EP4363523A1

EP4363523A1 - Chemical recycling facility and process with enhanced integration

Info

Publication number: EP4363523A1
Application number: EP22833956.0A
Authority: EP
Inventors: Xianchun Wu; Daryl Bitting; Kenny Randolph Parker; Michael Gary POLASEK; David Eugene SLIVENSKY
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2021-06-30
Filing date: 2022-06-24
Publication date: 2024-05-08
Also published as: WO2023278261A1; CN117580929A

Abstract

Processes and facilities for providing recycled content hydrocarbon products (r-products) from recycled content pyrolysis oil (r-pyoil) and recycled content pyrolysis gas (r-pygas). Processing schemes provided herein maximize use of recycled content pyrolysis products to provide a variety of recycled content end products.

Description

CHEMICAL RECYCLING FACILITY AND PROCESS WITH ENHANCED INTEGRATION

BACKGROUND

[0001] Waste plastic pyrolysis plays a part in a variety of chemical recycling technologies. The pyrolysis of waste plastic produces heavy components (e.g., waxes, tar, and char) as well as recycled content pyrolysis oil (r-pyoil) and recycled content pyrolysis gas (r-pygas). When the pyrolysis facility is located near another processing facility, such as a cracker facility, it is desirable to send as much of the r-pyoil and r-pygas as possible to the downstream processing facility to be used as a feedstock in forming other recycled content products (e.g., olefins, paraffins, etc.).

[0002] However, in some cases, particularly when it is part of the existing infrastructure, a single downstream processing facility may not be configured to accept both r-pyoil and r-pygas or may not be configured to accept the entire volume of r-pyoil and/or r-pygas produced by the pyrolysis facility. In such circumstances, it may be economically efficient to burn the r-pyoil as fuel or otherwise dispose of it, but this runs counter to one of the main goals of chemical recycling, which is to transform as much as of the waste plastic as possible into new products. Thus, a processing scheme that provides better utilization of r-pyoil and r-pygas formed by pyrolysis of waste plastic is needed.

SUMMARY

[0003] In one aspect, the present technology concerns a chemical recycling process, the process comprising: (a) pyrolyzing waste plastic to thereby provide a recycled content pyrolysis effluent (r-pyrolysis effluent); (b) separating at least a portion of said r-pyrolysis effluent to provide a recycled content pyrolysis gas (r-pygas) and recycled content pyrolysis oil (r-pyoil); (c) introducing at least a portion of said r-pygas into a cracker facility; and (d) introducing at least a portion of said r-pyoil into another downstream location, wherein said downstream location is not within the cracker facility. [0004] In one aspect, the present technology concerns a chemical recycling process, the process comprising: (a) pyrolyzing waste plastic to thereby provide a recycled content pyrolysis effluent (r-pyrolysis effluent); (b) separating at least a portion of said r-pyrolysis effluent to provide a recycled content pyrolysis gas (r-pygas) and recycled content pyrolysis oil (r-pyoil); and (c) introducing at least a portion of said r-pyoil into one or more of the following locations (i) through (ix) - (i) a storage vessel; (ii) a transportation apparatus; (iii) a fluidized catalytic cracker; (iv) a carbon reformer; (v) a distillation column or zone; (vi) a fine chemical facility; (vii) a burner; (viii) an MTO facility; and (ix) an oil refinery.

BRIEF DESCRIPTION OF THE DRAWINGS

[0005] FIG. 1 is a block flow diagram illustrating the main steps of a process and facility for utilizing recycled content pyrolysis gas (r-pygas) and recycled content pyrolysis oil (r-pyoil) formed by pyrolyzing waste plastic in one or more downstream process facilities.

DETAILED DESCRIPTION

[0006] We have discovered new methods and systems for utilizing recycled content pyrolysis gas (r-pygas) and recycled content pyrolysis oil (r- pyoil). In particular, we have found that r-pygas can be routed to a cracker facility, while the r-pyoil can be used in processing facilities different from the cracker facility. As a result, maximum utilization of both the r-pygas and r- pyoil can be achieved, regardless of the configuration of the cracking or other downstream processing facility.

[0007] FIG. 1 illustrates one embodiment of a process and system for use in chemical recycling of waste plastic. The process/facility shown in FIG. 1 includes a pyrolysis step/facility 20 and a cracking step/facility 40. The pyrolysis facility 20 and cracker facility 40 may be co-located or may be located remotely from one another. As used herein, the term “co-located” refers to the characteristic of at least two objects being situated on a common physical site, and/or within 0.5 or 1 mile of each other. As used herein, the term “located remotely” refers to a distance of greater than 1 , greater than 5, greater than 10, greater than 50, greater than 100, greater than 500, greater than 1000, or greater than 10,000 miles between two facilities, sites, or reactors.

[0008] When two or more facilities are co-located, the facilities may be integrated in one or more ways. Examples of integration include, but are not limited to, heat integration, utility integration, waste-water integration, mass flow integration via conduits, office space, cafeterias, integration of plant management, IT department, maintenance department, and sharing of common equipment and parts, such as seals, gaskets, and the like.

[0009] In some embodiments, the pyrolysis facility/process 20 is a commercial scale facility/process receiving the waste plastic feedstock 110 at an average annual feed rate of at least 100, or at least 500, or at least 1 ,000, at least 2,000, at least 5,000, at least 10,000, at least 50,000, or at least 100,000 pounds per hour, averaged over one year. Further, the pyrolysis facility can produce the r-pyoil 114 and r-pygas 116 in combination at an average annual rate of at least 100, or at least 1 ,000, or at least 5,000, at least 10,000, at least 50,000, or at least 75,000 pounds per hour, averaged over one year.

[0010] Similarly, the cracker facility/process 40 can be a commercial scale facility/process receiving hydrocarbon feed 120 at an average annual feed rate of at least at least 100, or at least 500, or at least 1 ,000, at least 2,000, at least 5,000, at least 10,000, at least 50,000, or at least 75,000 pounds per hour, averaged over one year. Further, the cracker facility can produce at least one recycled content product stream (r-product) at an average annual rate of at least 100, or at least 1 ,000, or at least 5,000, at least 10,000, at least 50,000, or at least 75,000 pounds per hour, averaged over one year. When more than one r-product stream is produced, these rates can apply to the combined rate of all r-products. [0011] As shown in FIG. 1 , the process starts with a pyrolysis step where waste plastic 110 is pyrolyzed in a pyrolysis reactor 22. The pyrolysis reaction involves chemical and thermal decomposition of the sorted waste plastic introduced into the reactor 22. Although all pyrolysis processes may be generally characterized by a reaction environment that is substantially free of oxygen, pyrolysis processes may be further defined, for example, by the pyrolysis reaction temperature within the reactor, the residence time in the pyrolysis reactor, the reactor type, the pressure within the pyrolysis reactor, and the presence or absence of pyrolysis catalysts.

[0012] The pyrolysis reactor 22 represented in FIG. 1 can be, for example, a film reactor, a screw 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, or an autoclave.

[0013] The pyrolysis reaction can involve heating and converting the waste plastic feedstock in an atmosphere that is substantially free of oxygen or in an atmosphere that contains less oxygen relative to ambient air. For example, the atmosphere within the pyrolysis reactor 22 may comprise not more than 5, not more than 4, not more than 3, not more than 2, not more than 1 , or not more than 0.5 weight percent of oxygen.

[0014] The temperature in the pyrolysis reactor 22 can be adjusted to facilitate the production of certain end products. In some embodiments, the peak pyrolysis temperature in the pyrolysis reactor can be at least 325°C, or at least 350°C, or at least 375°C, or at least 400°C. Additionally or alternatively, the peak pyrolysis temperature in the pyrolysis reactor can be not more than 800°C, not more than 700°C, or not more than 650°C, or not more than 600°C, or not more than 550°C, or not more than 525°C, or not more than 500°C, or not more than 475°C, or not more than 450°C, or not more than 425°C, or not more than 400°C. More particularly, the peak pyrolysis temperature in the pyrolysis reactor can range from 325 to 800°C, or 350 to 600°C, or 375 to 500°C, or 390 to 450°C, or 400 to 500°C. [0015] The residence time of the feedstock within the pyrolysis reactor 22 can be at least 1 , or at least 5, or at least 10, or at least 20, or at least 30, or at least 60, or at least 180 seconds. Additionally, or alternatively, the residence time of the feedstock within the pyrolysis reactor 22 can be less than 2, or less than 1 , or less than 0.5, or less than 0.25, or less than 0.1 hours. More particularly, the residence time of the feedstock within the pyrolysis reactor 22 can range from 1 second to 1 hour, or 10 seconds to 30 minutes, or 30 seconds to 10 minutes.

[0016] The pyrolysis reactor 22 can be maintained at a pressure of at least 0.1 , or at least 0.2, or at least 0.3 barg and/or not more than 60, or not more than 50, or not more than 40, or not more than 30, or not more than 20, or not more than 10, or not more than 8, or not more than 5, or not more than 2, or not more than 1.5, or not more than 1.1 barg. The pressure within the pyrolysis reactor 22 can be maintained at atmospheric pressure or within the range of 0.1 to 60, or 0.2 to 10, or 0.3 to 1.5 barg.

[0017] The pyrolysis reaction in the reactor can be thermal pyrolysis, which is carried out in the absence of a catalyst, or catalytic pyrolysis, which is carried out in the presence of a catalyst. When a catalyst is used, the catalyst can be homogenous or heterogeneous and may include, for example, certain types of zeolites and other mesostructured catalysts.

[0018] As shown in FIG. 1 , a pyrolysis effluent 112 is removed from the reactor 22 and can be separated in a separator 24 to produce a recycled content pyrolysis oil (r-pyoil) 114, a recycled content pyrolysis gas (r-pygas) 116, and a recycled content pyrolysis residue (r-pyrolysis residue) 118. As used herein, the term “r-pygas” refers to a composition obtained from waste plastic pyrolysis that is gaseous at 25°C at 1 atm. As used herein, the terms “r-pyoil” refers to a composition obtained from waste plastic pyrolysis that is liquid at 25°C and 1 atm. As used herein, the term “r-pyrolysis residue” refers to a composition obtained from waste plastic pyrolysis that is not r-pygas or r- pyoil and that comprises predominantly pyrolysis char and pyrolysis heavy waxes. As used herein, the term “pyrolysis char” refers to a carbon- containing composition obtained from pyrolysis that is solid at 200°C and 1 atm. As used herein, the term “pyrolysis heavy waxes” refers to C20+ hydrocarbons obtained from pyrolysis that are not pyrolysis char, pyrolysis gas, or pyrolysis oil.

[0019] In some embodiments, the r-pygas includes C2 and/or C3 components each in an amount of 5 to 60, 10 to 50, or 15 to 45 weight percent, C4 components in an amount of 1 to 60, 5 to 50, or 10 to 45 weight percent, and C5 components in an amount of 1 to 25, 3 to 20, or 5 to 15 weight percent.

[0020] In some embodiments, the r-pyoil comprises at least 50, at least 75, at least 90, or at least 95 weight percent of C4 to C30, C5 to C25, C5 to C22, or C5 to C20 hydrocarbon components. The r-pyoil can have a 90% boiling point in the range of from 150 to 350°C, 200 to 295°C, 225 to 290°C, or 230 to 275°C. As used herein, “boiling point” refers to the boiling point of a composition as determined by ASTM D2887-13. Additionally, as used herein, an “90% boiling point,” refers to a boiling point at which 90 percent by weight of the composition boils per ASTM D-2887-13.

[0021] In some embodiments, the r-pyoil can comprise heteroatom- containing compounds in an amount of less than 20, less than 10, less than 5, less than 2, less than 1 , or less than 0.5 weight percent. As used herein, the term “heteroatom-containing” compound includes any compound or polymer containing nitrogen, sulfur, or phosphorus. Any other atom is not regarded as a “heteroatom” for purposes of determining the quantity of heteroatoms, heterocompounds, or heteropolymers present in the r-pyoil. Heteroatom- containing compounds include oxygenated compounds. Often, such compounds exist in the r-pyoil when the pyrolyzed waste plastic includes polyethylene terephthalate (PET) and/or polyvinyl chloride (PVC). Thus, little to no PET and/or PVC in the waste plastic 110 results in little to no heteroatom-containing compounds in the r-pyoil.

[0022] As shown in FIG. 1 , at least a portion of the r-pygas 116 can be introduced into a cracker facility 40. In some embodiments, at least 50, at least 75, at least 90, or at least 95 percent of the r-pygas 116 from the pyrolysis facility 20 can be introduced into the cracker facility. All or a portion of the r-pygas 116 may be introduced into at least one location upstream of the furnace 42. Additionally, or alternatively, all or a portion of the r-pygas 116 may be introduced into at least one location downstream of the furnace 42.

[0023] When introduced into a location downstream of the cracker furnace 42, the r-pygas 116 may be introduced into one or more of the following locations: (i) the quench zone 44, which cools and partially condenses the furnace effluent; (ii) the compression zone 46, which compresses the vapor portion of the furnace effluent in two or more compression stages; and (iii) the separation zone 48, which separates the compressed stream into two or more recycled content products (r-products). In some cases, the r-pygas 116 may be introduced into only one of these locations, while, in other cases, the r- pygas 116 may be divided into additional fractions and each fraction introduced into a different location. In such cases, the fractions of the r-pygas 116 may be introduced into at least two, three, or all of the locations shown in FIG. 1.

[0024] When introduced into the quench zone 44, the r-pygas 116 can be introduced into a separation or quench vessel, or into the inlet or effluent of the quench zone 44. In some cases, this may include heating and/or compressing the r-pygas 116 so that it has a temperature within about 150, about 125, or about 100°C and/or a pressure within about 75, about 50, or about 25 psi of the stream or vessel into which the r-pygas 116 is being introduced.

[0025] When introduced into the compression section 46, the r-pygas 116 may be introduced upstream of the first compression stage, upstream or downstream of the last compression stage, or upstream of one or more intermediate compression stages.

[0026] When introduced into the separation zone 48, the r-pygas 116 may be introduced into the inlet of one or more of the separation columns (including the first or last column), or may be combined with a stream, such as an overhead or bottoms stream, withdrawn from one or more of the separation columns.

[0027] When introduced upstream of the furnace 42, the r-pygas 116 may be combined with the hydrocarbon feed 120 introduced into the inlet of cracker furnace 42. The hydrocarbon feed 120 may comprise predominantly C3 to C5 hydrocarbon components, C5 to C22 hydrocarbon components, or C3 to C22 hydrocarbon components, or even predominantly C2 components. The hydrocarbon feed 120 may include recycled content from one or more sources, or it may include non-recycled content. Additionally, in some cases, the hydrocarbon feed 120 may not include any recycled content.

[0028] As shown in FIG. 1 , the combined stream including r-pygas and hydrocarbon feed may be introduced into the cracker furnace 42, wherein it can be thermally cracked to form a lighter hydrocarbon effluent. The effluent stream can then be cooled in the quench zone 44 and compressed in the compression zone 46. The compressed stream from the compression zone 46 can be further separated in the separation zone 48 to produce at least one recycled content product (r-product) 122. Examples of recycled content products include, but are not limited to, recycled content ethane (r-ethane), recycled content ethylene (r-ethylene), recycled content propane (r-propane), recycled content propylene (r-propylene), recycled content butane (r-butane), recycled content butenes (r-butenes), recycled content butadiene (r- butadiene), and recycled content pentanes and heavier (r-C5+). In some embodiments, at least a portion of the recycled content stream (e.g., r-ethane or r-propane) may be returned to the inlet of the cracker furnace as a reaction recycle stream.

[0029] In some embodiments, the r-pygas 116 may be introduced into the cracker facility 40 at multiple locations both upstream and downstream of the cracker furnace 42. In such cases, furnace effluent formed by cracking at least a portion of one of the r-pygas fractions may be combined with another the r-pygas fraction introduced downstream of the cracker furnace 42. [0030] As shown in FIG. 1 , at least a portion or all of the r-pyoil can be introduced into a downstream location 50. The downstream location 50 may not be within the cracker facility 40, as shown in FIG. 1. In some embodiments, at least 75, at least 85, at least 90, at least 95, at least 97, or at least 98 weight percent of the r-pyoil 114 may not be sent to the cracker facility 40.

[0031] The downstream location 50 may include one or more downstream processing, storage, and/or transportation facilities suitable for reacting, separating, storing, and/or moving at least a portion of the r-pyoil 114. In some embodiments, the downstream location 50 can comprise at least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, or all of a storage vessel, a transportation apparatus, a fluidized catalytic cracker (FCC), a carbon reformer, a distillation column or zone, a fine chemical facility, a burner, a methanol-to-olefins (MTO) facility, and an oil refinery. In some cases, the downstream location 50 can be a different cracker facility other than the cracker facility 40 to which the r- pygas is introduced.

[0032] In some embodiments, the downstream location 50 can include a storage and/or a transportation apparatus. The storage/transportation apparatus can be an insulated, cooled, and/or pressurized tank, conduit, and/or pipeline. The tank can be a stationary tank or a tank located on a rail car, truck, trailer, or ship. As used herein, the term “pipeline” as applied to a transportation apparatus refers to a pipeline used to transport materials more than 2, more than 5, more than 10, more than 100, more than 1000, or more than 2500 miles. Such pipelines move material from one site to another are not the same as intra-facility piping that moves material between co-located reactors, vessels, and facilities.

[0033] In some embodiments, the downstream location 50 can include an oil refinery. Oil refineries are multi-process facilities that convert crude oil or similarly heavy hydrocarbons to lighter hydrocarbon products such as gasoline, diesel, jet fuel, as well as C4 and lighter hydrocarbons and heavier streams such as gas oils. When a portion of the r-pyoil 114 is introduced into an oil refinery, it may undergo one or more processing steps to produce a recycled content fuel (r-fuel).

[0034] In some embodiments, the r-pyoil introduced into a refinery can be subjected to a cracking step to reduce the molecular weight of the hydrocarbon molecules through catalytic and/or thermal cracking. Examples of catalytic crackers include fluidized or fixed bed catalytic crackers. A coker is one example of a thermal cracker.

[0035] Additionally, or alternatively, the r-pyoil can be introduced into a reformer, such as a naphtha reformer, and/or an isomerization unit, wherein the molecular structure of the hydrocarbons can be rearranged, often in the presence of a catalyst. For example, the paraffin/alkane components of the r- pyoil may be converted to olefin/alkene components in a reformer. The resulting recycle content product streams from these units can be used as an r-fuel or as a blending component to form one or more of the r-fuels mentioned previously.

[0036] In some embodiments, the r-pyoil can be introduced into at least one separation vessel, such as for example, a distillation column. The column can be configured to separate various components from the r-pyoil and one or more of these components can be used in or as the r-fuel. Examples of distillation columns in an oil refinery can include, but are not limited to, a crude oil tower, an FCC main fractionator, a coker main fractionator, a naphtha splitter, and combinations of these.

[0037] Examples of r-fuel products from the oil refinery can include, but are not limited to, recycled content gasoline-range fuel (r-gasoline) having a 50% boiling point from 100 to 250°C, recycled content diesel-range fuel (r-diesel) having a 50% boiling point from 250 to 300°C, a recycled content gas oil- range fuel (r-gas oil) having a 50% boiling point from 300 to 400°C, a residual oil-range fuel (r-residual oil) having a 50% boiling point from 400 to 500°C, and a recycled content solid product such as asphalt or coke (r-asphalt or r- coke). As used herein with reference to fuels, the term “50% boiling point” refers to the temperature at which 50% of the fuel mixture has boiled off as determined by ASTM D-86.

[0038] In some embodiments, the downstream location 50 can include a fine chemical facility used to produce starting materials for pharmaceuticals, agrochemicals, insecticides, pigments, and other end products. The fine chemical facility may utilize one or more of amination, condensation, esterification, Friedel-Crafts, Gringnard, halogenation, and/or hydrogenation to provide one or more recycled content fine chemicals (r-chemical), including one or more of the types listed previously.

[0039] In some embodiments, the downstream location 50 can include a distillation column. The distillation column may be a single distillation column for separating one or more components from the r-pyoil stream, or it may include two or more columns in series configured to form multiple recycled content hydrocarbon streams. The distillation column may be present in another type of facility (e.g., an oil refinery or fine chemical facility) or may be present in a separation facility configured only to form recycled content hydrocarbon products.

[0040] In some embodiments, the downstream location 50 can include a burner such as, for example, a burner of a furnace or other energy generation facility. The furnace may be used to generate energy for the pyrolysis facility 20 shown in FIG. 1 or for another type of facility including, for example, an oil refinery or fine chemical facility. In other embodiments, the burner may be used to generate energy in a motor or engine when, for example, the r-pyoil is used directly as a fuel source (e.g., a ship or train).

[0041] In some embodiments, the downstream location 50 can include a carbon reformer so that the r-pyoil 114 can be subjected to carbon reforming to produce a recycled content syngas (r-syngas) and a recycled content hydrogen (r-H2). In one embodiment, the carbon reforming is partial oxidation gasification fed with a non-recycled content liquid or gaseous hydrocarbon and the r-pyoil. In some embodiments, the carbon reforming can include catalytic reforming, while in other embodiments, the carbon reforming can include steam reforming.

[0042] As used herein, the term “partial oxidation” refers to high temperature conversion of a carbon-containing feed into syngas (carbon monoxide, hydrogen, and carbon dioxide), where the conversion is carried out with an amount of oxygen that is less than the stoichiometric amount of oxygen needed for complete oxidation of carbon to C02. The feed to POX gasification can include solids, liquids, and/or gases.

[0043] In some embodiments, the carbon reforming may include a gasifier that can comprise a gas-fed gasifier, a liquid-fed gasifier, a solid-fed gasifier, or a combination thereof. More particularly, the carbon reforming can include liquid-fed partial oxidation gasification. As used herein, “liquid-fed partial oxidation gasification” refers to a partial oxidation gasification process where the feed to the process comprises predominately components that are liquid at 25°C and 1 atm. Additionally, the carbon reforming may comprise gas-fed partial oxidation gasification. As used herein, “gas-fed partial oxidation gasification” refers to a partial oxidation gasification process where the feed to the process comprises predominately components that are gaseous at 25°C and 1 atm.

[0044] In some embodiments, the carbon reforming includes partial oxidation gasification. During partial oxidation gasification, the gasifier is operated in an oxygen-lean environment, relative to the amount needed to completely oxidize 100 percent of the carbon and hydrogen bonds. For example, the total oxygen requirements for the gasifier may be at least 5, 10, 15, or 20 percent in excess of the amount theoretically required to convert the carbon content of the gasification feedstock to carbon monoxide. In general, satisfactory operation may be obtained with a total oxygen supply of 10 to 80 percent in excess of the theoretical requirements. For example, examples of suitable amounts of oxygen per pound of carbon may be in the range of 0.4 to 3.0, 0.6 to 2.5, 0.9 to 2.0, or 1.2 to 2.0 pounds free oxygen per pound of carbon. [0045] When partial oxidation gasification is used for the carbon reforming step, the type of gasification technology employed can be a partial oxidation entrained flow gasifier that generates syngas. This technology is distinct from fixed bed (alternatively called moving bed) gasifiers and from fluidized bed gasifiers. In fixed bed (or moving bed gasifiers), the feedstock stream moves in a countercurrent flow with the oxidant gas, and the oxidant gas typically employed is air. The feedstock stream falls into the gasification chamber, accumulates, and forms a bed of feedstock. Air (or alternatively oxygen) flows from the bottom of the gasifier up through the bed of feedstock material continuously while fresh feedstock continuously falls down from the top by gravity to refresh the bed as it is being combusted. The combustion temperatures are typically below the fusion temperature of the ash and are non-slagging.

[0046] In some embodiments, when the carbon reforming includes gasification, the gasifier can include at least the following properties: (i) single stage; (ii) slagging; (iii) downflow; (iv) entrained flow; (v) high pressure; (vi) high temperature; (vii) slurry fed; (viii) coal or PET fed; and/or (ix) quenching gasifier.

[0047] In some embodiments, the downstream location 50 can include a methanol-to-olefins (MTO) facility. In such embodiments, the r-pyoil would first be converted into methanol and the methanol then reacted to form olefins such as ethylene and propylene. The r-pyoil could optionally undergo initial reactions such as gasification and separation before being used to form methanol. In some embodiments, r-pyoil fed to a carbon reformer could then be introduced into an MTO facility for conversion into methanol and olefins. [0048] In some embodiments, the r-pyoil 114 can be combined with at least one non-recycled content hydrocarbon stream and the combined stream may be subjected to further processing in the downstream location. When combined with another stream, the r-pyoil 114 can make up 5 to 95 percent,

10 to 80 percent, or 25 to 75 weight percent of the combined stream. Combining the r-pyoil 114 with other streams maximizes use of existing facilities when processing the r-pyoil into other products.

[0049] In some embodiments, the r-pyoil 114 may be divided into two or more fractions and each fraction may be introduced into a different downstream location 50. In some cases, the r-pyoil 114 may be divided such that one fraction includes 5 to 95, 10 to 80, 15 to 75, or 25 to 60 weight percent of the total amount of r-pyoil removed from the pyrolysis facility 20. In other embodiments, at least 90, at least 95, at least 97, or at least 99 percent of the r-pyoil 114 from the pyrolysis facility 20 may be introduced into a single downstream location 50.

DEFINITIONS

[0050] It should be understood that the following is not intended to be an exclusive list of defined terms. Other definitions may be provided in the foregoing description, such as, for example, when accompanying the use of a defined term in context.

[0051] As used herein, the terms “a,” “an,” and “the” mean one or more.

[0052] As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

[0053] As used herein, the phrase “at least a portion” includes at least a portion and up to and including the entire amount or time period.

[0054] As used herein, the term “chemical recycling” refers to a waste plastic recycling process that includes a step of chemically converting waste plastic polymers into lower molecular weight polymers, oligomers, monomers, and/or non-polymeric molecules (e.g., hydrogen, carbon monoxide, methane, ethane, propane, ethylene, and propylene) that are useful by themselves and/or are useful as feedstocks to another chemical production process(es). [0055] As used herein, the term “co-located” refers to the characteristic of at least two objects being situated on a common physical site, and/or within one mile of each other.

[0056] As used herein, the term “commercial scale facility” refers to a facility having an average annual feed rate of at least 500 pounds per hour, averaged over one year.

[0057] As used herein, the terms “comprising,” “comprises,” and “comprise” are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject.

[0058] As used herein, the term “cracking” refers to breaking down complex organic molecules into simpler molecules by the breaking of carbon- carbon bonds.

[0059] As used herein, the terms “including,” “include,” and “included” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

[0060] As used herein, the term “located remotely” refers to a distance of greater than 1, 5, 10, 50, 100, 500, 1000, or 10,000 miles between two facilities, sites, or reactors.

[0061] As used herein, the term “predominantly” means more than 50 percent by weight. For example, a predominantly propane stream, composition, feedstock, or product is a stream, composition, feedstock, or product that contains more than 50 weight percent propane.

[0062] As used herein, the term “pyrolysis” refers to thermal decomposition of one or more organic materials at elevated temperatures in an inert (i.e., substantially oxygen free) atmosphere.

[0063] As used herein, the terms “pyrolysis gas” and “pygas” refer to a composition obtained from pyrolysis that is gaseous at 25°C. [0064] As used herein, the terms “pyrolysis oil” or “pyoil” refers to a composition obtained from pyrolysis that is liquid at 25°C and 1 atm.

[0065] As used herein, the term “pyrolysis residue” refers to a composition obtained from pyrolysis that is not pyrolysis gas or pyrolysis oil and that comprises predominantly pyrolysis char and pyrolysis heavy waxes.

[0066] As used herein, the term “recycled content” refers to being or comprising a composition that is directly and/or indirectly derived from recycled material.

[0067] As used herein, the term “waste material” refers to used, scrap, and/or discarded material.

[0068] As used herein, the terms “waste plastic” and “plastic waste” refer to used, scrap, and/or discarded plastic materials.

ADDITIONAL CLAIM SUPPORTING DESCRIPTION - FIRST EMBODIMENT [0069] In a first embodiment of the present technology there is provided a chemical recycling process, the process comprising: (a) pyrolyzing waste plastic in a pyrolysis facility to thereby provide a recycled content pyrolysis effluent (r-pyrolysis effluent); (b) separating at least a portion of said r- pyrolysis effluent to provide a recycled content pyrolysis gas (r-pygas) and recycled content pyrolysis oil (r-pyoil); (c) introducing at least a portion of said r-pygas into a cracker facility; and (d) introducing at least a portion of said r- pyoil into a downstream location, wherein the downstream location is not within the cracker facility.

[0070] The first embodiment described in the preceding paragraph can also include one or more of the additional aspects/features listed in the following bullet pointed paragraphs. Each of the below additional features of the first embodiment can be standalone features or can be combined with one or more of the other additional features to the extent consistent. Additionally, the following bullet pointed paragraphs can be viewed as dependent claim features having levels of dependency indicated by the degree of indention in the bulleted list (i.e., a feature indented further than the feature(s) listed above it is considered dependent on the feature(s) listed above it).

• wherein the pyrolysis facility and the cracker facility are co-located.

• wherein at least 50, 75, 90, or 95 percent of the r-pygas formed in the pyrolysis facility is introduced into the cracker facility.

• wherein the r-pygas is introduced into the cracker facility at a location downstream of a cracker furnace. o wherein the r-pygas is introduced into a quench section of the cracker facility. o wherein the r-pygas is introduced into a compression section of the cracker facility.

^■ wherein the r-pygas is introduced upstream of the first compression stage.

^■ wherein the r-pygas is introduced upstream of the last compression stage. o wherein the r-pygas is introduced into a separation section of the cracker facility.

^■ wherein the r-pygas is introduced upstream of the first column of the separation section.

• wherein at least a portion of the r-pygas is introduced into the cracker facility upstream of a cracker furnace and further comprising, cracking at least a portion of the r-pygas to form a recycled content furnace effluent (r-furnace effluent). o further comprising combining another portion of the r-pygas with the r-furnace effluent and introducing the combined stream into at least one of a quench section, a compression section, and a separation section of the cracker facility.

• further comprising, dividing the r-pyoil into two or more portions and introducing a first portion of the r-pyoil into the downstream location. o wherein the second portion of the r-pyoil is introduced into the inlet of the cracker furnace. o wherein the first portion of the r-pyoil is at least 5, 20, 45 and/or not more than 90, 75, 50 percent of the total r-pyoil removed from the pyrolysis facility.

• wherein the r-pyoil comprises at least 50, 75, 90, 95 weight percent of C4 to C30 (C5 to C25, C5 to C22, or C5 to C20) hydrocarbon compounds.

• wherein the r-pyoil has a 90% boiling point in the range of from 150 to 350°C, 200 to 295°C, 225 to 290°C, or 230 to 275°C.

• wherein the r-pyoil comprises heteroatom-containing compounds in an amount of not more than 20, 10, 2, 0.5, or 0.1 weight percent.

• wherein the r-pygas comprises C2 hydrocarbon components in an amount of 5 to 60, 10 to 50, or 15 to 45 weight percent, C3 hydrocarbon components in an amount of 5 to 60, 10 to 50, or 15 to 45 weight percent, C4 hydrocarbon components in an amount of 1 to 60, 5 to 50, or 10 to 45 weight percent, and C5 hydrocarbon components in an amount of 1 to 25, 3 to 20, or 5 to 15 percent.

• wherein the downstream location is a carbon reformer. o wherein the carbon reformer is a partial oxidation gasifier o wherein the carbon reformer is a steam reformer o wherein the carbon reformer is plasma gasifier o wherein the carbon reformer is a catalytic reformer.

• wherein the downstream location is an oil refinery and further comprising processing at least a portion of the r-pyoil to thereby produce a recycled content fuel (r-fuel). o wherein the r-fuel is a gasoline range fuel o wherein the r-fuel is a diesel range fuel o wherein the r-fuel is a gas oil range fuel o wherein the r-fuel is a residual oil range fuel o wherein the r-fuel is asphalt or coke. o further comprising cracking at least a portion of the r-pyoil in the refinery to thereby provide the r-fuel. ^■ wherein the cracking comprises catalytic cracking.

^■ wherein the cracking comprises thermal cracking.

• wherein the cracking comprises coking. o further comprising reforming at least a portion of the r-pyoil to thereby provide the r-fuel.

^■ wherein the reforming comprises catalytic reforming. o further comprising isomerizing at least a portion of the r-pyoil to thereby provide the r-fuel. o further comprising fractionating at least a portion of the r-pyoil to form the r-fuel.

• wherein the downstream location is a burner of a furnace.

• wherein the downstream location is a storage or transportation apparatus.

• wherein the downstream location is another cracker facility. o further comprising introducing at least a portion of the r-pyoil into a cracker furnace of another cracker facility.

• wherein the downstream location is a fine chemicals production facility. o further comprising processing at least a portion of said r-pyoil in one or more processing sections of the fine chemicals facility to thereby produce a recycled content chemical (r-chemical).

• further comprising cracking a hydrocarbon feedstock in a cracker furnace of the cracker facility to produce a furnace effluent stream, and wherein the furnace effluent stream comprises a recycled content furnace effluent stream (r-furnace effluent). o further comprising combining at least a portion of the r-pygas with the furnace effluent stream to provide the r-furnace effluent. o further comprising introducing at least a portion of the r-pygas into the inlet of the cracker furnace to provide the r-furnace effluent. o wherein the hydrocarbon feedstock is a predominantly C2 to C4 hydrocarbon stream. o wherein the hydrocarbon feedstock is a predominantly C5 to C22 stream. o wherein the hydrocarbon feedstock comprises recycled content. o wherein the hydrocarbon feedstock comprises non-recycled content.

• further comprising forming at least one recycled content product (r- product) from at least a portion of said r-pyoil.

• further comprising forming at least one recycled content product (r- product) from the r-pygas from the cracker facility. o wherein the r-product comprises a recycled content ethane (r- ethane). o wherein the r-product comprises a recycled content ethylene (r- ethylene). o wherein the r-product comprises a recycled content propane (r- propane). o wherein the r-product comprises a recycled content propylene (r- propylene). o wherein the r-product comprises a recycled content butylene (r- butylene). o wherein the r-product comprises a recycled content butane (r- butane). o wherein the r-product comprises a recycled content C5 and heavier (r-C5+).

ADDITIONAL CLAIM SUPPORTING DESCRIPTION - SECOND EMBODIMENT

[0071] In a second embodiment of the present technology there is provided a chemical recycling process, the process comprising: (a) pyrolyzing waste plastic to thereby provide a recycled content pyrolysis effluent (r- pyrolysis effluent); (b) separating at least a portion of said r-pyrolysis effluent to provide a recycled content pyrolysis gas (r-pygas) and recycled content pyrolysis oil (r-pyoil); (c) introducing at least a portion of said r-pygas into a cracker facility; and (d) introducing at least a portion of said r-pyoil into one or more of the following locations (i) through (x): (i) a storage apparatus; (ii) a transportation apparatus; (iii) a fluidized catalytic cracker; (iv) a carbon reformer; (v) a distillation column or zone; (vi) a fine chemical facility; (vii) a burner; (vii) an MTO facility; (ix) a different cracker; and (x) an oil refinery. [0072] The second embodiment described in the preceding paragraph can also include one or more of the additional aspects/features listed in the following bullet pointed paragraphs. Each of the below additional features of the first embodiment can be standalone features or can be combined with one or more of the other additional features to the extent consistent. Additionally, the following bullet pointed paragraphs can be viewed as dependent claim features having levels of dependency indicated by the degree of indention in the bulleted list (i.e., a feature indented further than the feature(s) listed above it is considered dependent on the feature(s) listed above it).

• wherein the pyrolysis facility and the cracker facility are co-located.

^■ wherein the r-pygas is introduced upstream of the first compression stage.

^■ wherein the r-pygas is introduced upstream of the last compression stage. o wherein the r-pygas is introduced into a separation section of the cracker facility. ^■ wherein the r-pygas is introduced upstream of the first column of the separation section.

• wherein the downstream location is an oil refinery and further comprising processing at least a portion of the r-pyoil to thereby produce a recycled content fuel (r-fuel). o wherein the r-fuel is a gasoline range fuel o wherein the r-fuel is a diesel range fuel o wherein the r-fuel is a gas oil range fuel o wherein the r-fuel is a residual oil range fuel o wherein the r-fuel is asphalt or coke. o further comprising cracking at least a portion of the r-pyoil in the refinery to thereby provide the r-fuel.

^■ wherein the cracking comprises catalytic cracking.

^■ wherein the cracking comprises thermal cracking.

• wherein the cracking comprises coking o further comprising reforming at least a portion of the r-pyoil to thereby provide the r-fuel.

• wherein the downstream location is a burner of a furnace.

• wherein the downstream location is a storage or transportation apparatus.

CLAIMS NOT LIMITED TO DISCLOSED EMBODIMENTS [0073] The preferred forms of the invention described above are to be used as illustration only and should not be used in a limiting sense to interpret the scope of the present invention. Modifications to the exemplary embodiments, set forth above, could be readily made by those skilled in the art without departing from the spirit of the present invention.

[0074] The inventors hereby state their intent to rely on the Doctrine of Equivalents to determine and assess the reasonably fair scope of the present invention as it pertains to any apparatus not materially departing from but outside the literal scope of the invention as set forth in the following claims.

Claims

CLAIMS What is claimed is -

1 . A chemical recycling process, the process comprising:

(a) pyrolyzing waste plastic in a pyrolysis facility to thereby provide a recycled content pyrolysis effluent (r-pyrolysis effluent);

(b) separating at least a portion of said r-pyrolysis effluent to provide a recycled content pyrolysis gas (r-pygas) and recycled content pyrolysis oil (r- pyoii);

(c) introducing at least a portion of said r-pygas into a cracker facility; and

(d) introducing at least a portion of said r-pyoil into a downstream location, wherein the downstream location is not within the cracker facility.

2. The process of claim 1 , wherein the pyrolysis facility and the cracker facility are co-located.

3. The process of claim 1 , wherein the r-pygas is introduced into the cracker facility at a location downstream of a cracker furnace.

4. The process of claim 3, wherein the r-pygas is introduced into at least one of a quench section, a compression section, and a separation section of the cracker facility.

5. The process of claim 1 , wherein at least a portion of the r-pygas is introduced into the cracker facility upstream of a cracker furnace and further comprising, cracking at least a portion of the r-pygas to form a recycled content furnace effluent (r-furnace effluent).

6. The process of claim 1 , further comprising, dividing the r-pyoil into two or more portions and introducing a first portion of the r-pyoil into the downstream location.

7. The process of claim 1 , wherein the r-pyoil comprises at least 50 weight percent of C4 to C30 hydrocarbon compounds.

8. The process of claim 1 , wherein the r-pyoil comprises heteroatom- containing compounds in an amount of not more than 20 weight percent.

9. The process of claim 1 , wherein the r-pygas comprises C2 hydrocarbon components in an amount of 5 to 60 weight percent, C3 hydrocarbon components in an amount of 5 to 60 weight percent, C4 hydrocarbon components in an amount of 1 to 60 weight percent, and C5 hydrocarbon components in an amount of 1 to 25 weight percent.

10. The process of claim 1 , wherein the downstream location is a carbon reformer.

11. The process of claim 1 , wherein the downstream location is an oil refinery and further comprising processing at least a portion of the r-pyoil to thereby produce a recycled content fuel (r-fuel).

12. The process of claim 1 , wherein the downstream location is a burner of a furnace.

13. The process of claim 1 , wherein the downstream location is another cracker facility.

14. The process of claim 1 , wherein the downstream location is a fine chemicals production facility.

15. The process of claim 1 , further comprising cracking a hydrocarbon feedstock in a cracker furnace of the cracker facility to produce a furnace effluent stream, and wherein the furnace effluent stream comprises a recycled content furnace effluent stream (r-furnace effluent).

16. The process of any of claims 1 to 15, wherein the pyrolysis facility and the cracker facility are both commercial scale facilities.

17. A chemical recycling process, the process comprising:

(a) pyrolyzing waste plastic to thereby provide a recycled content pyrolysis effluent (r-pyrolysis effluent);

(c) introducing at least a portion of said r-pygas into a cracker facility; and

(d) introducing at least a portion of said r-pyoil into one or more of the following locations (i) through (x) -

(i) a storage apparatus;

(ii) a transportation apparatus;

(iii) a fluidized catalytic cracker;

(iv) a carbon reformer;

(v) a distillation column or zone;

(vi) a fine chemical facility;

(vii) a burner;

(viii) an MTO facility;

(ix) a different cracker; and

(x) an oil refinery.

18. The process of claim 17, wherein the r-pyoil comprises heteroatom- containing compounds in an amount of not more than 20 weight percent, and wherein the r-pygas comprises C2 hydrocarbon components in an amount of 5 to 60 weight percent, C3 hydrocarbon components in an amount of 5 to 60 weight percent, C4 hydrocarbon components in an amount of 1 to 60 weight percent, and C5 hydrocarbon components in an amount of 1 to 25 percent.

19. The process of claim 17, wherein the introducing of step (c) includes introducing at least a portion of said r-pyoil into two or more of the locations (i) through (x).

20. The process of any of claims 17 to 19, wherein the pyrolysis facility and the cracker facility are co-located and both the pyrolysis facility and the cracker facility are commercial scale.