace is described in further detail below.

[0250] Now turn to Figure 5 , shows a schematic diagram of a cracking furnace suitable for use in an embodiment or in combination with any embodiment mentioned herein.

[0251] In one embodiment or in combination with any embodiment described herein or in combination with any mentioned embodiment, although not shown, an evaporator may be provided to evaporate the condensed feed of C2-C5 hydrocarbons 350 to ensure that the feed to the coil inlet in the convection box 312 or the inlet of the convection zone 310 is primarily a vapor phase feed.

[0252] Figure 5 The cracking furnace shown in FIG. 300 includes a convection section or zone 310, a radiation section or zone 320, and a cross section or zone 330 located between the convection section and the radiation sections 310 and 320. The convection section 310 is a portion of the furnace 300 that receives heat from the hot flue gases and includes a row of tubes or coils 324 through which the cracker stream 350 passes. In the convection section 310, the cracker stream 350 is heated by convection from the hot flue gases passing therethrough. The radiation section 320 is a section of the furnace 300 that transfers heat to the heater tubes primarily by radiation from the high temperature gases. The radiation section 320 also includes a plurality of burners 326 for introducing heat into the lower portion of the furnace. The furnace includes a combustion chamber 322 that surrounds and accommodates the tubes within the radiation section 320, and the burners are directed into the combustion chamber. The crossover section 330 includes conduits for connecting the convection section 310 and the radiant section 320 and can transfer the heated cracker stream from inside or outside one section to another section within the furnace 300.

[0253] As the hot combustion gases rise upward through the furnace, the gases may pass through a convection section 310, wherein at least a portion of the waste heat may be recovered and used to heat the cracker stream passing through the convection section 310. In one embodiment or in combination with any of the embodiments mentioned herein, the cracking furnace 300 may have a single convection (preheat) section 310 and a single radiant section 320, while in other embodiments, the furnace may include two or more radiant sections that share a common convection section. At least one induced draft (ID) fan 316 near the furnace may control the flow of the hot flue gases and the distribution of heat through the furnace, and one or more heat exchangers 340 may be used to cool the furnace effluent 370. In one embodiment or in combination with any of the embodiments mentioned herein (not shown), in addition to or in lieu of Figure 5 An exchanger such as that shown in FIG. 5 (eg, a transfer line heat exchanger or TLE) may be used to cool the cracked olefin-containing effluent using a liquid quench.

[0254] The furnace 300 also includes at least one furnace coil 324 through which the cracker stream passes through the furnace. The furnace coil 324 can be formed of any material that is inert to the cracker stream and suitable for withstanding the high temperatures and thermal stresses within the furnace. The coil can have any suitable shape and can, for example, have a circular or elliptical cross-sectional shape.

[0255] The diameter of the coils or tubes within the coils in the convection section 310 can be at least 1, or at least 1.5, or at least 2, or at least 2.5, or at least 3, or at least 3.5, or at least 4, or at least 4.5, or at least 5, or at least 5.5, or at least 6, or at least 6.5, or at least 7, or at least 7.5, or at least 8, or at least 8.5, or at least 9, or at least 9.5, or at least 10, or at least 10.5, in each case cm, and / or no more than 12, or no more than 11.5, or no more than 11, 1, or no more than 0.5, or no more than 10, or no more than 9.5, or no more than 9, or no more than 8.5, or no more than 8, or no more than 7.5, or no more than 7, or no more than 6.5, in each case cm. All or a portion of one or more coils can be substantially straight, or one or more coils can include spirals, twists, or spiral segments. One or more coils can also have a U-tube or split U-tube design. In one embodiment or in combination with any embodiment mentioned herein, the interior of the tube can be smooth or substantially smooth, or a portion (or all) can be roughened to minimize coking. Alternatively, or in addition, the interior of the tube can include inserts or fins and / or surface metal additives to prevent coke accumulation.

[0256] In one embodiment or in combination with any embodiment mentioned herein, all or a portion of one or more furnace coils 324 passing through the convection section 310 may be oriented horizontally, while all or at least a portion of the furnace coils passing through the radiant section 322 may be oriented vertically. In one embodiment or in combination with any embodiment mentioned herein, a single furnace coil may extend through both the convection section and the radiant section. Alternatively, at least one coil may be divided into two or more tubes at one or more points in the furnace so that the cracker stream may pass in parallel along multiple paths. For example, the cracker stream (including r-pyrolysis oil) 350 may be introduced into multiple coil inlets in the convection zone 310, or into multiple tube inlets in the radiated section 320 or the cross section 330. When multiple coils or tube inlets are introduced simultaneously or nearly simultaneously, the amount of r-pyrolysis oil introduced into each coil or tube may not be adjusted. In one embodiment or in combination with any embodiment mentioned herein, the r-pyrolysis oil and / or the cracker stream may be introduced into a common header, which then guides the r-pyrolysis oil to multiple coils or tube inlets.

[0257] A single furnace may have at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8 or more, in each case, a coil. Each coil may be 5 to 100, 10 to 75, or 20 to 50 meters long and may include at least 1, or at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 10, or at least 12, or at least 14 or more tubes. The tubes of a single coil may be arranged in many configurations and, in one embodiment or in combination with any of the embodiments mentioned herein, may be connected by one or more 180° ("U" shaped) bends. Figure 6 One example of a furnace coil 410 having a plurality of tubes 420 is shown in FIG.

[0258] The olefin plant can have a single cracking furnace, or it can have at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8 or more cracking furnaces operating in parallel. Any one or each furnace can be a gas cracker or a liquid cracker or a cracking furnace. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the furnace is a gas cracker that receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, the cracker feed stream containing at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, or at least 90 wt.% of ethane, propane, LPG, or a combination thereof, based on the weight of all cracker feeds to the furnace. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the furnace is a liquid or naphtha cracker that receives a cracker feed stream passing through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, wherein the cracker feed stream contains at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.% liquid hydrocarbons having carbon numbers of C5-C22 (when measured at 25°C and 1 atm), based on the weight of all cracker feeds to the furnace. In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the cracker is a cracking furnace which receives a cracker feed stream through the furnace, or through at least one coil in the furnace, or through at least one tube in the furnace, wherein the cracker feed stream contains at least 50 wt.%, or at least 75 wt.%, or at least 85 wt.%, or at least 90 wt.% ethane, propane, LPG or a combination thereof, and receives a cracker feed stream containing at least 0.5 wt.%, or at least 0.1 wt.%, or at least 1 wt.%, or at least 2 wt.%, or at least 5 wt.%, or at least 7 wt.%, or at least 10 wt.%, or at least 13 wt.%, or at least 15 wt.%, or at least 20 wt.% liquid and / or r-pyrolysis oil (when measured at 25°C and 1 atm), each based on the weight of all cracker feeds to the furnace.

[0259] Now turn to Figure 7 , showing several possible locations for introducing the feed stream containing r-pyrolysis oil and the non-recovery cracker feed stream into the cracking furnace.

[0260] In one embodiment or in combination with any embodiment mentioned herein, the feed stream 550 containing r-pyrolysis oil can be combined with the non-recovery cracker feed 552 upstream of the convection section to form a combined cracker feed stream 554, which can then be introduced into the convection section 510 of the furnace. Alternatively or additionally, the feed 550 containing r-pyrolysis oil can be introduced into the first furnace coil, while the non-recovery cracker feed 552 is introduced into a separate or second furnace coil, in the same furnace or in the same convection zone. The two streams can then travel parallel to each other through the convection section 510, the crossover 530, and the radiant section 520 in the radiant box 522, so that each stream is substantially fluidly isolated from the other stream over most or all of the path of travel from the inlet to the outlet of the furnace. The pyrolysis stream introduced into any heating zone in the convection section 510 can flow through the convection section 510 and flow into the radiant box 522 as the vaporized stream 514b. In other embodiments, the feed stream 550 containing r-pyrolysis oil may also be introduced into the non-recovery cracker stream 552 as it flows through the furnace coils in the convection section 510 into the cross section 530 of the furnace to form the combined cracker stream 514a, also as shown in FIG. Figure 7 as shown in .

[0261] In one embodiment or in combination with any embodiment mentioned herein or in combination with any mentioned embodiment, the Figure 7 The first heating zone or the second heating zone shown introduces r-pyrolysis oil 550 into the first furnace coil, or an additional amount into the second furnace coil. The r-pyrolysis oil 550 may be introduced into the furnace coils at these locations via nozzles. A convenient method of introducing the r-pyrolysis oil feed is via one or more dilution steam feed nozzles, which are used to feed steam into the coils in the convection zone. The services of one or more dilution steam nozzles may be used to inject r-pyrolysis oil, or new nozzles may be fastened to the coils dedicated to the injection of r-pyrolysis oil. In one embodiment or in combination with any embodiment mentioned herein or in combination with any of the mentioned embodiments, both steam and r-pyrolysis oil may be co-fed into the furnace coils via nozzles downstream of the coil inlet and upstream of the crossover, optionally in the first or second heating zone within the convection zone, such as Figure 7 shown.

[0262] 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.

[0263] Back to Figure 6, the cracker feed stream (non-recycled cracker feed stream or when combined with an r-pyrolysis oil feed stream) 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 section, and dilution steam can be added at some points to control the temperature and cracking severity in the radiant section. 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. In one embodiment or in combination with any of the mentioned embodiments or in combination with any of the embodiments mentioned herein, steam can be used in the same furnace ( Figure 4 Steam 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 of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90.

[0264] a heated cracker stream, which typically has a temperature of at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or 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, or not more than 650, in each case °C, or in the range of 500 to 710°C, in the range of 620 to 740°C, in the range of 560 to 670°C or in the range of 510 to 650°C, and then can be transferred from the convection section of the furnace via the crossover zone to the radiant section.

[0265] In one embodiment or in combination with any of the mentioned embodiments or in combination with any of the embodiments mentioned herein, a feed stream containing r-pyrolysis oil can be added to the cracker stream at the crossover zone. When introduced into the furnace at the crossover zone, the r-pyrolysis oil can be at least partially vaporized or atomized before combining with the cracker stream at the crossover.

[0266] In one embodiment or in combination with any of the embodiments mentioned herein, the vapor liquid separator 640 may include a flash tank, while in other embodiments, it may include a fractionation column. As the stream 614 passes through the vapor liquid separator 640, the gas stream impinges on and flows through the trays, and the liquid from the trays falls to the bottom stream 642. The vapor liquid separator may also include a demister or chevron or other device located near the vapor outlet to prevent liquid from being carried from the vapor liquid separator 640 into the gas outlet.

[0267] 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.

[0268] refer to Figure 5 and 6 , the cracker feed stream (non-recycled cracker feed stream or when combined with an r-pyrolysis oil feed stream) 350 and 650 can be introduced into the furnace coils at or near the entrance of the convection section. The cracker feed stream can then pass through at least a portion of the furnace coils in the convection sections 310 and 610, and dilution steam 360 and 660 can be added at some points to control the temperature and cracking severity in the radiant sections 320 and 620. The amount of steam added can depend on the furnace operating conditions, including the feed type and the desired product distribution, but can be added to achieve a steam to hydrocarbon ratio in the range of 0.1 to 1.0, 0.15 to 0.9, 0.2 to 0.8, 0.3 to 0.75, or 0.4 to 0.6 by weight. In one embodiment or in combination with any embodiment described herein, steam can be used in the same furnace ( Figure 5Steam 360 and 660 may be added to the cracker feed (or any intermediate cracker feed stream within the furnace) when the cracker feed stream has a vapor fraction by weight of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90, or by volume in one embodiment or in combination with any of the mentioned embodiments.

[0269] The heated cracker stream typically has a temperature of at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case ° C, and / or no more than 850, or no more than 840, or no more than 830, or no more than 820, or no more than 810, or no more than 800, or no more than 790, or no more than 780, or no more than 770 , or not more than 760, or not more than 750, or not more than 740, or not more than 730, or not more than 720, or not more than 710, or not more than 705, or not more than 700, or not more than 695, or not more than 690, or not more than 685, or not more than 680, or not more than 675, or not more than 670, or not more than 665, or not more than 660, or not more than 655°C, or not more than 650°C, in each case °C, or in the range of 500 to 710°C, 620 to 740°C, 560 to 670°C, or 510 to 650°C, and then may pass from the convection section 610 of the furnace via the crossover section 630 to the radiant section 620. In one embodiment or in combination with any embodiment mentioned herein, the feed stream 550 containing r-pyrolysis oil may be added to the cracker stream at the crossover section 530, such as Figure 6As shown. When introduced into the furnace at the intersection section, the r-pyrolysis oil can be at least partially vaporized or atomized before combining with the cracker stream at the intersection. The temperature of the cracker stream passing through the intersection 530 or 630 can be at least 400, 425, 450, 475, can be at least 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 840, or no more than 850, or no more than 860, or no more than 870, or no more than 880, or no more than 890, or no more than 900, or no more than 910, or no more than 920, or no more than 930, or no more than 940, or no more than 950, or no more than 960, or no more than 970, or no more than 980, or no more than 990, or no more than 10 ... More than 810, or not more than 800, or not more than 790, or not more than 780, or not more than 770, or not more than 760, or not more than 750, or not more than 740, or not more than 730, or not more than 720, or not more than 710, or not more than 705, or not more than 700, or not more than 695, or not more than 690, or not more than 685, or not more than 680, or not more than 675, or not more than 670, or not more than 665, or not more than 660, or not more than 655°C, or not more than 650°C, in each case in°C, or in the range of 620 to 740°C, 550 to 680°C, or 510 to 630°C.

[0270] The resulting cracker feed stream then passes through a radiant section, wherein the feed stream containing the r-pyrolysis oil is thermally cracked to form lighter hydrocarbons, including olefins such as ethylene, propylene and / or butadiene. The residence time of the cracker feed stream in the radiant section may be at least 0.1, or at least 0.15, or at least 0.2, or at least 0.25, or at least 0.3, or at least 0.35, or at least 0.4, or at least 0.45, in each case seconds, and / or no more than 2, or no more than 1.75, or no more than 1.5, or no more than 1.25, or no more than 1, or no more than 0.9, or no more than 0.8, or no more than 0.75, or no more than 0.7, or no more than 0.65, or no more than 0.6, or no more than 0.5, in each case seconds. The temperature at the inlet of the furnace coil is at least 500, or at least 510, or at least 520, or at least 530, or at least 540, or at least 550, or at least 560, or at least 570, or at least 580, or at least 590, or at least 600, or at least 610, or at least 620, or at least 630, or at least 640, or at least 650, or at least 660, or at least 670, or at least 680, in each case ° C, and / or does not exceed 850, or does not exceed 840, or does not exceed 830, or does not exceed 820, or does not exceed 810, or does not exceed 800, or does not exceed 890, or does not exceed 880, or does not exceed 890, or does not exceed 810. 770°C, or not more than 760°C, or not more than 750°C, or not more than 740°C, or not more than 730°C, or not more than 720°C, or not more than 710°C, or not more than 705°C, or not more than 700°C, or not more than 695°C, or not more than 690°C, or not more than 685°C, or not more than 680°C, or not more than 675°C, or not more than 670°C, or not more than 665°C, or not more than 660°C, or not more than 655°C, or not more than 650°C, in each case in the range of 550 to 710°C, 560 to 680°C, or 590 to 650°C, or 580 to 750°C, 620 to 720°C, or 650 to 710°C.

[0271] 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 no more than 970, or no more than 960, or no more than 950, or no more than 940, or no more than 930, or no more than 920, or no more than 910, or no more than 900, or no more than 890, or no more than 880, or no more than 875, or no more than 870, or no more than 860, or no more than 850, or no more than 840, or no more than 830, in each case ° C, in the range of 730 to 900 ° C, 750 to 875 ° C, or 750 to 850 ° C. In one embodiment or in combination with any embodiment mentioned herein, the mass velocity of the cracker feed stream through at least one or at least two radiant coils (for clarity, as determined across the entire coil as opposed to the tubes within the coil) is between 60 and 165 kilograms per second (kg / s) per square meter (m 2 ) cross-sectional area (kg / s / m 2 ), 60 to 130 (kg / s / m 2 ), 60 to 110 (kg / s / m 2 ), 70 to 110 (kg / s / m 2 ) or 80 to 100 (kg / s / m 2 When steam is present, the mass velocity is based on the total flow rate of hydrocarbon and steam.

[0272] In one embodiment or in combination with any of the embodiments mentioned or in combination with any of the embodiments mentioned herein, the burners in the radiant zone provide an average heat flux into the coil of 60 to 160 kW / m 2 , or 70 to 145kW / m 2 , or 75 to 130kW / m 2 The highest (hottest) coil surface temperature is in the range of 1035 to 1150°C, or 1060 to 1180°C. The pressure at the inlet of the furnace coil in the radiant section is in the range of 1.5 to 8 bar absolute pressure (bara), or 2.5 to 7 bara, and the outlet pressure of the furnace coil in the radiant section is in the range of 15 to 40 psia, or 15 to 30 psia. The pressure drop across the furnace coil in the radiant section can be 1.5 to 5 bara, or 1.75 to 3.5 bara, or 1.5 to 3 bara, or 1.5 to 3.5 bara.

[0273] In one embodiment or in combination with any of the embodiments mentioned or in combination with any of the embodiments 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 product mass / raw material mass × 100%. The olefin-containing effluent stream comprises at least about 30, or at least 40, or at least 50, or at least 60, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case as a weight percentage of ethylene, propylene, or ethylene and propylene, based on the total weight of the effluent stream.

[0274] In one embodiment or in combination with any of the embodiments mentioned, the olefin-containing effluent stream comprises MAPD (methylacetylene and propadiene). 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 total weight of the effluent stream from the furnace.

[0275] In one embodiment or in combination with any of the mentioned embodiments, the olefin-containing effluent stream comprises acetylene. The amount of acetylene can be at least 2000 ppm, or at least 5000 ppm, or at least 8000 ppm, or at least 10,000 ppm, based on the total weight of the effluent stream from the furnace.

[0276] Now go to Fig. 9 , a block diagram illustrating the major elements of the furnace effluent processing section is shown.

[0277] like Fig. 9 As shown, the olefin-containing effluent stream from the cracking furnace 700, which includes the recovered components, is rapidly cooled (e.g., quenched) in a transfer line exchange ("TLE") 680, as shown. Figure 8 As shown, to prevent the production of large amounts of undesirable byproducts and to minimize fouling in downstream equipment, as well as to produce steam. In one embodiment or in combination with any of the embodiments mentioned herein, the temperature of the effluent containing the r-composition from the furnace can be reduced by 35 to 485°C, 35 to 375°C, or 90 to 550°C to a temperature of 500 to 760°C. The cooling step is performed immediately after the effluent stream leaves the furnace, such as within 1 to 30, 5 to 20, or 5 to 15 milliseconds. In one embodiment or in combination with any of the embodiments mentioned herein, the quenching step is performed in the quench zone 710 by heating the effluent in a heat exchanger (sometimes referred to as a transfer line exchanger, such as Figure 5 The TLE 340 is shown in Figure 8 In some embodiments, the quenching step is performed by indirect heat exchange with high pressure water or steam in the effluent (shown as TLE 680 in FIG. 1 ), while in other embodiments, the quenching step is performed by direct contact of the effluent with a quenching liquid 712 (shown as Fig. 9 ). The temperature of the quench liquid may be at least 65, or at least 80, or at least 90, or at least 100, in each case, ° C, and / or no more than 210, or no more than 180, or no more than 165, or no more than 150, or no more than 135, in each case, ° C. When a quench liquid is used, contacting may be conducted in a quench tower, and a liquid stream comprising gasoline and other similar boiling range hydrocarbon components may be removed from the quench tower. In some cases, a quench liquid may be used when the cracker feed is primarily liquid, and a heat exchanger may be used when the cracker feed is primarily vapor.

[0278] The resulting cooled effluent stream is then subjected to vapor-liquid separation, and the vapor is compressed in compression zone 720, such as in a gas compressor having, for example, 1 to 5 compression stages, with optional interstage cooling and liquid removal. The gas stream pressure at the outlet of the first set of compression stages is in the range of 7 to 20 bar gauge (barg), 8.5-18 psig (0.6 to 1.3 barg), or 9.5 to 14 barg.

[0279] The resulting compressed stream is then treated in an acid gas removal zone 722 to remove acid gases, including CO, CO2, and H2S, by contacting with an acid gas removal agent. Examples of acid gas removal agents may include, but are not limited to, caustic amines and various types of amines. In one embodiment or in combination with any of the embodiments mentioned herein, a single contactor may be used, while in other embodiments, a dual tower absorber-stripper configuration may be employed.

[0280] Then, the treated compressed olefin-containing stream can be further compressed via a compressor in another compression zone 724, optionally with interstage cooling and liquid separation. The resulting compressed stream has a pressure of 20 to 50 barg, 25 to 45 barg or 30 to 40 barg. Any suitable dehumidification method can be used, including, for example, molecular sieves or other similar methods to dry the gas in the drying zone 726. Then, the resulting stream 730 can be sent to a fractionation section, where olefins and other components can be separated into various high-purity products or intermediate streams.

[0281] Now go to Fig.10, a schematic diagram of the main steps of the fractionation section is provided. In one embodiment or in combination with any of the embodiments mentioned herein, the initial tower of the fractionation system may not be a demethanizer 810, but may be a deethanizer 820, a depropanizer 840, or any other type of tower. As used herein, the term "demethanizer" refers to a tower whose light bonds are methane. Similarly, "deethanizer" and "depropanizer" refer to towers with ethane and propane as light bond components, respectively.

[0282] like Fig.10 As shown, the feed stream 870 from the quench stage can be introduced into a demethanizer (or other) 810, wherein methane and lighter (CO, CO2, H2) components 812 are separated from ethane and heavier components 814. The demethanizer is operated at a temperature of at least -145, or at least -142, or at least -140, or at least -135, in each case ° C, and / or no more than -120, -125, -130, -135 ° C. The bottoms stream 814 from the demethanizer is then introduced into a deethanizer 820, wherein C2 and lighter components 816 are separated from C3 and heavier components 818 by fractionation, the bottoms stream comprising at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%, in each case as a percentage, of the total amount of ethane and heavier components introduced into the column. The deethanizer 820 may be operated at a top temperature of at least -35, or at least -30, or at least -25, or at least -20, in each case, °C, and / or no more than -5, -10, -10, -20 °C, and a top pressure of at least 3, or at least 5, or at least 7, or at least 8, or at least 10, in each case, barg, and / or no more than 20, or no more than 18, or no more than 17, or no more than 15, or no more than 14, or no more than 13, in each case, barg. The deethanizer 820 recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case, percent of the total amount of C2 and lighter components introduced into the column in the top stream. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 816 removed from the deethanizer comprises at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case weight percent ethane and ethylene, based on the total weight of the overhead stream.

[0283] like Fig.10As shown, the C2 and lighter overhead stream 816 from the deethanizer 820 is further separated in an ethane-ethylene fractionator (ethylene fractionator) 830. In the ethane-ethylene fractionator 830, an ethylene and lighter component stream 822 can be taken from the overhead of the column 830, or as a side stream from the top of the column, while ethane and any remaining heavier components are removed in a bottoms stream 824. The ethylene fractionator 830 can be operated at a top temperature of at least -45, or at least -40, or at least -35, or at least -30, or at least -25, or at least -20, in each case ° C, and / or no more than -15, or no more than -20, or no more than -25, in each case ° C, and a top pressure of at least 10, or at least 12, or at least 15, in each case barg, and / or no more than 25, 22, 20 barg. The ethylene-rich overhead stream 822 can contain at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 98, or at least 99, in each case weight percent ethylene, based on the total weight of the stream, and can be sent to downstream processing units for further processing, storage or sale. The overhead ethylene stream 822 produced during cracking of a cracker feed containing r-pyrolysis oil is an r-ethylene composition or stream. In one embodiment or in combination with any of the embodiments mentioned herein, the r-ethylene stream can be used to prepare one or more petrochemical products.

[0284] The bottoms stream of the ethane-ethylene fractionator 824 can include at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98 weight percent ethane in each case, based on the total weight of the bottoms stream. As previously described, all or a portion of the recovered ethane can be recycled to the cracking furnace as additional feedstock, either alone or in combination with a feed stream containing r-pyrolysis oil.

[0285] The liquid bottoms stream 818 from the deethanizer may be enriched in C3 and heavier components and may be separated in the depropanizer 840, such as Fig.10In the depropanizer 840, C3 and lighter components are removed as an overhead vapor stream 826, while C4 and heavier components may leave the column in a liquid bottoms stream 828. The depropanizer 840 may be operated at an overhead temperature of at least 20, or at least 35, or at least 40, in each case, °C, and / or no more than 70, 65, 60, 55 °C, and at an overhead pressure of at least 10, or at least 12, or at least 15, in each case, barg, and / or no more than 20, or no more than 17, or no more than 15, in each case, barg. The depropanizer 840 recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case, a percentage of the total amount of C3 and lighter components introduced into the column in the overhead stream 826. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 826 removed from the depropanizer 840 comprises at least or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98, in each case weight percent of propane and propylene, based on the total weight of the overhead stream 826.

[0286] The overhead stream 826 from the depropanizer 840 is introduced into a propane-propylene fractionator (propylene fractionator) 860, wherein propylene and any lighter components are removed in an overhead stream 832, while propane and any heavier components exit the column in a bottoms stream 834. The propylene fractionator 860 may be operated at an overhead temperature of at least 20, or at least 25, or at least 30, or at least 35, in each case °C, and / or no more than 55, 50, 45, 40 °C, and an overhead pressure of at least 12, or at least 15, or at least 17, or at least 20, in each case barg, and / or no more than 20, or no more than 17, or no more than 15, or no more than 12, in each case barg. The overhead stream 860 rich in propylene can contain at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 98, or at least 99, in each case, propylene weight percent, based on the gross weight of the stream, and can be sent to a downstream processing unit for further processing, storage or sale. The overhead propylene stream produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-propylene composition or stream. In one embodiment or in combination with any embodiment mentioned herein, the stream can be used to prepare one or more petrochemical products.

[0287] 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.

[0288] Refer again Fig.10 The bottom stream 828 from the depropanizer 840 can be sent to the debutanizer 850 for separating the C4 components, including butenes, butanes and butadiene, from the C 5+ Component separation. The debutanizer can be operated at a tower top temperature of at least 20, or at least 25, or at least 30, or at least 35, or at least 40, in each case ° C, and / or no more than 60, or no more than 65, or no more than 60, or no more than 55, or no more than 50, in each case ° C, and a tower top pressure of at least 2, or at least 3, or at least 4, or at least 5, in each case barg, and / or no more than 8, or no more than 6, or no more than 4, or no more than 2, in each case barg. The debutanizer recovers at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 97, or at least 99, in each case a percentage of the total amount of C4 and lighter components introduced into the tower in the tower top stream 836. In one embodiment or in combination with any embodiment mentioned herein, the overhead stream 836 removed from the debutanizer contains at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, in each case weight percent butadiene, based on the total weight of the overhead stream. The overhead stream 836 produced during the cracking of the cracker feed containing r-pyrolysis oil is an r-butadiene composition or stream. The bottoms stream 838 from the debutanizer mainly contains at least 50, or at least 60, or at least 70, or at least 80, or at least 90, or at least 95 weight percent of C5 and heavier components, based on the total weight of the stream. The debutanizer bottoms stream 838 can be sent for further separation, processing, storage, sale or use.

[0289] 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.

[0290] PVA method

[0291] In one embodiment or in combination with any of the mentioned embodiments, there is now provided a method of processing pr-A by feeding pr-A into a reactor in which a polyvinyl acetal or PVA composition is prepared. In another embodiment, there is provided a method of preparing r-PVA or pr-PVA by reacting pr-A with an aldehyde composition to produce a PVA effluent, the PVA effluent optionally containing a pr-PVA composition. Also provided is an r-PVA or pr-PVA having monomers derived from the pr-A composition. Also provided is an r-PVA, and integral interlayers prepared therefrom, and other articles prepared therefrom.

[0292] In one embodiment or in combination with any of the embodiments mentioned, the r-PVA composition and resin can be a resin product prepared by condensing all or part of the hydroxyl groups of rA or pr-A with PVOH or incompletely hydrolyzed polyvinyl ester in the presence of an acid catalyst. Optionally, at least a portion of rA or pr-A is directly or indirectly derived from the cracking of r-pyrolysis oil.

[0293] R-PVA resins generally have residual hydroxyl content, ester content and acetal content. Residual hydroxyl content (calculated as PVOH) refers to the weight percent of the part with hydroxyl groups retained on the polymer chain. For example, r-PVA can be by hydrolyzing polyvinyl acetate into PVOH, then PVOH and rA or pr-A, such as r-acetaldehyde, r-propionaldehyde, r-butyraldehyde, pr-acetaldehyde, pr-propionaldehyde, pr-butyraldehyde, etc., and react r-butyraldehyde or pr-butyraldehyde desirably to prepare a polymer with repeating vinyl butyral units. Aldehydes (C5-10) with higher carbon numbers can be used, or they can also be used in combination with aldehydes with lower carbon numbers. For example, 2-ethylhexanal can be used as other n-butyraldehyde or isobutyraldehyde, or used in combination with n-butyraldehyde or isobutyraldehyde.

[0294] In the process of hydrolyzing polyvinyl acetate, usually not all of the acetate side groups are converted to hydroxyl groups. In addition, the reaction with aldehydes usually does not result in all of the hydroxyl groups on the PVOH being converted to acetal groups. Therefore, in any finished r-PVA, there will usually be residual ester groups, such as acetyl groups (as vinyl acetate groups) and residual hydroxyl groups (as vinyl hydroxyl groups) as side groups on the polymer chain, and acetal (e.g., butyral) groups (as vinyl acetal groups). As used herein, the residual hydroxyl content is measured in weight percent according to ASTM 1396.

[0295] In one embodiment or in combination with any other mentioned embodiment, a reaction medium is formed by combining rA with a PVOH composition, an acid catalyst and a solvent. In the presence of an acid catalyst, rA condenses with the hydroxyl groups of the PVOH composition to produce r-PVA precipitated from the reaction medium. The r-PVA in the organic solvent medium can be recovered by adding water to precipitate it from the solvent medium. The precipitated crude resin contains r-PVA, residues of the acid catalyst and residues of unreacted aldehydes, and as a result, the crude r-PVA resin is washed and dried.

[0296] In one embodiment or in combination with any of the mentioned embodiments, the concentration of pr-A introduced into the reactor vessel is at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 99 wt.% of aldehyde compounds based on the weight of pr-A fed to the reactor.

[0297] The aldehyde compound can be acetaldehyde, butyraldehyde, n-butyraldehyde and iso-butyraldehyde, or a combination thereof. Desirably, the aldehyde compound is, and pr-A contains at least an n-butyraldehyde compound. In one embodiment or in combination with any of the mentioned embodiments, the amount of r-n-butyraldehyde or pr-n-butyraldehyde can be at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 99 wt.%, based on the weight of the aldehyde, or as fed to the reactor. In one embodiment or in combination with any of the mentioned embodiments, the concentration of pr-A introduced into the reactor vessel is at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 99 wt.%, based on the weight of the aldehyde composition fed to the reactor.

[0298] In one embodiment or in combination with any of the mentioned embodiments, the aldehyde fed to the reaction vessel contains no recycled components. In another embodiment, at least a portion of the aldehyde composition is derived directly or indirectly from the cracking of r-pyrolysis oil or obtained from r-pyrolysis gas. For example, at least 0.005 wt.%, or at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, or at least 0.15 wt.%, or at least 0.2 wt.%, or at least 0.25 wt.%, or at least 0.3 wt.%, or at least 0.35 wt.%, or at least 0.4 wt.%, or at least 0.45 wt.%, or at least 0.5 wt.%, or at least 0.6 wt.%, or at least 0.7 wt.%, or at least 0.8 wt.%, or at least 0.9 wt.%, or at least 1 wt.%, or at least 2 wt.%, or at least 3 wt.%, or at least 4 wt.%, or at least 5 wt.%, or at least 6 wt.%, Or at least 7 wt.%, or at least 8 wt.%, or at least 9 wt.%, or at least 10 wt.%, or at least 11 wt.%, or at least 13 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 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.%, or 100 wt.% of the aldehyde composition is rA or pr-A. Additionally or alternatively, at most 100wt.%, or at most 98wt.%, or at most 95wt.%, or at most 90wt.%, or at most 80wt.%, or at most 75wt.%, or at most 70wt.%, or at most 60wt.%, or at most 50wt.%, or at most 40wt.%, or at most 30wt.%, or at most 20wt.%, or at most 10wt.%, or at most 8wt.%, or at most 5wt.%, or at most 4wt.%, or at most 3wt.%, or at most 2wt.%, or at most 1wt.%, or At most 0.8 wt.%, or at most 0.7 wt.%, or at most 0.6 wt.%, or at most 0.5 wt.%, or at most 0.4 wt.%, or at most 0.3 wt.%, or at most 0.2 wt.%, or at most 0.1 wt.%, or at most 0.09 wt.%, or at most 0.07 wt.%, or at most 0.05 wt.%, or at most 0.03 wt.%, or at most 0.02 wt.%, or at most 0.01 wt.% of the aldehyde composition is r-A or pr-A, optionally from cracked r-pyrolysis oil, based on the weight of the aldehyde composition.In each case, the amounts recited apply not only to the aldehyde fed to the reactor, but may alternatively or additionally apply to the aldehyde composition feedstock supplied to the PVA manufacturer, or may be used as a basis for correlating or calculating the amount of recycled content in the r-PVA, such as when a pr-A source is blended with non-recycled components AD to prepare an aldehyde composition having the above amounts of pr-A.

[0299] In one embodiment or in combination with any of the aforementioned embodiments, the PVA composition has associated therewith, or contains, or is labeled, advertised, or certified as containing, an amount of recycled content 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 18wt.%, or at most 16wt.%, or at most 15wt.%, or at most 14wt.%, or at most 13wt.%, or at most 11wt.%, or at most 10wt.%, or at most 8wt.%, or at most 6wt.%, or at most 5wt.%, or at most 4wt.%, or at most 3wt.%, or at most 2wt.%, or at most 1wt.%, or at most 0.9wt.%, or at most 0.8wt.%, or at most 0.7wt.%, based on the weight of the PVA composition. The recycled component associated with PVA can be established by applying the recycled component value to PVA, such as by deducting the recycled component value from the recycled stock filled with a quota (credit or allocation), or by reacting rA raw materials to prepare r-PVA. The quota can be included in a recycled stock created, maintained or operated by or for a PVA manufacturer. The quota is obtained from any source along any manufacturing chain of the product. In one embodiment, the source of the allowances is derived indirectly from pyrolysis recycled waste, or from cracked r-pyrolysis oil or r-pyrolysis gas.

[0300] The amount of recycled content in the rA feedstock fed to the PVA reactor, or the amount of recycled content applied to the r-PVA, or the amount of rA required to be fed to the reactor to require the desired amount of recycled content in the PVA if all recycled content from rA is applied to the PVA, can be determined or calculated by any of the following methods:

[0301] (i) the quota associated with rA used to feed the reactor is determined by the amount certified or declared by the supplier of the aldehyde composition transferred to the PVA manufacturer, or

[0302] (ii) the amount declared by the PVA manufacturer as fed to the PVA reactor, or

[0303] (iii) using a mass balance approach to back-calculate the minimum amount of recycled content in the feedstock from the amount of recycled content declared, advertised, or claimed by the manufacturer, whether or not accurate, as applied to PVA products, or

[0304] (iv) Using a proportional mass method, blending non-recycled content with recycled content feedstock AD, or combining recycled content with a portion of the feedstock

[0305] Satisfying any one of methods (i)-(iv) is sufficient to establish the portion of rA derived directly or indirectly from the cracking of recycled waste, pyrolysis of recycled waste, pyrolysis gas produced by pyrolysis of recycled waste, and / or r-pyrolysis oil produced by pyrolysis of recycled waste. In the case where the rA feed is blended with recycled feed from other recycled sources, the percentage in the statement attributable to rA directly or indirectly obtained from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced by pyrolysis of recycled waste, and / or r-pyrolysis oil produced by pyrolysis of recycled waste is determined by the ratio of the mass of rA directly or indirectly obtained from the cracking of recycled waste, pyrolysis of recycled waste, pyrolysis gas produced by pyrolysis of recycled waste, and / or r-pyrolysis oil produced by pyrolysis of recycled waste to the mass of recycled aldehydes from other sources.

[0306] Methods (i)-(ii) do not require calculations because they are determined based on what the AD manufacturer or PVA manufacturer or supplier states, claims, or otherwise communicates to each other or to the public. Calculation methods (iii) and (iv).

[0307] In one embodiment or in combination with any of the mentioned embodiments, the minimum amount of recycled content AD fed to the reactor can be determined by knowing the amount of recycled content associated with the final product PVA and assuming that all recycled content in the PVA is attributable to the rA fed to the reactor and not to the PVOH or PVAc fed to the reactor. The minimum portion of the rA content of the PVA product directly or indirectly derived from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced by pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced by pyrolysis of recycled waste to produce the product associated with a specific amount of recycled content can be calculated as:

[0308]

[0309] wherein P represents the minimum portion of rA or pr-A, or alternatively from cracked r-pyrolysis oil, and

[0310] %D represents the percentage of recycled content declared in the product r-PVB, and

[0311] a% refers to the weight percent of the aldehyde segments present in the PVA polymer, for example, when the aldehyde is butyraldehyde, it is usually expressed as the weight percent of the polyvinyl butyral segments, and

[0312] Pm refers to the molecular weight of the segment unit containing the aldehyde, and

[0313] Em refers to the molecular weight of the aldehyde portion of the aldehyde-containing segment unit, not exceeding the molecular weight of the aldehyde reactant, and

[0314] Y represents the percentage yield of the product, such as PVB, which is determined as an average annual yield, regardless of whether the feedstock is rA. If the average annual yield is unknown, it can be assumed that the yield is the industry average yield using the same process technology.

[0315] As an example, it is stated that the supply of PVB has 10% recycled content, the recycled content is attributable to n-butyraldehyde, the yield of PVB is 95%, and the polyvinyl butyral content is specified to be 70 wt%. In this case, the molecular weight of the butyraldehyde segment is (C8H 14 O2) or 142.2 g / mol, and the mass of the butyraldehyde part is 72.11 g / mol. The minimum amount of recycled content in butyraldehyde fed to the reactor from a PVB composition certified or advertised to have 10% recycled content is calculated as follows:

[0316]

[0317] If the designation of recycled content in PVB is only 10%, the amount of recycled content in the r-butyraldehyde feed can be greater than 26.77%, resulting in excess recycled content remaining. For example, rA can contain 50% recycled content and only 10% belongs to PVB, with the remainder being available for products held in a credit stock. Excess recycled content can be stored in the recycled stock and applied to other PVA products that are not made with rA or that have insufficient amounts of rA recycled content relative to the amount of recycled content that is desired to be applied to PVA. However, regardless of whether the manufacturer of the PVA actually specifies that the rA raw material contains a minimum amount of recycled content, it is assumed that the r-PVA specified to contain a certain recycled content is made from an rA raw material containing the minimum recycled content as calculated above.

[0318] In the case of the proportional mass approach in method (iv), the portion of rA derived directly or indirectly from cracking of recycled waste, pyrolysis of recycled waste, pyrolysis gas produced from pyrolysis of recycled waste and / or r-pyrolysis oil produced from pyrolysis of recycled waste will be calculated based on the mass of recycled content available to the PVA manufacturer through purchase or transfer, or generated in the case of AD incorporation into rA production, attributed to the daily run feedstock divided by the mass of rA feedstock, or:

[0319]

[0320] where P represents the percentage of recovered components in the AD feed stream, and

[0321] where Mr is the mass of recovered components attributed to stream rA per day, and

[0322] Ma is the mass of all AD raw materials used to prepare PVA on the corresponding day.

[0323] For example, if a PVA manufacturer has access to 1000 kg of a recycling allotment or credit derived from pyrolysis recycled waste, and the PVA manufacturer elects to attribute 10 kg of the recycling allotment to the AD feedstock used to make the PVA, and the AD feedstock is employed at 100 kg / day to make the PVA, then the portion P of the rA feedstock derived directly or indirectly from cracked pyrolysis oil would be 10 kg / 100 kg, or 10 wt%. The AD feedstock composition would be considered the rA composition because a portion of the recycling allotment is applied to the AD feedstock used to make the PVA.

[0324] In another embodiment, methods are provided for distributing recycled content in various products manufactured by a PVA manufacturer, or in products manufactured by any one or combination of entities in a family of entities of which the PVA manufacturer is a part. For example, any combination or all of a family of entities, or a PVA manufacturer of a site, may:

[0325] Adopt a symmetrical distribution of recycled content values ​​in its products based on the same fractional percentage of recycled content in one or more feedstocks, or based on the amount of quota received. For example, if 5 wt.% of the AD feedstock is r-AD, or if the quota value is 5 wt.% of all AD feedstock, then all PVA made with AD feedstock may contain a 5 wt.% recycled content value. In this case, the amount of recycled content in the product is proportional to the amount of recycled content in the feedstock from which the product is made; or

[0326] Adopting an asymmetric distribution of recycled content values ​​in its products based on the same fractional percentage of recycled content in one or more raw materials, or based on the quota amount received. For example, if 5wt.% of the AD raw material is rA, or if the quota value is 5wt.% of the total AD raw material, one PVA volume or batch can receive a greater amount of recycled content value than other PVA batches or volumes produced, provided that the total amount of recycled content does not exceed the total amount of rA received or allocated, or the total amount of recycled content in the recycled stock. One batch of PVA can contain 5% recycled content and another batch can contain 0% recycled content, even if both volumes are made from the same volume of AD raw materials. In an asymmetric distribution of recycled content, manufacturers can tailor the recycled content to the volume of PVA sold as needed among customers, thereby providing flexibility among customers, some of whom may require more recycled content in the volume of PVA than other customers.

[0327] Symmetrical distribution and asymmetric distribution of recycled 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, recycled component input (recycled component raw material or quota) can be to a site, and the recycled component value from the input is applied to one or more products manufactured at the same site, and at least one of the products manufactured at the site is PVA, and optionally, at least a portion of the recycled component value is applied to the PVA product. The recycled component value can be applied to the product of the site symmetrically or asymmetrically. The recycled component value can be applied to different PVA volumes symmetrically or asymmetrically, or applied to the combination of PVA and other products prepared at the site. For example, the recycled component value is transferred to the recycled stock located at the site, generated at the site, or the raw material containing the recycled component value reacts at the site (collectively referred to as "recycled input"), and the recycled component value obtained from the input is:

[0328] a. symmetrically distributed over at least a portion or all of the volume of PVA prepared at said site over a period of time (e.g., within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously); or

[0329] b. symmetrically distributed over at least a portion or all of the volume of PVA produced at the site and over at least a portion or a second different product produced at the same site, each within the same time period (e.g., within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously); or

[0330] c. The recycled content is symmetrically distributed over the same time period (e.g., within the same day, or within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously) across all products manufactured at the site that actually have recycled content applied. While a variety of products may be manufactured at a site, in this option, not all products necessarily receive a recycled content value, but rather the distribution is symmetrical for all products that do receive a recycled content value or have a recycled content value applied; or

[0331] d. Asymmetrically distributed over at least two volumes of PVA manufactured at the same site, optionally within the same time period (e.g., within 1 day, or within 1 week, or within 1 month, or within 6 months, or within a calendar year, or continuously), or as sold to at least two different customers. For example, one volume of PVA produced may have a greater recycled content value than a second volume of PVA manufactured at the site, or one volume of PVA manufactured at the site and sold to one customer may have a greater recycled content value than a second volume of PVA manufactured at the site and sold to a second, different customer, or

[0332] e. Asymmetrically distributed over at least one volume of PVA and at least one volume of a different product prepared at the same site, each optionally within the same time period (e.g., within 1 day, or within 1 week, or within 1 month, or within 6 months, or within a calendar year, or continuously), or sold to at least two different customers.

[0333] In one embodiment or in combination with any of the embodiments mentioned, a recycled component input or generation (a recycled component raw material or quota) can be to or at a first site, and the recycled component value from the input is transferred to a second site and applied to one or more products prepared at the second site, and at least one of the products prepared at the second site is PVA, and optionally, at least a portion of the recycled component value is applied to the PVA product prepared at the second site. The recycled component value can be applied symmetrically or asymmetrically to the products at the second site. The recycled component value can be applied symmetrically or asymmetrically to different PVA volumes, or to a combination of PVA and other products prepared at the second site. For example, the recycled component value is transferred to a recycled stock located at the first site, generated at the first site, or a raw material containing the recycled component value is reacted at the first site (collectively referred to as "recycled input"), and the recycled component value obtained from the input is:

[0334] a. symmetrically distributed over at least a portion or all of the volume of PVA prepared at a second station over a period of time (e.g., within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously); or

[0335] b. symmetrically distributed over at least a portion or all of the volume of PVA produced at a second site and over at least a portion or a second different product produced at the same second site, each within the same time period (e.g., within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously); or

[0336] c. The recycled content is symmetrically distributed over all products that actually have the recycled content applied to them that are manufactured at the second site over the same time period (e.g., within the same day, or within 1 week, or within 1 month, or within 6 months, or within the same calendar year, or continuously). Although a variety of products may be manufactured at the second site, in this option, not all products necessarily receive a recycled content value, but rather the distribution is symmetrical for all products that do receive a recycled content value or have a recycled content value applied to them; or

[0337] d. Asymmetrically distributed over at least two volumes of PVA manufactured at the same second site, optionally within the same time period (e.g., within 1 day, or within 1 week, or within 1 month, or within 6 months, or within a calendar year, or continuously), or as sold to at least two different customers. For example, one volume of PVA produced may have a greater recycled content value than a second volume of PVA manufactured at a second site, or one volume of PVA manufactured at a second site and sold to one customer may have a greater recycled content value than a second volume of PVA manufactured at the second site and sold to a second, different customer, or

[0338] e. Asymmetrically distributed over at least one volume of PVA and at least one volume of a different product prepared at the same second station, each optionally within the same time period (e.g., within 1 day, or within 1 week, or within 1 month, or within 6 months, or within a calendar year, or continuously), or sold to at least two different consumers.

[0339] In one embodiment or in combination with any of the mentioned embodiments, a PVA manufacturer or one of its family of entities may prepare PVA by obtaining an aldehyde composition from any source from a supplier, or process AD, or process AD and prepare r-PVA, or prepare r-PVA, whether or not such aldehyde composition has any direct or indirect recycled content, and:

[0340] i. an aldehyde composition from the same supplier, also receiving a recycled content quota, or

[0341] ii. Obtaining a recovery component quota from any person or entity without providing the aldehyde composition from the person or entity to which the recovery component quota is transferred.

[0342] The quota in (i) is obtained from an AD supplier, and the AD supplier also supplies AD to the PVA manufacturer or within its entity family. The situation described in (ii) allows the PVA manufacturer to obtain a supply of an aldehyde composition as a non-recovered component AD, and also obtains a recycled component quota from the AD supplier. In one embodiment or in combination with any of the embodiments mentioned, the AD supplier transfers the recycled component quota to the PVA manufacturer, and transfers the supply of AD to the PVA manufacturer, wherein the recycled component quota is not associated with the supplied AD, or even with any AD prepared by the AD supplier. The recycled component quota does not have to be related to the amount of recycled components in the aldehyde composition or the amount of any monomer used to prepare PVA, but the recycled component quota transferred by the AD supplier can be directly or indirectly derived from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced by pyrolysis of recycled waste, and / or other products of cracking of r-pyrolysis oil produced by pyrolysis of recycled waste, or any downstream compound obtained by pyrolysis of recycled waste. Related, the downstream compound is such as r-ethylene, r-propylene, r-butadiene, r-aldehyde, r-alcohol, r-benzene, etc. For example, an AD supplier can transfer the recycled content associated with r-propylene to a PVA manufacturer and also supply a certain amount of ethylene oxide, even though the r-propylene is not used in the synthesis of ethylene oxide. This allows flexibility between the AD supplier and the PVA manufacturer to allocate the recycled content among the various products they each manufacture.

[0343] In one embodiment or in combination with any of the mentioned embodiments, the AD supplier transfers a recycled content quota to the PVA manufacturer and transfers the supply of AD to the PVA manufacturer, where the recycled content quota is associated with the AD. In this case, the transferred AD does not have to be rA (AD derived directly or indirectly from the pyrolysis of recycled waste); rather, the AD provided by the supplier can be any AD, such as non-recycled component AD, as long as the allocated amount provided is associated with the manufacture of the AD. Alternatively, the supplied AD can be rA, and at least a portion of the transferred recycled content quota can be a recycled component in rA. The recycled content quota transferred to the PVA manufacturer can be provided in advance with the AD, optionally in batches, or with each batch of AD, or distributed between the parties as needed.

[0344] The quota in (ii) is obtained by the PVA manufacturer (or its entity family) from any individual or entity without obtaining the supply of AD from the individual or entity. The individual or entity may be an AD manufacturer that does not provide AD to the PVA manufacturer or its entity family, or the individual or entity may be a manufacturer that does not manufacture AD. In either case, the situation of (ii) allows the PVA manufacturer to obtain the recycling component quota without having to purchase any AD from the entity that supplies the recycling component quota. For example, an individual or entity can transfer the recycling component quota to the PVA manufacturer or its entity family through a buy / sell model or contract without the need to buy or sell quotas (e.g., as a product exchange for products that are not AD), or an individual or entity can directly sell the quota to one of the PVA manufacturer or its entity family. Alternatively, an individual or entity can transfer products other than AD to the PVA manufacturer together with their associated recycling component quotas. This is attractive to PVA manufacturers with diversified businesses that manufacture various products other than PVA, and the raw materials required for these products are not ADs that individuals or entities can provide to the PVA manufacturer.

[0345] The PVA Manufacturer may deposit this allowance into the recycled stock. The PVA Manufacturer also manufactures PVA, whether or not recycled content is applied to the PVA so manufactured, and, if applied to the PVA, whether or not the recycled content value is taken from the recycled stock. For example, the PVA Manufacturer or any entity in its family of entities may:

[0346] a. deposit the allowances into the recycling stock and store them only; or

[0347] b. deposit that allowance into recycled stock and apply the recycled content value from the recycled stock to products other than PVA manufactured by the PVA manufacturer, or

[0348] c. Sell or transfer allowances from the recycling stock into which the allowances acquired as described above are deposited.

[0349] However, if desired, any quota may be deducted from the recovery stock and applied to the PVA product in any amount at any time prior to the point of sale or transfer of the PVA to a third party. Thus, the recovery component quota applied to the PVA may be derived directly or indirectly from pyrolysis recovery waste, or the recovery component quota applied to the PVA may not be derived directly or indirectly from pyrolysis recovery waste. For example, a recovery stock with quotas from various sources for creating quotas may be generated. Some recovery component quotas (credits) may be derived from methanolysis of recovery waste, or from gasification of recovery waste, or from mechanical recovery of waste plastics or metal recovery, and / or from pyrolysis recovery waste, or from any other chemical or mechanical recovery technology. The recovery stock may or may not track the source or basis for obtaining the recovery component, or the recovery stock may not allow the source or basis of the allocation to be associated with the allocation applied to the PVA. Therefore, in this embodiment, it is sufficient to deduct the recycled content value from the recycled stock and apply it to the PVA, regardless of the source or origin of the recycled content value, provided that a quota derived from pyrolytic recycled waste is also obtained by the PVA manufacturer as specified in step (i) or step (ii), regardless of whether the quota is actually deposited in the recycled stock. In one embodiment or in combination with any of the mentioned embodiments, the quota obtained in step (i) or (ii) is deposited in the recycled stock of the quota. In one embodiment or in combination with any of the mentioned embodiments, the recycled content value deducted from the recycled stock and applied to the PVA originates from pyrolytic recycled waste.

[0350] As used in the full text, the recycling stock of the quota can be owned by the PVA manufacturer, operated by the PVA manufacturer, owned or operated by other manufacturers except the PVA manufacturer, but at least partially used for the PVA manufacturer, or licensed by the PVA manufacturer. And, as used in the full text, the PVA manufacturer may also include its entity family. For example, although the PVA manufacturer may not own or operate the recycling stock, one of its entity families may own such a platform, or license it from an independent supplier, or operate for the PVA manufacturer. Alternatively, an independent entity can own and / or operate the recycling stock, and operate and / or manage at least a portion of the recycling stock for the PVA manufacturer for a service fee.

[0351] In one embodiment or in combination with any of the mentioned embodiments, the PVA manufacturer obtains a supply of AD from a supplier and also obtains a quota from (i) the supplier or (ii) any other person or entity, wherein such quota is derived from recycled waste, pyrolysis of recycled waste, pyrolysis gas produced by pyrolysis of recycled waste, and / or cracking of r-pyrolysis oil produced by pyrolysis of recycled waste, and optionally, the quota is obtained from the AD supplier and may even be with the aid of obtaining a quota of rA from the AD supplier. The PVA manufacturer is considered to obtain a supply of aldehyde from a supplier if the supply of aldehyde is obtained by a person or entity in the entity family of the PVA manufacturer. The PVA manufacturer then performs one or more of the following steps:

[0352] a. Apply the quota to PVA prepared from the supply of AD;

[0353] b. applying the quota to PVA not produced from supplies of AD, such as where PVA has already been produced and stored in recycling stock, or to PVA produced in the future; or

[0354] c. depositing the allowance into the recycled stock, deducting the recycled content value from the recycled stock, and applying at least a portion of the recycled content value to:

[0355] i.PVA, thereby obtaining r-PVA, or

[0356] ii. a compound or composition other than PVA, or

[0357] iii. Both;

[0358] Regardless of whether rA is used to prepare the PVA composition, and regardless of whether the recycled content value applied to the PVA is derived from the recycled content value in a quota obtained in step (i) or step (ii) or deposited in a recycled stock; or

[0359] d. As mentioned above, it can simply be deposited into recycling inventory and stored.

[0360] It is not necessary in all embodiments to use rA to prepare the r-PVA composition, or to obtain the recovered r-PVA from the recovery component quota associated with the aldehyde composition. In addition, it is not necessary to apply the quota to the raw material to prepare the PVA to which the recovery component is applied. Instead, as described above, when the aldehyde composition is obtained from the supplier, the quota can be deposited into the electronic recovery stock even if the quota is associated with the aldehyde composition. However, in one embodiment or in combination with any of the mentioned embodiments, rA is used to prepare the r-PVA composition. In one embodiment or in combination with any of the mentioned embodiments, r-PVA is obtained from the recovery component quota associated with the alkylene composition. In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the rA quota is applied to PVA to prepare r-PVA.

[0361] The polyvinyl acetal composition can be prepared from an aldehyde composition from any source, whether or not the aldehyde composition is rA, and whether or not the AD is obtained from a supplier or prepared by a PVA manufacturer or prepared within its family of entities. Once a PVA composition is prepared, it can be designated as having a recycled component based on and derived from at least a portion of the quota, again, whether or not rA is used to prepare an r-PVA composition, and regardless of the source of the AD used to prepare the PVA. The allocated amount can be taken out or deducted from the recycled stock. The amount deducted and / or applied to the PVA can correspond to any of the methods described above, such as a mass balance method.

[0362] In one embodiment or in combination with any of the embodiments mentioned, the recycled component polyvinyl acetal composition can be prepared by reacting an aldehyde composition obtained from any source in the synthesis process to prepare PVA, and the recycled component value can be applied to at least a portion of PVA, thereby obtaining r-PVA. Alternatively, the recycled component value can be obtained by deducting from the recovered stock. The total amount of the recycled component value in PVA can correspond to the recycled component value deducted from the recovered stock. The recycled component value deducted from the recovered stock can be applied to PVA and products or compositions other than PVA manufactured by individuals or entities in the PVA manufacturer or its entity family. The aldehyde composition can be obtained from a third party, or manufactured by a PVA manufacturer, or manufactured and transferred to the PVA manufacturer by individuals or entities in the entity family of the PVA manufacturer. In another example, the PVA manufacturer or its entity family can have a first facility for preparing aldehydes in a first site, and a second facility in the first site or a second facility in the second site, wherein the second facility prepares PVA, and transfers aldehydes from the first facility or the first site to the second facility or the second site. Facilities or sites can be fluidly connected or pipelined to each other directly or indirectly, continuously or discontinuously. The recycled content value is then applied to (e.g., assigned to, assigned corresponding to, attributed to, or associated with) the PVA to produce r-PVA. At least a portion of the recycled content value applied to the PVA is obtained from recycled stock.

[0363] Optionally, it can be communicated to a third party that the r-PVA has recycled content or is obtained or derived from recycled waste. In one embodiment or in combination with any of the embodiments mentioned, recycled content information about the PVA can be transmitted to a third party, wherein such recycled content information is based on or derived from at least a portion of the allocated amount or credit. The third party can be a customer of a PVA manufacturer or supplier, or can be any other individual or entity or government organization other than the entity that owns the PVA. The transmission can be electronic, by document, by advertisement, or any other communication means.

[0364] In one embodiment or in combination with any of the mentioned embodiments, the recycled content polyvinyl alcohol acetal composition is obtained by preparing a first r-PVA or by simply owning (for example, by purchase, transfer or other means) a first r-PVA that already has recycled content and transferring the recycled content value between the recycled stock and the first r-PVA to obtain a second r-PVA having a recycled content value different from that of the first r-PVA.

[0365] In one embodiment or in combination with any of the mentioned embodiments, the recycled content value transferred above is deducted from the recycled stock and applied to the first r-PVA to obtain a second r-PVA having a second recycled content value greater than that contained in the first r-PVA, thereby increasing the recycled content in the first r-PVA.

[0366] The recycled content in the first r-PVA need not be obtained from a recycled stock, but can be attributed to PVA by any of the methods described herein (e.g., by using rA as a reactant feed), and the PVA manufacturer can seek to further increase the recycled content in the first r-PVA so prepared. In another example, a PVA distributor may have r-PVA in its stock and seek to increase the recycled content value of the first r-PVA it owns. The recycled content in the first r-PVA can be increased by applying the recycled content value taken from the recycled stock.

[0367] The amount of recycled content value deducted from the recycled stock is flexible and will depend on the amount of recycled content applied to the PVA. In one embodiment or in combination with any of the embodiments mentioned, it is at least sufficient to correspond to at least a portion of the recycled content in the r-PVA. As described above, if a portion of the PVA is made of rA, wherein the recycled content value in the rA is not deposited into the recycled stock, resulting in r-PVA, and it is desirable to increase the recycled content in the r-PVA by applying the recycled content value taken out from the recycled stock, then this is useful; or wherein r-PVA is owned (by purchase, transfer or otherwise) and it is desirable to increase its recycled content value. Alternatively, all recycled content in the r-PVA can be obtained by applying the recycled content value to the PVA obtained from the recycled stock.

[0368] The method for calculating the recovery component value is not limited, and can include mass balance method or the above-mentioned calculation method. The recovery stock can be established based on any basis and can be a mixture of basis. The example of the source of the quota for obtaining the storage in the recovery stock can be from pyrolysis recovery waste, gasification recovery waste, depolymerization recovery waste, such as by hydrolysis or methanolysis, etc. In one embodiment or in combination with any of the embodiments mentioned, at least a portion of the allocated amount stored in the recovery stock can be attributed to pyrolysis recovery waste (such as obtained from cracking r-pyrolysis oil or obtained from r-pyrolysis gas). The recovery stock can track or may not track the source of the recovery component value stored in the recovery stock. In one embodiment or in combination with any of the embodiments mentioned, the recovery stock distinguishes the recovery component value (i.e., pyrolysis recovery component value) obtained by pyrolysis recovery waste and the recovery component value (i.e., recovery component value) having its source in other technologies. This can be done simply by assigning a distinguishing unit of measurement to the recycled content value with its origin in the pyrolytic recycled waste, or by tracking the assigned origin by assigning amounts or placing them into a unique module, unique spreadsheet, unique column or row, unique database, unique tag agent associated with the unit of measurement, etc. to distinguish:

[0369] the origin of the technology used to generate the quota, or

[0370] the type of compound having the recovered component from which the allocated amount was obtained, or

[0371] Vendor or site identity, or

[0372] Its combination.

[0373] The recycled content value applied to PVA from the recycled stock need not be obtained from a quota having its source in pyrolysis recycled waste. The recycled content value deducted from the recycled stock and / or applied to PVA can be derived from any technology used to produce an allocation from recycled waste, such as by methanolysis or gasification of recycled waste. However, in one embodiment or in combination with any of the mentioned embodiments, the recycled content value applied to PVA or taken / deducted from the recycled stock is derived from or derived from a quota obtained from pyrolysis recycled waste.

[0374] The following are examples of applying a recycled content value or quota (specifying, allocating or declaring recycled content) to a PVA or aldehyde composition:

[0375] 1. applying at least a portion of the recycled content value to the PVA composition, wherein the recycled content value is obtained directly or indirectly from recycled content ethylene or propylene, wherein such recycled content ethylene or propylene is obtained directly or indirectly from cracked r-pyrolysis oil or from r-pyrolysis gas, and the aldehyde composition used to prepare the PVA does not contain any recycled content or does contain recycled content; or

[0376] 2. applying at least a portion of the recycled content value to the PVA composition, wherein the recycled content value is directly or indirectly derived from cracked r-pyrolysis oil or obtained from r-pyrolysis gas; or

[0377] 3. applying at least a portion of the recovered content value to a PVA composition, wherein the recovered content value is derived directly or indirectly from rA, regardless of whether such aldehyde volume is used to prepare PVA; or

[0378] 4. applying at least a portion of the recycled content value to a PVA composition, wherein the recycled content value is directly or indirectly derived from rA, and rA is used as a raw material to prepare r-PVA applied to the recycled content value, and:

[0379] a. Use all the recovered components in r-aldehyde to determine the amount of recovered components in PVA, or

[0380] b. using only a portion of the recycled content in the r-aldehyde to determine the amount of recycled content applied to the PVA, with the remainder stored in a recycled stock for use in future PVA, or for use in other existing PVA made from r-aldehyde that does not contain any recycled content, or to increase the recycled content of existing r-PVA, or a combination thereof, or

[0381] Any recycled content in cr-aldehyde is not applied to PVA but is stored in a recycled stock and the recycled content from any source or origin is deducted from the recycled stock and applied to PVA; or

[0382] 5. applying at least a portion of the recycled content value to an aldehyde composition used to prepare PVA, thereby obtaining r-PVA, wherein the recycled content value is obtained by transferring or purchasing the same aldehyde composition used to prepare PVA, and the recycled content value is associated with the recycled content in the aldehyde composition; or

[0383] 6. applying at least a portion of the recycled content value to an aldehyde composition used to prepare PVA, thereby obtaining r-PVA, wherein the recycled content value is obtained by transferring or purchasing the same aldehyde composition used to prepare PVA, and the recycled content value is not associated with the recycled content in the aldehyde composition, but is associated with the recycled content of the monomer used to prepare the aldehyde composition, such as propylene or ethylene; or

[0384] 7. applying at least a portion of the recycled content value to an aldehyde composition used to prepare PVA, thereby obtaining r-PVA, wherein the recycled content value is not obtained by transferring or purchasing the aldehyde composition, and the recycled content value is associated with the recycled content in the aldehyde composition; or

[0385] 8. applying at least a portion of the recycled content value to an aldehyde composition used to prepare PVA, thereby obtaining r-PVA, wherein the recycled content value is not obtained by transferring or purchasing the aldehyde composition, and the recycled content value is not associated with the recycled content in the aldehyde composition, but is associated with the recycled content of any monomer used to prepare the aldehyde composition, such as a recycled content value associated with the recycled content in propylene or ethylene; or

[0386] 9. Obtaining recycled content value derived directly or indirectly from pyrolysis recycled waste, such as from cracking of r-pyrolysis oil, or obtained from r-pyrolysis gas, or associated with r-composition, or associated with r-aldehyde, and:

[0387] a. No part of the recovered component value is applied to the aldehyde composition to prepare PVA, and at least a portion is applied to PVA to prepare r-PVA; or

[0388] b. Applying less than all of the portion to the aldehyde composition used to make PVA, and storing the remainder in a recycling stock or applying to future made PVA or to existing PVA in the recycling stock.

[0389] As used throughout, the step of deducting the allocation amount from the recycling stock does not need to be applied to the PVA product. Deduction does not mean that the amount of deduction disappears or is removed from the stock log. Deduction can be the adjustment of entries, withdrawal, addition of entries as debits, or any other algorithm that adjusts input and output based on the amount of the recycling component associated with the product and one of the recycling stock or the accumulated allocation amount deposited. 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 recycling component value to the PVA product does not require the recycling component value or allocation amount to be physically applied to the PVA product or any issued document associated with the PVA product sold. For example, a PVA manufacturer can ship the PVA product to a customer, and by electronically transmitting the recycling component credit or certification document to the customer, or by applying the recycling component value to the packaging or container containing PVA or rA, the "application" of the recycling component value to the PVA product is met.

[0390] Some PVA manufacturers may be integrated into the manufacture of downstream products using PVA as a raw material, such as making films or sheets, dispersions, and laminates with or on glass, or sandwiched between layers of glass, or laminated with other polymer sheets that may subsequently be laminated to or between layers of glass. They and other non-integrated PVA manufacturers may also promise to sell or market PVA that contains or obtains a certain amount of recycled content. Recycled content designations may also be found on or associated with downstream products made with PVA.

[0391] In one embodiment or in combination with any of the mentioned embodiments, the amount of recycled content in rA or r-PVA will be based on the allocation or credit obtained by the manufacturer of the PVA composition or the amount available in the recycled stock of the PVA manufacturer. Some or all of the recycled content value in the allocation or credit obtained or owned by the PVA manufacturer can be designated and allocated to rA or r-PVA on a mass balance basis. The allocated value of the recycled content of rA or PVA should not exceed the total amount of all allocated amounts and / or credits available to the PVA manufacturer or other entity authorized to allocate recycled content value to PVA.

[0392] There is also now provided a method for introducing or establishing a recycled component in polyvinyl acetal without having to use an r-aldehyde raw material. In this method,

[0393] a. Olefin Suppliers:

[0394] i. cracking a cracker feed comprising a recycled pyrolysis oil to produce an olefin composition, at least a portion of which is obtained by cracking said recycled pyrolysis oil (r-olefins), or

[0395] ii. Producing pyrolysis gas, at least a portion of which is recycled into a waste stream by pyrolysis (r-pyrolysis gas)

[0396] obtain, or

[0397] iii. Both; and

[0398] b. Polyvinyl acetal manufacturers:

[0399] i. obtaining quotas derived directly or indirectly from said r-olefins or said r-pyrolysis gas from a supplier or a third party to whom said quotas are transferred,

[0400] ii. Preparation of polyvinyl acetal from aldehyde, and

[0401] iii. associating at least a portion of the quota with at least a portion of the polyvinyl acetal, whether or not the aldehyde used to prepare the polyvinyl acetal contains r-aldehyde.

[0402] In this method, the polyvinyl acetal manufacturer does not need to purchase r-aldehyde from any entity or from an aldehyde supplier, and does not need the polyvinyl acetal manufacturer to purchase olefins, r-olefins or aldehydes from a specific source or supplier, and does not need the polyvinyl acetal manufacturer to use or purchase an aldehyde composition with r-aldehyde to successfully establish a recovery component in the polyvinyl acetal composition. The aldehyde manufacturer can use any aldehyde source, and at least a portion of the allocation or credit is applied to at least a portion of the aldehyde raw material or at least a portion of the polyvinyl acetal product. When the allocation or credit is applied to the raw material aldehyde, this will be an example of an r-aldehyde raw material indirectly derived from cracked r-pyrolysis oil or obtained from r-pyrolysis gas. The association of the polyvinyl acetal manufacturer can appear in any form, whether it is through recovery of inventory, internal accounting methods, or statements or claims made to a third party or the public.

[0403] In another embodiment, the exchanged recycled content value is subtracted from the first r-PVA and added to the recycled stock to obtain a second r-PVA having a second recycled content value lower than that contained in the first r-PVA, thereby reducing the recycled content in the first r-PVA. In this embodiment, the above description of adding the recycled content value from the recycled stock to the first r-PVA applies in reverse to subtracting the recycled content from the first r-PVA and adding it to the recycled stock.

[0404] The quota can be obtained from various sources in the manufacturing chain starting from pyrolysis recycled waste until the manufacture and sale of rA. The recycled content value applied to PVA or the allocated amount deposited into the recycled stock does not need to be associated with rA. In one embodiment or in combination with any of the mentioned embodiments, the method of preparing r-PVA can be flexible and allow the allocation to be obtained anywhere along the manufacturing chain to prepare PVA starting from pyrolysis recycled waste. For example, r-PVA can be prepared by the following steps:

[0405] a. pyrolyzing a pyrolysis feed comprising recycled waste material to form a pyrolysis effluent containing r-pyrolysis oil and / or r-pyrolysis gas. Quotas associated with the r-pyrolysis oil or r-pyrolysis gas are automatically generated by generating the pyrolysis oil or pyrolysis gas from the recycled waste stream. The quotas may travel with the pyrolysis oil or pyrolysis gas or be separated from the pyrolysis oil or pyrolysis gas, for example by depositing the quotas into a recycling inventory; and

[0406] b. optionally cracking a cracker feed containing at least a portion of the r-pyrolysis oil produced in step a) to thereby produce a cracker effluent containing r-olefins; or optionally cracking a cracker feed not containing r-pyrolysis oil to produce olefins and applying a recovery component value to the olefins so produced by deducting the recovery component value from a recovery inventory (where available, operated or beneficial to the olefin producer or its family of entities) and applying the recovery component value to the olefins to produce the r-olefins;

[0407] c. reacting any olefin volume in a synthesis process to produce an aldehyde composition; optionally using the olefin produced in step b) and optionally using the r-olefin produced in step b), and optionally applying the recovery component value associated with the production of the produced aldehyde to produce rA; and

[0408] d. reacting any aldehyde in the synthesis process to prepare polyvinyl acetal; optionally using the aldehyde prepared in step c) and optionally using rA prepared in step c); and

[0409] e. applying a recycled content value to at least a portion of the polyvinyl acetal composition based on:

[0410] i. Feed rA as raw material or

[0411] ii. depositing at least a portion of the quota obtained from any one or more of steps a) or b) or c) into a recycled stock, and deducting a recycled component value from said stock, and applying at least a portion of either or both of said values ​​to PVA, thereby obtaining r-PVA.

[0412] In one embodiment or in combination with any of the mentioned embodiments, there is also provided an integrated process for preparing recycled content polyvinyl acetal by:

[0413] a. preparing r-olefins by cracking r-pyrolysis oil or separating olefins from r-pyrolysis gas; and

[0414] b. converting at least a portion of the r-olefin in a synthesis process to produce an aldehyde, and

[0415] c. converting at least a portion of any of said aldehydes into polyvinyl acetal; and

[0416] d. applying the recycled content value to the polyvinyl acetal to prepare r-PVA; and

[0417] e. Optionally, r-pyrolysis oil or r-pyrolysis gas or both are prepared by pyrolysis recovery of raw materials.

[0418] In this embodiment, all steps a)-d) may be performed by or within a family of entities, or optionally at the same site.

[0419] In another method, the direct method, the recycled content can be introduced or established in the polyvinyl acetal by the following steps:

[0420] obtaining a recovered aldehyde composition, at least a portion of which is derived directly from cracked r-pyrolysis oil or obtained from r-pyrolysis gas ("rA"),

[0421] preparing a polyvinyl acetal composition from a raw material comprising rA,

[0422] The recycled content value is applied to at least a portion of any polyvinyl acetal composition prepared by the same entity as that preparing the polyvinyl acetal composition in step b), and is based at least in part on the amount of recycled content contained in said rA.

[0423] In another more detailed direct method, the recycled content can be introduced or established in the polyvinyl acetal by the following steps:

[0424] a. preparing a recycled olefin composition (e.g. ethylene or propylene), at least a portion of which is derived directly from the pyrolysis of recycled waste or from cracked r-pyrolysis oil or from r-pyrolysis gas ("dr-propylene"),

[0425] b. preparing aldehydes from raw materials containing dr-propylene;

[0426] c. designating at least a portion of the aldehyde as a recovered component containing at least a portion of the amount of dr-propylene contained in the feedstock to obtain dr-aldehyde,

[0427] d. preparing polyvinyl acetal using a raw material containing r-aldehyde,

[0428] e. designating at least a portion of the polyvinyl acetal as containing a recovered component corresponding to at least a portion of the amount of dr-aldehyde contained in the raw material to obtain dr-polyvinyl acetal,

[0429] f. and optionally providing an offer to sell or sell r-polyvinyl acetal containing or obtained from recycled content corresponding to the designation.

[0430] In these direct methods, the r-aldehyde component for preparing polyvinyl acetal will be traceable to the olefins prepared by the supplier through cracking r-pyrolysis oil or obtained from r-pyrolysis gas. Not all the amounts of r-olefins for preparing aldehyde need to be specified or associated with aldehyde. For example, if 1000kg of r-propylene or r-ethylene is used to prepare rA, the AD manufacturer can specify less than 1000kg of recycled components for the raw materials of a specific batch of AD, and the amount of 1000kg of recycled components can be alternatively dispersed in various production runs for preparing aldehyde. Aldehyde manufacturers can choose to promise to sell their dr-polyvinyl acetals, and when doing so, they can also choose to indicate that the r-polyvinyl acetals sold contain recycled components, or are obtained from sources containing recycled components.

[0431] rA can be obtained by hydroformylation ethylene or recovery propylene, and this depends on whether people wish to use propionaldehyde or butyraldehyde as rA feed to prepare r-PVA. The method for preparing r-butyraldehyde is discussed below, but it should be understood that the method can also be used to prepare r-propionaldehyde or other r-aldehydes. In addition, although the method is described with respect to propylene, it should be understood that other olefins such as ethene can be used, and the olefins can be non-recovered olefins, or r-olefins, or pr-olefins, or olefins (for example propylene, r-propylene, pr-propylene, or pr-propylene obtained by cracking r-pyrolysis oil or by gas cracker) obtained. Although any technology of r-propylene being converted into (C4)-alkanal (for example butyraldehyde) can be used, in view of the high catalyst activity and selectivity and low pressure and low temperature requirements of rhodium catalytic process or low pressure hydroformylation process, it is an ideal synthetic route.

[0432] More specifically, the hydroformylation process for preparing r-(C4)alkanal comprises contacting propylene with synthesis gas (H2, CO) and a catalyst complex in a reaction zone at high temperature and high pressure for a sufficient time to react propylene with the synthesis gas to form (C4)alkanal. Suitable methods for preparing (C4)alkanal include high pressure and low pressure carbonyl synthesis processes, wherein r-propylene is hydroformylated to prepare (C4)alkanal. The hydroformylation reaction temperature can be any temperature from 50°C to about 250°C, and the reaction pressure can be from 15 psig to about 5100 psig. The hydroformylation process can be a high pressure or low pressure process. In a high pressure hydroformylation process, the temperature in the reaction zone can be at least 140°C, or at least 150°C, or at least 160°C, or at least 170°C. Additionally or alternatively, the temperature can be up to 250°C, or up to 240°C, or up to 230°C, or up to 220°C, or up to 210°C, or up to 200°C. In the low pressure hydroformylation process, the temperature in the reaction zone may be at least 50° C., or at least 60° C., or at least 70° C., or at least 75° C., or at least 80° C., or at least 90° C. Additionally or alternatively, the temperature may be up to 160° C., or up to 150° C., or up to 140° C., or up to 135° C., or up to 130° C., or up to 125° C., or up to 115° C., or up to 110° C., or up to 100° C. Typically, the reaction temperature is from 60° C. to 115° C., or from 60° C. to 110° C., or from 60° C. to 105° C., or from 60° C. to 100° C., or from 60° C. to 95° C.

[0433] Typically, the mol ratio of hydrogen and carbon monoxide introduced into the reactor or the mol ratio in the reactor remain in the range of about 0.1:1 to about 10:1, or 0.5:1 to 4:1, or 0.9:1 to 4:1, or 1:1 to 4:1. In many hydroformylations, the productivity of reaction rate and (C4) alkanal can be increased to more than 4.0 by the mol ratio of hydrogen and carbon monoxide, and at most about 10.0 or higher to improve. In one embodiment, the summation of the absolute partial pressure of hydrogen and carbon monoxide can be in the range of 15psig to 430psig. The hydrogen partial pressure in the reactor can remain in the range of 35psig to about 215psig. The carbon monoxide partial pressure in the reactor can remain in the range of 35psig to 215psig, or 40psig to 110psig. In one embodiment, H2 is 0.9:1-1.1:1 with the ratio of CO, which is particularly suitable for high pressure hydroformylation process. In one embodiment, the ratio of H2 to CO is greater than 1:1, such as at least 1.1:1, or at least 1.2:1, or at least 1.3:1, or at least 1.4:1, or at least 1.5:1, or at least 1.7:1, or at least 2:1, or at least 2.1:1, which is particularly suitable in a low pressure hydroformylation process. Additionally or alternatively, the ratio of H2 to CO can be at most 5:1, or at most 4.5:1, or at most 4:1, or at most 3.5:1, or at most 3:1, or at most 2.8:1, or at most 2.5:1. Typically, a suitable H2 to CO molar ratio in a low pressure process is at least 1.1:1 to 3:1, or 1.2:1 to 2.25:1, or 1.2:1 to 2:1.

[0434] In the gas sparge reaction, hydrogen plus carbon monoxide gases may be present in molar excess relative to propylene (total moles of H2 + CO). Suitable molar ratios of syngas to propylene may be from 0.5 to about 20, or from 1.2 to about 6. In a liquid overflow reactor, the molar ratio of syngas to propylene may be as low as 0.02:1.

[0435] Suitable hydroformylation catalysts include any known catalysts that effectively catalyze the conversion of propylene into (C4) alkanals. Examples of such catalysts are metals complexed with ligands. Suitable metals include cobalt, rhodium and ruthenium metals. Metal compounds that can be used as metal sources for the catalyst complex include metals in their +1, +2 or +3 oxidation states, and can include di-, tri-, tetra-metals, such as compounds with carboxylic acids or carbonyl compounds. The catalyst may be tris(triphenylphosphine)rhodium(I)carbonylhydride, premixed or formed in situ in the liquid phase within the hydroformylation zone, and may be introduced as a precursor, such as acetylacetonato dicarbonylrhodium(I) {Rh(CO)2(acac)}, rhodium oxide {Rh2O3}, carbonyl rhodium {Rh4(CO)12, Rh6(CO)16}, tris(acetylacetonato)rhodium(I) {Rh(acac)3}, triarylphosphine-substituted rhodium carbonyl {Rh(CO)2(PAr3)}2, wherein Ar is an aromatic group, or tetraacetate dirhodium dihydrate, rhodium acetate, rhodium isobutyrate, rhodium 2-ethylhexanoate, rhodium benzoate and rhodium octanoate, Rh4(CO)12, Rh6(CO)I6 and acetylacetonato dicarbonyl rhodium, and tris(triphenylphosphine)carbonyl hydride rhodium.

[0436] Suitable ligands include organic phosphine compounds such as tertiary (trisubstituted), mono- and di-phosphines and phosphites and can be represented by the general formula:

[0437]

[0438] Where R 1 , R 2 and R 3 are the same or different, each being a hydrocarbon group containing up to about 12 carbon atoms, R 4 It is a divalent hydrocarbylene group connecting two phosphorus atoms through a chain of 2 to 8 carbon atoms. The ligand may also include a fluorophosphite compound.

[0439] Based on the amount of r-propylene fed to the reactor zone, the amount of catalyst metal employed may be as little as about 1×10 -6 mole of metal (e.g., rhodium, calculated on a rhodium metal basis) per mole of olefin. Approximately 1×10 -5 About 5×10 -2 The concentration of molar metal (e.g. rhodium) is about 1×10 -4 Up to 1×10 -3The metal (e.g., rhodium) concentration in the range of 100 to 200 is also useful and desirable. The upper catalyst concentration is substantially unrestricted and appears to be determined primarily by the high cost of the catalyst metal and any limitation on the lack of yield increase as the amount of catalyst increases. Since r-propylene is a feedstock, the drive for high catalyst activity and high conversion is dominant relative to selectivity. Therefore, the amount of catalyst can be increased to increase the reaction rate without producing unwanted isomers, which would otherwise be produced when hydroformylating higher olefins.

[0440] The conversion of the propylene molecules in the r-propylene may be 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%.

[0441] The hydroformylation effluent by r-propylene hydroformylation production with carbon monoxide and hydrogen comprises at least (C4) alkanal (or other aldehydes, depending on the corresponding olefins adopted).Hydroformylation effluent also can contain unreacted propylene, propane, carbon monoxide, hydrogen, solvent and catalyst or catalyst part.In one embodiment or with any other embodiment combination of mentioning, (C4) alkanal or contain at least a hydroformylation effluent in (C4) alkanal and propylene, propane, carbon monoxide, hydrogen, solvent and catalyst or catalyst part as gas from reactor and remove.Alternately, (C4) alkanal can be used as liquid and catalyst combination and remove from reactor.

[0442] Hydroformylation effluent, for example steam, can carry out one or more separation processes to reclaim (C4) alkanal product, as mainly comprising butyraldehyde or mainly comprising mixture or composition of isobutyraldehyde.For example, hydroformylation effluent is separated into rich (C4) alkanal crude stream and rich catalyst stream.Separation can be carried out by the hydroformylation effluent being fed to the separation zone contained in the first separation vessel.Can use any suitable container for separating gaseous components, for example vapor-liquid separator, for example vapor-liquid knockout drum (knockout drum) (horizontal, vertical and side or tangential feeding).

[0443] The (C4) alkanal-rich crude stream contains (C4) alkanal and hydrogen and optional solvent, carbon monoxide, propane, propylene, ethane, ethylene and methane and other non-condensable gases. The concentration of (C4) alkanal in the crude (C4) alkanal stream is enriched relative to the concentration of (C4) alkanal in the hydroformylation effluent. The rich (C4) alkanal can be further processed to separate the isomers (i.e. butyraldehyde and isobutyraldehyde) of (C4) alkanal.

[0444] Rich (C4) alkanal crude stream is taken out from separator as gaseous stream, desirably takes out as overhead product.Rich catalyst stream contains catalyst ligand and optional catalyst metal and solvent.With respect to the concentration of catalyst ligand in the hydroformylation effluent, it has enriched the concentration of catalyst ligand.Rich catalyst stream, as the liquid from separator, takes out as bottoms stream ideally.Then, before catalyst ligand and optional catalyst metal and solvent are turned back to reactor, rich catalyst stream can be directly or reclaimed back to the upper half of hydroformylation reactor to further process this stream through intermediate step.

[0445] Then the rich (C4) alkanal crude stream is further separated into a rich (C4) alkanal purification stream and a gas stream. The rich (C4) alkanal purification stream can be purified to separate the isomer (i.e. butyraldehyde or isobutyraldehyde) of (C4) alkanal. The rich (C4) alkanal crude stream can be separated in a second separation zone comprising at least a second separation container. In the second separation zone, the rich (C4) alkanal crude stream can be fully cooled to condense (C4) alkanal, and the rich (C4) alkanal crude stream containing condensed (C4) alkanal and uncondensed gas can be fed to a second separation container, for example a vapor-liquid separator, for example a vapor-liquid separation container or a flash tank or a distillation tower.

[0446] The (C4)alkanal-rich purified stream is enriched in (C4)alkanal concentration relative to the (C4)alkanal-rich crude stream. It is desirably the liquid bottoms stream withdrawn from the second separation vessel.

[0447] The purified (C4) alkanal-rich stream, desirably withdrawn as a liquid understream from the second separation vessel, may be recovered as product, or it may alternatively be used as a scrubber in a syngas scrubber.

[0448] Propylene hydroformylation produces (C4) alkanals including butyraldehyde and isobutyraldehyde. (C4) alkanals can be purified to enrich butyraldehyde or isobutyraldehyde or both thereof. Enrichment can be carried out by any purification method known in the art. However, a distillation process can be used for purifying the isomers of (C4) alkanals. The purification of (C4) alkanal isomers can be purified immediately after the preparation of (C4) alkanals.

[0449] In one embodiment or any of the mentioned embodiments, the (C4) alkanal is purified (e.g., distilled) to obtain an enriched butyraldehyde composition, which may contain 80 wt.% to 98 wt.% n-butyraldehyde, or 85 wt.% to 98 wt.% n-butyraldehyde, or 90 wt.% to 98 wt.% n-butyraldehyde, or 95 wt.% to 98 wt.% n-butyraldehyde, or 80 wt.% to 95 wt.% n-butyraldehyde, or 85 wt.% % to 95 wt. % n-butyraldehyde, or 55 wt. % to 95 wt. % n-butyraldehyde, or 60 wt. % to 95 wt. % n-butyraldehyde, or 65 wt. % to 95 wt. % n-butyraldehyde, or 70 wt. % to 95 wt. % n-butyraldehyde, or 75 wt. % to 95 wt. % n-butyraldehyde, or 80 wt. % to 90 wt. % n-butyraldehyde, or 85 wt. % to 90 wt. % n-butyraldehyde, based on the total weight of the butyraldehyde composition.

[0450] In one embodiment or any of the mentioned embodiments, the (C4) alkanal is purified (e.g., distilled) to obtain an enriched isobutyraldehyde composition, which may contain 80 wt.% to 98 wt.% isobutyraldehyde, or 85 wt.% to 98 wt.% isobutyraldehyde, or 90 wt.% to 98 wt.% isobutyraldehyde, or 95 wt.% to 98 wt.% isobutyraldehyde, or 80 wt.% to 95 wt.% isobutyraldehyde, or 85 wt.% % to 95 wt. % isobutyraldehyde, or 55 wt. % to 95 wt. % isobutyraldehyde, or 60 wt. % to 95 wt. % isobutyraldehyde, or 65 wt. % to 95 wt. % isobutyraldehyde, or 70 wt. % to 95 wt. % isobutyraldehyde, or 75 wt. % to 95 wt. % isobutyraldehyde, or 80 wt. % to 90 wt. % isobutyraldehyde, or 85 wt. % to 90 wt. % isobutyraldehyde, based on the total weight of the isobutyraldehyde composition.

[0451] In one embodiment or in any of the mentioned embodiments, the amount of impurities present in the r-propylene composition, or the amount of impurities present in the (C4)alkanal composition prepared with a feed containing r-propylene, can be:

[0452] a. Formaldehyde: at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 25 ppm, or at least 30 ppm, or

[0453] b. Methyl chloride: at least 1 ppm, or at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, or

[0454] c. Total nitrogen compounds: at least 0.5 ppm, or at least 1 ppm, or at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, or

[0455] d. Acetone: greater than 25 ppb, or at least 30 ppb, or at least 50 ppb, or at least 100 ppb, or at least 500 ppb, or at least 1000 ppb, or

[0456] e. Methanol: greater than 3, or at least 5, or at least 10, or at least 15, or at least 20,

[0457] f. Acetaldehyde: greater than 5ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 30ppm,

[0458] g. Oxygen-containing compounds other than acetone, methanol, CO and CO2: greater than 0.5 ppm, or at least 0.75 ppm, or at least 1 ppm, or at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, or

[0459] h.COS: 0.5ppm, or at least 0.75ppm, or at least 1ppm, or at least 2ppm, or at least 5ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 30ppm,

[0460] i.MAPD: greater than 1 ppm, or at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm.

[0461] In one embodiment or in any of the foregoing embodiments, the (C4)alkanal composition comprises one or more of these impurities, and may also comprise aldol condensation products such as propanol, which remain in the overhead of the hydroformylation reactor with the (C4)alkanal.

[0462] When the r-propylene stream is fed to the hydroformylation reactor after the non-recovered propylene stream is fed, the change of impurities that may be present in the (C4) alkanal composition taken out from the top of the hydroformylation reactor or in the (C4) alkanal composition stream that is recovered and / or separated may be more pronounced. Therefore, a method for introducing impurities into the (C4) alkanal composition by the following steps is also provided:

[0463] a. preparing (C4) alkanal from a first propylene feedstock; and

[0464] b. preparing (C4) alkanals from a second r-propylene feedstock or pr-propylene feedstock, or alternatively from cracked r-pyrolysis oil or obtained from r-pyrolysis gas, and comprising impurities not present in the first propylene feedstock or present in an amount greater than that present in the first propylene feedstock and originating from the cracking of recycled pyrolysis oil; and

[0465] c. preparing a (C4) alkanal composition comprising (C4) alkanal and impurities by step (b), which composition may be an intermediate, a crude composition or a refined composition; and

[0466] d. optionally recovering the (C4)alkanal composition containing impurities.

[0467] In this technique, at least one impurity or multiple impurity types or amounts resulting from the use of a propylene feedstock, at least a portion of which is obtained by pyrolysis recovery of waste, or alternatively from cracking r-pyrolysis oil or from r-pyrolysis gas, can be readily detected. Optionally, one or more of these impurities may be removed, for example by distillation or solvent extraction, prior to recovery or separation of the (C4) alkanal composition.

[0468] The above disclosure applies to acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 3-methyl-butyraldehyde, 2-methyl-butyraldehyde, 2,2-dimethyl-propionaldehyde, and their anhydrides and r-, pr-, and those obtained from cracked or gas cracked r-pyrolysis oils.

[0469] Also provided is the use of aldehydes derived directly or indirectly from cracked r-pyrolysis oil or obtained from r-pyrolysis gas, which use comprises converting the r-aldehyde in any synthesis process to prepare polyvinyl acetal.

[0470] Also provided is the use of an r-aldehyde quota or an r-olefin quota, which comprises converting an aldehyde in a synthesis process to prepare polyvinyl acetal, and applying at least a portion of the r-aldehyde quota or the r-olefin quota to the polyvinyl acetal. The r-aldehyde quota or the r-olefin quota is a quota generated by pyrolysis recovery of waste. Desirably, the quota is derived from the cracking of r-pyrolysis oil, or the cracking of r-pyrolysis oil in a gas furnace, or from r-pyrolysis gas.

[0471] Also provided is the use of an aldehyde compound to prepare polyvinyl acetal by reacting the aldehyde compound with rA, wherein rA is optionally derived directly or indirectly from pyrolysis recycled waste or cracking r-pyrolysis oil in a gas furnace.

[0472] Also provide the purposes of aldehyde, by making AD and PVOH or PVAc react to prepare polyvinyl acetal, and at least a portion of the recovery component quota is applied to at least a portion of polyvinyl acetal to prepare r-polyvinyl acetal.At least a portion of the recovery stock from which the recovery component quota is applied to polyvinyl acetal is derived from the quota of pyrolysis recovery waste.Desirably, the quota is derived from the cracking of r-pyrolysis oil, or the cracking of r-pyrolysis oil in a gas furnace, or is derived from r-pyrolysis gas.In addition, the quota applied to polyvinyl acetal can be a recovery component quota derived from pyrolysis recovery waste.

[0473] In one embodiment or in combination with any of the mentioned embodiments, there is also provided the use of a recycled stock by converting any aldehyde composition in a synthesis process to prepare a polyvinyl acetal composition ("PVA"); deducting a recycled component value from the recycled stock and applying at least a portion of the deducted recycled component value to the PVA, and at least a portion of the stock comprises a recycled component quota. The recycled component quota may be present in the stock at the time the recycled component value is deducted from the recycled stock, or the recycled component quota is deposited in the recycled stock before the deduction of the recycled component value (but need not be present or considered when making the deduction), or it may be present within one year after the deduction, or within the same calendar year as the deduction, or within the same month as the deduction, or within the same week as the deduction. In one embodiment or in combination with any of the mentioned embodiments, the recycled component deduction is taken for the recycled component quota.

[0474] In one embodiment or in combination with any of the mentioned embodiments, there is provided a polyvinyl acetal composition obtained by any of the above methods.

[0475] The same operator, owner of a family of entities may implement each of these steps, or one or more steps may be implemented between different operators, owners, or families of entities.

[0476] The aldehyde, such as rA, can be stored in storage containers and transferred to a PVA manufacturing facility by truck, pipeline or ship, or as further described below, the AD manufacturing facility can be integrated with the PVA facility. The aldehyde can be transported or transferred to an operator or facility that prepares polyvinyl acetal.

[0477] In one embodiment or in combination with any of the mentioned embodiments, two or more facilities can be integrated and r-PVA can be prepared. The facilities for preparing r-PVA, aldehydes, olefins and r-pyrolysis oil and / or r-pyrolysis gas can be independent facilities or facilities integrated with each other. For example, a system for producing and consuming a recovered aldehyde composition can be established, at least a portion of which is directly or indirectly obtained from cracking r-pyrolysis oil or obtaining r-pyrolysis gas; or a method for preparing r-PVA, as follows:

[0478] a. providing an aldehyde manufacturing facility that at least partially produces an aldehyde composition ("AD");

[0479] b. providing a polyvinyl acetal manufacturing facility that prepares a polyvinyl acetal composition ("PVA") and includes a reactor configured to receive an AD; and

[0480] c. feeding at least a portion of the AD from an aldehyde manufacturing facility to a polyvinyl acetal manufacturing facility through a supply system providing fluid communication between the facilities;

[0481] Wherein either or both of the aldehyde manufacturing facility or the polyvinyl acetal manufacturing facility prepares or provides rA or r-PVA, respectively, and optionally, wherein the aldehyde manufacturing facility supplies rA to the PVA manufacturing facility via a supply system.

[0482] The feed in step c) may be a supply system providing fluid communication between the two facilities and capable of supplying the aldehyde composition of the aldehyde manufacturing facility to the PVA manufacturing facility, such as a piping system with continuous or discontinuous flow.

[0483] A PVA manufacturing facility can prepare r-PVA, and can prepare r-PVA directly or indirectly from the pyrolysis of recycled waste or the cracking of r-pyrolysis oil or from r-pyrolysis gas. For example, in a direct process, a PVA manufacturing facility can prepare r-PVA by receiving r-aldehyde from an aldehyde manufacturing facility and feeding the r-aldehyde as a feed stream to a reactor to prepare PVA. Alternatively, a PVA manufacturing facility can prepare r-PVA by accepting any aldehyde composition from an aldehyde manufacturing facility and applying the recycled components to PVA prepared with the aldehyde composition by deducting the recycled component value from its recycled stock, and applying them to the PVA, optionally in an amount using the above method. The quota obtained and stored in the recycled stock can be obtained by any of the above methods and does not have to be a quota associated with r-aldehyde.

[0484] In one embodiment or in combination with any of the mentioned embodiments, there is also provided a system for producing r-PVA as follows:

[0485] a. Providing an olefin manufacturing facility configured to produce an output composition comprising recycled content propylene or recycled content ethylene or both ("r-olefins");

[0486] b. providing an AD manufacturing facility configured to receive an olefin stream from an olefin manufacturing facility and to prepare an output composition comprising an aldehyde composition;

[0487] c. providing a polyvinyl acetal (PVA) manufacturing facility having a reactor configured to receive an aldehyde composition and produce an output composition comprising r-PVA; and

[0488] d. A supply system providing fluid communication between at least two of these facilities and capable of supplying the output composition of one manufacturing facility to another one or more of said manufacturing facilities.

[0489] PVA manufacturing facilities can prepare r-PVA, and can directly or indirectly prepare r-PVA by pyrolysis of recycled waste. In this system, olefin manufacturing facilities can make its output communicate with AD manufacturing facilities fluid, and in turn, AD manufacturing facilities can make its output communicate with PVA manufacturing facilities fluid. Alternatively, a) and b) manufacturing facilities can be fluidly connected separately, or only b) and c) fluidly connected. In the latter case, PVA manufacturing facilities can directly prepare r-PVA by converting all the r-olefins produced in olefin manufacturing facilities into PVA, or by accepting any aldehyde composition from AD manufacturing facilities and applying the recycled components to PVA by deducting the quota from its recycled stock and applying them to PVA in the amount of the above method. The quota obtained and stored in the recycled stock can be obtained by any of the above methods, and it is not necessary to be a quota associated with r-aldehydes or r-olefins. For example, the quota can be obtained from any facility or source, as long as they are derived from the pyrolysis of recycled waste or cracking r-pyrolysis oil or obtained from r-pyrolysis gas.

[0490] Fluid communication can be gas, or if compressed, can be liquid. Fluid communication does not need to be continuous, and can be interrupted by storage tank, valve or other purification or treatment facilities, as long as fluid can be transported to subsequent facilities from a facility by, for example, interconnected pipeline network and do not use truck, train, ship or airplane. For example, one or more storage containers can be placed in a supply system so that rA facilities are fed to storage facilities by rA, and rA can be taken out from storage facilities according to the needs of PVA manufacturing facilities, wherein valve and pump and compressor are used in series with pipeline network as required. In addition, facilities can share the same site, or in other words, a site can include 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 boundary lines.

[0491] In one embodiment or in combination with any of the embodiments mentioned, the integration method includes at least two facilities co-located within 5 miles, or within 3 miles, or within 2 miles, or within 1 mile of each other (measured in a straight line). In one embodiment or in combination with any of the embodiments mentioned, at least two facilities are owned by the same family of entities.

[0492] In one embodiment or in combination with any of the mentioned embodiments, an integrated r-olefin and r-PVA generation and consumption system is also provided. The system comprises:

[0493] a. Providing an olefin manufacturing facility configured to produce an output composition comprising recycled content propylene or recycled content ethylene or both ("r-olefins");

[0494] b. providing an AD manufacturing facility configured to receive an olefin stream from an olefin manufacturing facility and to prepare an output composition comprising an aldehyde composition;

[0495] c. providing a PVA manufacturing facility having a reactor configured to receive an aldehyde composition and produce an output composition comprising r-PVA; and

[0496] d. A piping system interconnecting at least two of the facilities, optionally with an intermediate processing facility or storage facility, capable of taking an output composition from one facility and receiving said output at any one or more of the other facilities.

[0497] The system does not necessarily need the fluid communication between the two facilities, although fluid communication is desirable. In the system, the ethylene or propylene prepared in the olefin manufacturing facility can be transported to the AD facility by an interconnected pipeline network, which can be interrupted by other processing facilities, and the other processing facilities are such as processing, purifying, pumping, compressing or suitable for merging the facilities or storage facilities of the stream, all of which facilities include optional metering, valves or interlocking facilities. The equipment can be fixed to the ground or fixed to the structure fixed to the ground. The interconnected pipeline does not need to be connected to the AD reactor or cracker, but is connected to the delivery and receiving point at the respective facilities. The same concept is applicable between the AD facility and the PVA facility. The interconnected pipeline system does not need to connect all three facilities to each other, but the interconnected pipeline system can be between the facility a)-b), or between b)-c), or between a)-b)-c).

[0498] It is also now possible to provide packaging or combinations of r-PVA and a recycled content identifier associated with the r-PVA, wherein the identifier is or includes a symbol that the PVA contains recycled content or is derived from recycled content or is associated with recycled content. The packaging can be any suitable packaging for containing polyvinyl acetal, such as plastic or metal drums, railroad cars, isotainers, totes, polytotes, IBC totes, bottles, drums, ocean containers, trailers, and plastic bags. The identifier may be a certification document, a product insert indicating recycled content, a label, a logo or certification mark from a certification body indicating that the article or packaging contains the content or that the PVA contains the content, or is made from a source or is associated with recycled content, or it may be an electronic statement by the PVA manufacturer accompanying a purchase order or product, or posted on a website as a statement, representation or mark indicating that the PVA contains or is made from a source that is associated with or contains recycled content, or it may 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 PVA. The identifier need not indicate or indicate that the recycled content is derived directly or indirectly from cracked r-pyrolysis oil or obtained from r-pyrolysis gas. Rather, it is sufficient that the PVA is at least partially obtained directly or indirectly from cracked r-pyrolysis oil, and the identifier may simply convey or communicate that the PVA has or is derived from recycled content, regardless of its source.

[0499] In one embodiment or in combination with any of the mentioned embodiments, there is provided a system or package comprising:

[0500] a. Polyvinyl acetal ("PVA") and

[0501] b. An identifier (such as a credit, label, or certification) associated with the polyvinyl acetal, the identifier being an indication that the polyvinyl acetal has recycled content or is made from a source having recycled content.

[0502] The system can be a physical combination, such as a package having at least some PVA as its contents, and the package having a label, such as a logo, that the component of the PVA has or is derived from recycled components. Alternatively, whenever a PVA having or is derived from recycled components is transferred or sold, the label or certification can be issued to a third party or customer as part of the standard operating procedure of the entity. The identifier does not have to be physically on the PVA or on the package, and does not have to be on any physical document accompanying or associated with the PVA. For example, the identifier can be an electronic credit or certification or representation electronically transmitted by the PVA manufacturer to a customer associated with the sale or transfer of the PVA product, and only because it is a credit, it represents that the PVA has recycled components. The identifier, such as a label (e.g., logo) or certification does not need to indicate or represent that the recycled components are directly or indirectly derived from cracked r-pyrolysis oil or obtained from r-pyrolysis gas. More precisely, it is sufficient that the PVA is at least partially obtained directly or indirectly from (i) pyrolysis recycled waste or (ii) recycled stock (wherein at least a portion of the deposit or credit in the recycled stock has their source of pyrolysis recycled waste). The identifier itself need only convey or communicate that the PVA has or is derived from recycled content, regardless of the source. In one embodiment or in combination with any of the mentioned embodiments, an article made from the PVA may have an identifier, such as a stamp or logo embedded in or adhered to the article. 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 derived directly or indirectly from pyrolytic recycled waste.

[0503] In one embodiment or in combination with any of the mentioned embodiments, there is provided a system or package comprising:

[0504] a. a single-ply interlayer, multi-ply interlayer or glass laminate (each of which is a "PVA-containing article"), in each case comprising PVA or PVB, and

[0505] b. An identifier (eg, a credit, label, or certification) associated with the PVA-containing article, the identifier being an indication that the PVA-containing article has recycled content or is made from a source having recycled content.

[0506] The PVA-containing article is combined with a recycled content identifier associated with the PVA-containing article, wherein the identifier is an indication that the PVA-containing article contains or is derived from or is associated with recycled content. The identifier can be a certification document, a product instruction sheet indicating the recycled content, a label, a logo or certification mark from a certification body, which indicates that the PVA-containing article contains or is derived from or is associated with recycled content, or it can be an electronic statement accompanying a purchase order or product by a PVA manufacturer or a PVA-containing article manufacturer, or published on a website as a statement, indication or mark, indicating that the PVA-containing article contains recycled content or is made from a source associated with recycled content or 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 PVA-containing article, or it can be an embossed, etched, stamped, printed, pontil or punt mark, engraved, molded or labeled, in each case directly on or in the PVA-containing article. The identifier need not indicate or indicate that the recycled content is directly or indirectly derived from cracked r-pyrolysis oil or obtained from r-pyrolysis gas. Rather, it is sufficient that the PVA is at least partially obtained directly or indirectly from cracked r-pyrolysis oil, and the identifier may convey or communicate only that the PVA has or is derived from recycled content, regardless of its source.

[0507] In one embodiment or in combination with any of the mentioned embodiments, r-PVA or articles made therefrom can be sold or offered for sale as articles containing or obtained from recycled content or containing recycled content or articles obtained from recycled content. The sale or offer for sale can be accompanied by a recycled content claim associated with the PVA or a certification or representation of the article made with the PVA.

[0508] The allocations and designations obtained (whether internally, such as through a bookkeeping or recycling stock tracking software program, or externally, through declarations, certifications, advertising, representations, etc.) can be made by the PVA manufacturer or within the PVA manufacturer family of entities. The designation of at least a portion of the PVA as corresponding to at least a portion of the quota (e.g., an allocation or credit) can be made in a variety of ways and according to the system employed by the PVA manufacturer, which can vary from manufacturer to manufacturer. For example, the designation can occur internally simply through a log entry in the books or files of the PVA manufacturer or other directory software program, or through instructions, packaging, advertising or declarations on the product, through a logo associated with the product, through a certification declaration associated with the product sold, or through a formula that calculates the amount to be deducted from the recycling stock relative to the amount of recycled content applied to the product.

[0509] Alternatively, the PVA can be sold. In one embodiment or in combination with any of the mentioned embodiments, there is provided a method of offering or selling polyvinyl acetal by:

[0510] a. converting the aldehyde composition in a synthesis process to prepare a polyvinyl acetal composition ("PVA"),

[0511] b. applying a recycled content value to at least a portion of said PVA, thereby obtaining a recycled PVA ("r-PVA"), and

[0512] c. Offering to sell or selling r-PVA that has recycled content or is obtained or derived from recycled waste.

[0513] The PVA manufacturer or its entity family can obtain the recycled component allocation, and the allocation can be obtained by any means described herein, and can be deposited into the recycled stock, and the recycled component allocation is directly or indirectly derived from the pyrolysis of recycled waste. The aldehyde converted in the synthesis process to prepare the polyvinyl acetal composition can be any aldehyde composition obtained from any source, including non-rA compositions, or can be an r-aldehyde composition. The r-PVA sold or promised to be sold can be designated as (for example, marked or certified or otherwise associated) with a recycled component value. In one embodiment or in combination with any of the embodiments mentioned, at least a portion of the recycled component value associated with r-PVA can be taken out from the recycled stock. In another embodiment, at least a portion of the recycled component value in PVA is obtained by converting rA. The recycled component value deducted from the recycled stock can be a non-pyrolysis recycled component value or can be a pyrolysis recycled component allocation; that is, its source is the recycled component value of the pyrolysis of recycled waste. The recycled stock can optionally include at least one entry, which is a allocation derived directly or indirectly from the pyrolysis of recycled waste. The designation may be an allocated amount deducted from the recycled stock, or the amount of recycled content declared or determined by the PVA manufacturer in its accounts. The amount of recycled content does not necessarily have to be physically applied to the PVA product. The designation may be an internal designation made to or by the PVA manufacturer or its family of entities, or a service provider with a contractual relationship with the PVA manufacturer or its family of entities. The amount of recycled content represented as included in the PVA sold or offered for sale 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 PVA offered for sale or sold and the amount of recycled content allocated or designated to the PVA by the PVA manufacturer.

[0514] The steps need not be sequential and may be independent of one another. For example, steps a) and b) may be performed simultaneously, such as would be the case if the rA composition is used to prepare the PVA, since rA is both an aldehyde composition and has a recycled content allocation associated therewith; or where the process for preparing the PVA is continuous and the use of recycled content values ​​for the PVA occurs during the manufacture of the PVA.

[0515] Turning again to the synthesis process for preparing r-PVA, the concentration of PVOH introduced into the PVA reaction vessel can be at least 5 wt.%, or at least 8 wt.%, or at least 10 wt.%, or at least 13 wt.%, or at least 15 wt.%, or at least 17 wt.%, or at least 20 wt.%, based on the weight of the PVOH composition fed into the reaction vessel. The balance is water, solvent, emulsifier or surfactant, catalyst.

[0516] The PVOH composition or feed stream may be dissolved in a solvent such as water before being introduced into the reaction zone. The PVOH feedstock may be heated to 80-95°C to dissolve the PVOH before entering the reaction zone, and may optionally be cooled to room temperature or lower after dissolution, and then reacted with AD in the presence of an acid catalyst. The PVOH stream may be premixed with AD and fed to the reaction vessel as a combined stream, or it may be fed as a separate stream from the aldehyde stream. The acid catalyst may be contained in the PVOH composition or fed to the reaction vessel separately.

[0517] The PVA reaction vessel may be a continuous stirred tank reactor, desirably equipped with an agitator, impeller or high shear mixer. Alternatively, the PVA reaction vessel may be an in-line high shear mixer.

[0518] In the reaction zone, the reaction temperature can be gradually increased during the reaction. For example, during at least a portion of the time when the AD and PVOH compositions are combined, the temperature can be increased to a first temperature, and then the temperature can be increased to a second temperature higher than the first temperature. During at least 25% or residence time, the reaction temperature can be maintained at at least about 50°C, or at least 60°C, and at most 110°C, or at most 100°C, or at most 95°C, or at most 90°C, or at most 85°C, or at most 80°C. During at least 25% of the time when or after the total amount of AD and PVOH compositions are combined in a batch reaction, the reaction temperature can be increased to at least 5°C higher than the first temperature, and at most 115°C. Alternatively, the reaction temperature can be 50°C to 110°C, or 80-100°C, at any time period or throughout the residence time. This is particularly true when the reaction is continuous.

[0519] The reaction pressure can be carried out without applying pressure, or at atmospheric pressure or near atmospheric pressure. The residence time is generally 1 to 5 hours. Further details on the preparation of PVA are also described in Vinyl Acetal Polymers, in Encyclopedia of Polymer Science & Technology, 3rd Edition, Vol. 8, pp. 381-399, BE Wade (2003) (Vinyl Acetal Polymers, in Encyclopedia of Polymer Science & Technology, 3rd Edition, Vol. 8, pp. 381-399).rd edition, Volume 8, pages 381-399, by B. E. Wade (2003)), the entire disclosure of which is incorporated herein by reference to the extent not inconsistent with the present disclosure.

[0520] The reaction can be batchwise, semi-batchwise or continuous. The reaction can be carried out in a single reaction vessel or in two or more reaction vessels arranged in parallel or in series. The contents of the reactor are desirably agitated or stirred during the reaction. For example, the reactor can be a continuously stirred tank reactor equipped with a high shear mixer.

[0521] As PVOH and AD react in the reaction zone, PVA resin particles precipitate and form a reaction slurry, which can be discharged from the reaction zone, neutralized, washed, and dried to a dry form, which can be handled and shipped as dry particles.

[0522] The structure of the PVA polymer (or r-PVA or pr-PVA) discharged from the reaction zone is shown below:

[0523]

[0524] Taking the above structure of polyvinyl butyral, the butyraldehyde or acetal content is based on the weight percent of unit A in the polymer, the OH content is based on the weight percent of unit B (PVOH portion) in the polymer, and the acetate or ester content is based on the weight percent of unit C in the polymer.

[0525] In one embodiment, r-PVA having at least one monomer derived from pr-A is now provided. pr-A may be derived directly or indirectly from the cracking of r-pyrolysis oil. The monomer unit derived from pr-A is unit A. In the acetal unit A, the amount of the monomer derived from pr-A may be 100 wt% or less of the amount of the acetal unit A. For example, the pr-A stream may be blended with an aldehyde composition that does not contain recycled components, and in this case, the amount of acetal unit A obtained from pr-A will be proportional to the weight ratio of the aldehyde raw material blend for preparing PVA. For example, if 30 wt.% of the aldehyde raw material is pr-A, then the amount of acetal unit A obtained from pr-A will also be 30 wt.% based on the weight of the acetal unit A present in the PVA. Based on the weight of PVA, if the amount of acetal unit A is, for example, 80 wt.% based on the weight of PVA, the amount of acetal unit A derived from pr-A will be 0.3×80 wt.%, or 24 wt.%, based on the weight of PVA. The amount of acetal units A derived from pr-A can be at least 1 wt%, or at least 3 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 95 wt%, or at least 98 wt%, or 100 wt%, based on the weight of acetal units A present in the PVA.

[0526] It is noteworthy that for a given type of plasticizer, the compatibility of the plasticizer in the polymer is primarily determined by the hydroxyl content of the PVA. PVA polymers with a larger residual hydroxyl content are generally associated with reduced plasticizer compatibility or capacity, which is generally due to the hydrophobicity of the plasticizer being more compatible with the fewer hydrophilic groups present on the polymer chain. In contrast, polymers with lower residual hydroxyl content will generally result in an increase in plasticizer compatibility or capacity. In general, this correlation between the residual hydroxyl content of the polymer and the plasticizer compatibility / capacity can be controlled and utilized to allow the addition of an appropriate amount of plasticizer to the polymer resin and to stably maintain differences in plasticizer content between multiple interlayers.

[0527] The hydroxyl content of the r-PVA resin is not particularly limited, but a suitable amount is at least about 6, or at least about 8, or at least about 10, or at least about 11, or at least about 12, or at least about 13, or at least about 14, or at least about 15, or at least about 16, or at least about 17, and in each case up to about 35 wt.% PVOH. For example, suitable weight percent (wt. %) ranges calculated as PVOH include about 6 to 35, or 6 to 30, or 6 to 25, or 6 to 23, or 6 to 20, or 6 to 18, or 6 to 17, or 6 to 16, or 6 to 15, or 7 to 35, or 7 to 30, or 7 to 25, or 7 to 23, or 7 to 20, or 7 to 18, or 7 to 17, or 7 to 16, or 7 to 15, or 8 to 35, or 8 to 30, or 8 to 25, or 8 to 23, or 8 to 20, or 8 to 18, or 8 to 17, or 8 to 16, or 8 to 15, or 9 to 35, or 9 to 30, or 9 to 25, or 9 to 23, or 9 to 20, or 9 to 18, or 9 to 17, or 9 to 16, or 9 to 15, or 10 to 35, or 10 to 30, or 10 to 25, or 10 to 23, or 10 to 20, or 10 to 18, or 10 to 17, or 10 to 16, or 10 to 15, or 11 to 35, or 11 to 30, or 11 to 25, or 11 to 23, or 11 to 20, or 11 to 18, or 11 11 to 16, or 11 to 15, or 12 to 35, or 12 to 30, or 12 to 25, or 12 to 23, or 12 to 20, or 12 to 18, or 12 to 17, or 12 to 16, or 12 to 15, or 13 to 35, or 13 to 30, or 13 to 25, or 13 to 23, or 13 to 20, or 13 to 18, or 13 to 17, or 13 to 16, or 13 to 15, or 14 to 35, or 14 to 30, or 14 to 25, or 14 to 23, or 14 to 2 0, or 14 to 18, or 14 to 17, or 14 to 16, or 14 to 15, or 15 to 35, or 15 to 30, or 15 to 25, or 15 to 23, or 15 to 20, or 15 to 18, or 15 to 17, or 15 to 16, or 16 to 35, or 16 to 30, or 16 to 25, or 16 to 23, or 16 to 20, or 16 to 18, or 16 to 17, or 17 to 35, or 17 to 30, or 17 to 25, or 17 to 23, or 17 to 20, or 17 to 18. If desired, the hydroxyl wt.% selected as PVOH can be at the lower end of this range. Generally, r-PVA polymers with lower hydroxyl wt.% have the ability to absorb more plasticizers and absorb plasticizers more effectively.

[0528] However, where optical clarity is desired, the hydroxyl wt.% may have an effect on the refractive index of the r-PVA resin. The hydroxyl wt.% of the r-PVA can be adjusted along with the amount of plasticizer to obtain a desired refractive index where optical clarity is desired. For example, a suitable range of hydroxyl wt.% calculated as PVOH units can be selected, which can be in the following ranges: 15 to 25, or 15 to 23, or 15 to 20, or 15 to 18, or 15 to 17, or 15 to 16, or 16 to 25, or 16 to 23, or 16 to 20, or 16 to 18, or 16 to 17, or 17 to 25, or 17 to 23, or 17 to 20, or 17 to 18 to improve the optical clarity of the integral interlayer laminated to glass.

[0529] The r-PVA resin may also contain 20 wt.% or less, or 17 wt.% or less, or 15 wt.% or less residual ester groups, including 13 wt.% or less, or 11 wt.% or less, or 9 wt.% or less, or 7 wt.% or less, or 5 wt.% or less, or 4 wt.% or less residual ester groups, based on the polyvinyl ester, such as acetate or units C, and in combination with units B, the balance being acetal, preferably butyraldehyde acetal, but optionally containing small amounts of other acetal groups, such as 2-ethylhexanal groups (see, for example, U.S. Pat. No. 5,137,954, the entire disclosure of which is incorporated herein by reference). Suitable ranges of residual ester groups by wt. % include 0 to 20, or 0 to 17, or 0 to 15, or 0 to 13, or 0 to 11, or 0 to 9, or 0 to 7, or 0 to 5, or 0 to 4, 1 to 20, or 1 to 17, or 1 to 15, or 1 to 13, or 1 to 11, or 1 to 9, or 1 to 7, or 1 to 5, or 1 to 4, or 1 to 20, or 1 to 17, or 1 to 15, or 1 to 13, or 1 to 11, or 1 to 9, or 1 to 7, or 1 to 5, or 1 to 4, or 2 to 20, or 2 to 17, or 2 to 15, or 2 to 13, or 2 to 11, or 2 to 7. or 4 to 7, or 4 to 5, or 6 to 20, or 6 to 17, or 6 to 15, or 6 to 13, or 6 to 11, or 6 to 9. As with the measurement of residual hydroxyl groups, the weight percent of residual ester groups (e.g., acetate) is based on the portion of the polymer backbone to which acetate groups (including pendant acetate groups) are attached.

[0530] The r-PVA resin used in the present invention may also have an acetal content (unit A) of at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.%, or at least 65 wt.%, or at least 70 wt.%, or at least 75 wt.%, or at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%. Additionally or alternatively, the acetal content may be at most 94 wt.%, or at most 93 wt.%, or at most 92 wt.%, or at most 91 wt.%, or at most 90 wt.%, or at most 89 wt.%, or at most 88 wt.%, or at most 86 wt.%, or at most 85 wt.%, or at most 84 wt.%, or at most 83 wt.%, or at most 82 wt.%, or at most 80 wt.%, or at most 78 wt.%, or at most 77 wt.%, or at most 75 wt.%, or at most 70 wt.%, or at most 65 wt.%.Suitable ranges of the acetal component in the r-PVA resin used in the present invention include 50 to 94, or 50 to 93, or 50 to 92, or 50 to 91, or 50 to 90, or 50 to 89, or 50 to 88, or 50 to 86, or 50 to 85, or 50 to 84, or 50 to 84, or 50 to 83, or 50 to 82, or 50 to 80, or 50 to 78, or 50 to 77, or 50 to 75, or 50 to 70, or 50 to 65, or 55 to 94, or 55 to 93, or 55 to 92, or 55 to 91, or 55 to 90, or 55 to 89, or 55 to 88, or 55 to 86, or 55 to 85, or 55 to 84, or 55 to 84 82, or 55 to 80, or 55 to 78, or 55 to 77, or 55 to 75, or 55 to 70, or 55 to 65, or 60 to 94, or 60 to 93, or 60 to 92, or 60 to 91, or 60 to 90, or 60 to 89, or 60 to 88, or 60 to 86, or 60 to 85, or 60 to 84, or 60 to 84, or 60 to 83, or 60 to 82, or 60 to 80, or 60 to 78, or 60 to 77, or 60 to 75, or 60 to 70, or 60 to 65, or 65 to 94, or 65 to 93, or 65 to 92, or 65 to 91, or 65 to 90, or 65 to 89, or 65 82, or 70 to 80, or 70 to 78, or 70 to 77, or 70 to 75, or 70 to 94, or 70 to 93, or 70 to 92, or 70 to 91, or 70 to 90, or 70 to 89, or 70 to 88, or 70 to 86, or 70 to 85, or 70 to 84, or 70 to 84, or 70 to 83, or 70 to 82, or 70 to 80, or 70 to 78, or 70 to 77, or 70 to 75, or 75 to 94, or 75 to 93, or 75 to 92, or 70 to 91, or 70 to 90, or 70 to 89, or 70 to 88, or 70 to 86, or 70 to 85, or 70 to 84, or 70 to 84, or 70 to 83, or 70 to 82, or 70 to 80, or 70 to 78, or 70 to 77, or 70 to 75, or 75 to 94, or 75 to 93, or 75 to 92, or 75 to 91, or 75 to 90, or 75 to 89, or 75 to 88, or 75 to 86, or 75 to 85, or 75 to 84, or 75 to 84, or 75 to 83, or 75 to 82, or 75 to 80, or 75 to 78, or 75 to 77, 80 to 94, or 80 to 93, or 80 to 92, or 80 to 91, or 80 to 90, or 89 to 89, or 80 to 88, or 80 to 86, or 80 to 85, or 80 to 84, or 80 to 83, or 80 to 82, or 85 to 94, or 85 to 93, or 85 to 92, or 85 to 91, or 85 to 90, or 85 to 89, or 85 to 88, or 85 to 86, or 80 to 84, or 80 to 83, or 80 to 82, or 85 to 94, or 85 to 93, or 85 to 92, or 85 to 91, or 85 to 90, or 85 to 89, or 85 to 88, or 85 to 86, or 90 to 94, or 90 to 93, or 90 to 92.

[0531] The acetal group is not particularly limited, and may be a vinyl propynyl group, a vinyl butyral group, or the like, and is desirably a vinyl butyral group.

[0532] There is no particular restriction on the weight average molecular weight of the r-PVA layer or at least one surface layer. w ) may be at least 20,000, or at least 30,000, or at least 40,000, or at least 50,000, or at least 60,000, or at least 70,000, with no particular upper limit, although in practice up to 300,000 daltons is suitable, and in each case is measured by size exclusion chromatography using the low angle laser light scattering (SEC / LALLS) method of Cotts and Ouano in tetrahydrofuran. The term "molecular weight" refers to the weight average molecular weight (M w ). The method for determining molecular...

Claims

1. A method for treating a recycled component aldehyde composition pr-A derived directly or indirectly from pyrolysis recycled waste, the method comprising feeding the pr-A to a reactor in which polyvinyl acetal is prepared, in, At least a portion of the recycled waste is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of the r-pyrolysis oil is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, wherein a cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and wherein the r-pyrolysis oil is not hydrotreated before the cracking.

2. The process of claim 1, wherein the non-recovery cracker feed stream comprises gasoline, naphtha, middle distillates, diesel or kerosene.

3. A method for preparing a recycled content polyvinyl acetal composition r-PVA, the method comprising reacting an aldehyde composition with a polyvinyl acetal composition to produce a PVA effluent comprising r-PVA, wherein at least a portion of the aldehyde composition pr-A is directly or indirectly derived from pyrolysis recycled waste, in, At least a portion of the recycled waste is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of the r-pyrolysis oil is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, wherein a cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein the r-pyrolysis oil is not hydrotreated before the cracking.

4. The process of claim 3, wherein the non-recovery cracker feed stream comprises gasoline, naphtha, middle distillates, diesel or kerosene.

5. A method of preparing PVA, comprising a PVA manufacturer or one of its family of entities: a. obtaining an aldehyde composition from a supplier, and: i. also obtain a pyrolysis recovery component quota or ii. obtaining a pyrolysis recovery component quota from any person or entity without supplying an aldehyde composition from the person or entity that transferred the pyrolysis recovery component quota; and b. depositing at least a portion of the pyrolysis recovery quota obtained in step a(i) or step a(ii) into a recovery inventory, and c. preparing a PVA composition from any aldehyde composition obtained from any source, wherein the recycled content quota is obtained from pyrolysis recycled waste, at least a portion of which is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of which is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, in, A cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein the r-pyrolysis oil is not hydrotreated before the cracking.

6. The process of claim 5, wherein the non-recovery cracker feed stream comprises gasoline, naphtha, middle distillates, diesel or kerosene.

7. A method for preparing a polyvinyl acetal composition PVA, the method comprising: a. The PVA manufacturer obtains the aldehyde composition from a supplier and: i. also obtain a pyrolysis recovery component quota or ii. obtaining a pyrolysis recovery component quota from any person or entity without supplying an aldehyde composition from the person or entity that transferred the pyrolysis recovery component quota; as well as b. the PVA manufacturer prepares PVA from any aldehyde composition obtained from any source; and c. Any of the following: i. applying the pyrolysis recovery component quota to PVA prepared by supplying the aldehyde obtained from step (a); or ii. applying the pyrolysis recovery component quota to PVA which is not prepared by supplying the aldehyde obtained in step (a), or iii. depositing the pyrolysis recovery component credit into a recovery inventory, deducting the recovery component value from the recovery inventory, and applying at least a portion of the value to: 1.PVA, thereby obtaining r-PVA, or 2. Compounds or compositions other than PVA, or 3. Both; Regardless of whether the recovered component value is obtained from the pyrolysis recovered component quota obtained in step a(i) or step a(ii), wherein the recycled content quota is obtained from pyrolysis recycled waste, at least a portion of which is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of which is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, wherein a cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein the r-pyrolysis oil is not hydrotreated before the cracking.

8. A method for preparing a recycled polyvinyl acetal composition r-PVA, the method comprising: a. reacting any aldehyde composition in a synthesis process to prepare a polyvinyl acetal composition PVA; and b. applying the recycled component value to at least a portion of the PVA to obtain a recycled component PVA composition r-PVA; and c. obtaining the recovered component value by deducting at least a portion of the recovered component value from a recovered inventory, optionally wherein the recovered inventory also contains a pyrolysis recovered component credit or a pyrolysis recovered component credit that has been incorporated into the recovered inventory prior to the deduction; and d. optionally communicating to a third party that the r-PVA has recycled content or is obtained or derived from recycled waste, wherein the r-PVA is derived directly or indirectly from pyrolysis recycled waste, at least a portion of which is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of which is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, wherein a cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein the r-pyrolysis oil is not hydrotreated before the cracking.

9. The process of claim 8, wherein the non-recovery cracker feed stream comprises gasoline, naphtha, middle distillates, diesel or kerosene.

10. The process of claim 8, wherein the r-PVA is derived directly or indirectly from cracking r-pyrolysis oil in a hot steam furnace.

11. The method of claim 8, wherein the aldehyde comprises r-butyraldehyde.

12. The method according to claim 11, wherein: The crude r-PVA solids are maintained in a wash solution containing water, a water-miscible solvent for the resin and an alkaline material dissolved therein to neutralize the acidic reaction slurry and maintained under active agitation.

13. The method according to claim 11, wherein: After the addition of r-butyraldehyde is nearly complete or complete, the temperature of the mixture in the PVA reactor is increased to a value between 60°C and 80°C.

14. A method for changing the recycled content value in a recycled content PVA composition r-PVA, the method comprising: a. Any of the following: i. reacting the recycled component aldehyde composition rA to prepare a recycled component PVA composition r-PVA having a first recycled component value, a first r-PVA; or ii. having a recycled content PVA composition r-PVA, the composition having a first recycled content value, and also a first r-PVA; and b. transferring recycled content values ​​between the recycled stock and the first r-PVA to obtain a second recycled content PVA composition, a second r-PVA, having a second recycled content value, the second recycled content value being different from the first recycled content value, wherein the transferring optionally comprises: i. deducting the recycled content value from the recycled stock and applying the recycled content value to the first r-PVA to obtain the second r-PVA having a second recycled content value, the second recycled content value being higher than the first recycled content value; or ii. deducting the recycled content value from the first r-PVA and adding the deducted recycled content value to the recycled stock to obtain the second r-PVA having a second recycled content value, the second recycled content value being lower than the first recycled content value, wherein the r-PVA is derived directly or indirectly from pyrolysis recycled waste, at least a portion of which is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of which is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, wherein a cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein the r-pyrolysis oil is not hydrotreated before the cracking.

15. A method for preparing a recycled component PVA composition r-PVA, the method comprising: a. pyrolyzing a pyrolysis feed comprising recycled waste material to form a pyrolysis effluent comprising recycled pyrolysis oil r- pyrolysis oil and recycled pyrolysis gas r- pyrolysis gas; b. cracking a cracker feed comprising at least a portion of the r-pyrolysis oil in a hot steam cracker, thereby producing a cracker effluent comprising r-olefins, wherein a cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein said r-pyrolysis oil is not hydrotreated prior to said cracking; and c. reacting any olefin volume in the synthesis process to produce an aldehyde composition; and d. reacting at least a portion of any aldehyde composition in a synthesis process to prepare a PVA composition; and e. applying a recycled content value to at least a portion of the PVA composition based on: i. The pyrolysis recovery component aldehyde composition pr-A is fed as a raw material or ii. depositing at least a portion of the quota obtained from any one or more of steps a) or b) into a recycled stock, and deducting a recycled content value from said stock, and applying at least a portion of said value to PVA, thereby obtaining said r-PVA.

16. Use of a recycled component aldehyde composition pr-A derived directly or indirectly from pyrolysis recycled waste, said use comprising converting said pr-A in a synthetic process to prepare a polyvinyl acetal composition, in, At least a portion of the recycled waste is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of the r-pyrolysis oil is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, wherein a cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein the r-pyrolysis oil is not hydrotreated before the cracking.

17. A method for indicating an identifier in a system or package, comprising providing: a. polyvinyl acetal composition PVA, and b. an identifier associated with the PVA, the identifier being an indication that the PVA has recycled content or is made from a source having a recycled content value, wherein the recycled content value is obtained from pyrolysis recycled waste, at least a portion of which is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of which is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, in, A cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein the r-pyrolysis oil is not hydrotreated before the cracking.

18. The process of claim 17, wherein the non-recovery cracker feed stream comprises gasoline, naphtha, middle distillates, diesel or kerosene.

19. An r-PVA having at least one monomer derived from a recycled content aldehyde composition, wherein the r-PVA is derived directly or indirectly from pyrolysis recycled waste, at least a portion of which is obtained from recycled pyrolysis oil r-pyrolysis oil produced by pyrolysis of waste plastics, at least a portion of which is cracked in a hot steam cracker to produce a cracker effluent comprising r-olefins, in, A cracker feed stream is fed into the hot steam cracker, the cracker feed comprising at least 1 wt% of r-pyrolysis oil based on the weight of the cracker feed stream, and at least 50 wt% of a C5-C 22 a non-recovered cracker feed stream of a hydrocarbon stream; and, wherein the r-pyrolysis oil is not hydrotreated before the cracking.

20. The r-PVA of claim 15, wherein the non-recovery cracker feed stream comprises gasoline, naphtha, middle distillates, diesel, or kerosene.

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