Coking method and coke composition containing trace metals

Abstract

A method of sequestering contaminant compounds from polymeric waste may include thermally cracking at least, a feedstock comprising a polymeric waste and a coker feedstock to produce at least coke and a coking effluent comprising hydrocarbons, wherein the polymeric waste comprises chlorine and / or chloride compounds, wherein at least a portion of the chlorine and / or chloride compounds are segregated into the coke, and wherein the coke comprises 0.01 wt.% to 1 wt.% of the chlorine and / or chloride compounds; and separating at least a portion of the coking effluent to form a coker naphtha.

Description

COKING METHOD AND COKE COMPOSITION CONTAINING TRACE METALSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 492775 filed March 28, 2023, the disclosure of which is incorporated herein by reference.FIELD

[0002] Systems and methods are provided for contaminant management in chemical recycling of plastic waste.BACKGROUND

[0003] Chemical recycling processes, such as pyrolysis, are used to break down plastic waste to form recycled hydrocarbons. Plastic waste often contains additives such as fillers, colorants, UV inhibitors, talc, CaCOs. metals such as Al and Mg, metal salts such as TiCU, CaCU, NaCl, and metal oxides such as TiO2 and SiO2, as well as metal fatty acid salts such as calcium stearate, magnesium stearate, and zinc stearate, for example. The recycled hydrocarbons are oftentimes contaminated with one or more of the additives which can negatively affect downstream processes through catalyst deactivation, corrosion, and accumulation within units, for example. Chloride containing compounds are often produced from chemical recycling of polymeric w aste which may be particularly difficult to treat in the recycled hydrocarbons. Although dedicated processing systems could be used for treating recycled hydrocarbons produced from polymeric waste recycling, such dedicated systems require substantial initial capital costs and a constant supply of waste feedstock.SUMMARY

[0004] Disclosed herein is an example method of sequestering contaminant compounds from polymeric waste which may include: thermally cracking at least, a feedstock comprising a polymeric waste and a coker feedstock to produce at least coke and a coking effluent comprising hydrocarbons, wherein the polymeric waste comprises chlorine and / or chloride compounds, wherein at least a portion of the chlorine and / or chloride compounds are segregated into the coke, and wherein the coke comprises 0.01 wl.% to 1 wt.% of the chlorine and / or chloride compounds; and separating at least a portion of the coking effluent to form a coker naphtha.

[0005] Further disclosed herein is a method of sequestering contaminant compounds from polymeric waste which may include: thermally cracking at least, a feedstock comprising a polymeric waste and a coker feedstock to produce at least coke and a coking effluentcomprising hydrocarbons, wherein the polymeric waste comprises a metal comprising at least titanium, wherein at least a portion of the metal is segregated into the coke, and wherein the coke comprises 0.01 wt.% to 2 wt.% of the metal; and separating at least a portion of the coking effluent to form a coker naphtha.

[0006] Further disclosed herein is an example petroleum coke composition comprising: at least 95 wt.% carbon; chlorine and / or chloride compounds in an amount of about 0.01 wt.% to about 1 wt.%.; titanium in an amount of about 0.01 wt.% to about 1 wt.%; aluminum in an amount of about 0.01 wt.% to about 1 wt.%; and vanadium in an amount of about 0.01 wt.% to about 1 wt .%.

[0007] These and other features and attributes of the disclosed methods and systems of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description which follows.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings, wherein:

[0009] FIG. 1 is an illustrate depiction of a process for pyrolysis of polymeric waste followed by coking.

[0010] FIG. 2 is an illustrative depiction of a fluidized bed coking system including a coker, a heater, and a gasifier in accordance with certain embodiments of the present disclosure.

[0011] FIG. 3 is an illustrative depiction of a fluidized bed coking system including a coker and a gasifier in accordance with certain embodiments of the present disclosure.

[0012] FIG. 4 is an illustrative depiction of a delayed coking system including a coker and a fractionator in accordance with certain embodiments of the present disclosure.

[0013] FIG. 5 is an x-ray image of a cross section of a coke ball produced by coking a polymeric waste with vacuum resid in accordance with certain embodiments of the present disclosure.

[0014] FIG. 6 is extracted spectra data from X-ray dispersive spectroscopy of a coke ball in accordance with certain embodiments of the present disclosure.

[0015] FIG. 7 is a graph of a themiogravimetric analysis profile of hydrolysis of iron (III) chloride in accordance with certain embodiments of the present disclosure.

[0016] FIG. 8 is a graph of a Fourier-transform infrared spectroscopy of hydrolysis of iron (III) chloride in accordance with certain embodiments of the present disclosure.DETAILED DESCRIPTION

[0017] In various embodiments, systems and methods are provided for chemical recycling of polymeric waste, such as plastic waste. Once challenge with chemical recycling of polymeric waste is that the resulting recycled products oftentimes contain contaminants which are incompatible with downstream processes. The contaminants may be difficult to treat when they are present in the recycled products thereby making the recycled products less valuable. In some embodiments, the polymeric waste contains chloride and / or chlorine containing compounds which can foul units and poison catalysts.

[0018] In some embodiments, the polymeric waste is chemically recycled by co-processing the polymeric waste with a co-feed in a coker to produce coking products. Coking products may include hydrocarbon gaseous and liquid products such as coker naphtha, as well as petroleum coke. Additionally, the coking process at least partially segregates and concentrates contaminants which may be present in the polymeric waste, thereby reducing the contaminants in the coker hydrocarbon products. Some illustrative contaminants may include, without limitation, chlorides and / or chloride containing compounds as well as metals such as titanium, aluminum, silicon, calcium, magnesium, and zinc for example. In embodiments, the concentration of contaminants, such as chloride and / or chlorine containing compounds in the coker hydrocarbon products, may be monitored and the feed to the coker may be adjusted to reduce the concentration of the contaminants in the coker hydrocarbon products.

[0019] The coker hydrocarbon products may be used to produce circular chemical products. Circular chemical products are chemical products derived from polymeric waste wherein the molecules of the chemical product can be attributed to the polymers in the polymeric waste, such as by crediting, allocating offsetting for other hydrocarbons, and / or substituting for other hydrocarbons in a mass or energy balance for a system. Circular chemical products include circular monomers, circular aromatics, and circular polymers, among others. Polymers that are certified for their circularity by third party certification may be referred to as certified circular. One example of such a certification is the mass balance chain of custody method set forth by the International Sustainability' and Carbon Certification.Coker Feed

[0020] In accordance with present embodiments, coking can be used to process a waste feedstock to produce coking products. In some embodiments, the waste feedstock is coprocessed with a conventional coking feedstock.

[0021] The waste feedstock for coking can include or consist essentially of one or more types of polymers, such as polymers corresponding to plastic waste which contain chlorineand / or chloride containing compounds. The systems and methods described herein can be suitable for processing polymeric waste corresponding to a single type of polymer and / or polymeric waste corresponding to a plurality of polymers. In aspects where the waste feedstock consists essentially of polymers, the feedstock can include one or more types of polymers as well as any additives, modifiers, packaging dyes, and / or other components typically added to a polymer during and / or after formulation. The waste feedstock can further include components (e.g., paper) typically found in polymeric waste.

[0022] In some embodiments, the waste feedstock includes polymeric waste obtained from any source including, but not limited to, municipal, industrial, commercial or consumer sources. In some embodiments, the waste feedstock includes post-consumer use plastics. The polymeric waste further may include plastics obtained from a common source or from mixed sources, including mixed plastic waste obtained from municipal or regional sources and / or from waste streams of PET, HDPE, LDPE, LLDPE, polypropylene, and / or polystyrene. Furthermore, the waste feedstock may include thermoplastic elastomers and thermoset rubbers, such as from tires and other articles made from natural rubber, polybutadiene, styrenebutadiene. butyl rubber and EPDM.

[0023] Even further, examples of suitable waste feedstocks may include any of various used polymeric articles without limitation. Some examples of the many types of polymeric articles may include: films (including cast, blown, and otherwise), sheets, fibers, woven and nonwoven fabrics, furniture (e.g., garden furniture), sporting equipment, bottles, food and / or liquid storage containers, transparent and semi-transparent articles, toys, tubing and pipes, sheets, packaging, bags, sacks, coatings, caps, closures, crates, pallets, cups, non-food containers, pails, insulation, and / or medical devices. Further examples include industrial waste streams, such as linear alpha olefins and polypropylene heavy streams (e.g., >50 wt.%). Further examples include automotive, aviation, boat and / or watercraft components (e.g., bumpers, grills, trim parts, dashboards, instrument panels and the like), wire and cable jacketing, agricultural films, geomembranes, playground equipment, and other such articles, whether blow molded, roto-molded, injection-molded, or the like. Any of the foregoing may include mixtures of polymeric and non-polymeric items (e.g., packaging or other articles may include inks, paperboards, papers, metal deposition layers, and the like). The ordinarily skilled artisan will appreciate that such polymeric articles may be made from any of various polymer and / or non-polymer materials, and that the polymer materials may vary widely (e.g., ethylenebased, propylene-based, butyl-based polymers, and / or polymers based on any C2 to C40 or even higher olefins, and further including polymers based on any one or more types of monomers,e.g., C2 to C40 a-olefin, di-olefin, cyclic olefin, etc. monomers). Common examples include ethylene, propylene, butylene, pentene, hexene, heptene, octene, and styrene; as well as multiolefinic (including cyclic olefin) monomers such as ethylidene norbomene (ENB) and vinylidene norbomene (VNB) (including, e.g., when such cyclic olefins are used as comonomers, e.g., with ethylene monomers).

[0024] In various embodiments, the waste feedstock can include one or more nitrogencontaining polymers. Examples of nitrogen-containing polymers include polyamides (such as Nylon 6), polyurethanes, and polynitriles. The nitrogen-containing polymers can correspond to 0.1 wt.% to 25 wt.% of the waste feedstock (relative to the weight of the waste feedstock), or 1.0 wt.% to 25 wt.%, or 5.0 wt.% to 25 wt.%, or 10 wt.% to 25 wt.%, or 1.0 wt.% to 15 wt.%, or 5.0 wt.% to 15 wt.%, or 1.0 wt.% to 10 wt.%. For example, nitrogen-containing polymers may be in the waste feedstock in an amount of 25 wt.% or less. 10 wt.% or less, 5 wt.% or less, 1 wt.% or less, or 0. 1 wt.% or less.

[0025] In some embodiments, the waste feedstock can include one or more chlorine- containing polymers. Examples of chlorine-containing polymers including PVC (polyvinyl chloride) and PVDC (poly vinylidene chloride). In some aspects, the chlorine-containing polymers can correspond to as 0.001 wt.% to 15 wt.% of the waste feedstock (relative to the weight of the waste feedstock), or 0. 1 wt.% to 15 wt.%, or 1.0 wt.% to 15 wt.%, or 0.001 wt.% to 10 wt.%, or 0.1 wt.% to 10 wt.%, or 1.0 wt.% to 10 wt.%, or 0.001 wt.% to 5.0 wt.%, or 0.001 wt.% to 1.0 wt.%. For example, the chlorine-containing polymers may be in the waste feedstock in an amount of 15 wt.% or less. 10 wt.% or less, 5 wt.% or less, 1 wt.% or less, or 0.1 wt.% or less.

[0026] In some embodiments, the waste feedstock can include at least one of polyethylene and polypropylene. The polyethylene can correspond to any convenient type of polyethylene, such as high density or low-density versions of polyethylene. Similarly, any convenient type of polypropylene can be used. Additionally, or alternately, the waste feedstock can include one or more of polystyrene, polyamide (e.g., nylon), polyethylene terephthalate, and ethylene vinyl acetate. Still other polyolefins can correspond to polymers (including co-polymers) of butadiene, isoprene, and isobutylene. In some embodiments, the polyethylene and polypropylene can be present in the mixture as a co-polymer of ethylene and propylene. More generally, the polyolefins can include co-polymers of various olefins, such as ethylene, propylene, butenes, hexenes, and / or any other olefins suitable for polymerization.

[0027] In this discussion, unless otherwise specified, weights of polymers in a feedstock correspond to weights relative to the total polymer content in the feedstock. Any additivesand / or modifiers and / or other components included in a formulated polymer are included in this weight. However, the weight percentages described herein exclude any solvents or carriers that might optionally be used to facilitate transport of the polymer into the coker.

[0028] In some embodiments, the waste feedstock includes 0.01 wt.% to 35 wt.% of polystyrene, or 0.1 wt.% to 35 wt.%, or 1 wt.% to 35 wt.%, or 0.01 wt.% to 20 wt.%, or 0.1 wt.% to 20 wt.%, or 1 wt.% to 20 wt.%, or 10 wt.% to 35 wt.%, or 5 w7t.% to 20 wt.%, or 0.01 wt.% to 10 wt.%, or 0.01 wt.% to 1 wt.%. In some embodiments, the waste feedstock can also include oxygen-containing polymers, such as polyterephthalates. It is noted that polyamides also contain oxygen as part of the polymer structure. In this discussion, a polymer that includes both oxygen and nitrogen as part of the repeat unit for forming the polymer is defined as a nitrogen-containing polymer for purposes of characterizing the waste feedstock.

[0029] In addition to polymers, a waste feedstock can include a variety of other components. Such other components can include additives, modifiers, packaging dyes, and / or other components typically added to a polymer during and / or after formulation. The waste feedstock can further include any components ty pically found in polymeric waste. Finally, the feedstock can further include a carrier fluid so that the waste feedstock to the cracking process corresponds to a solution or slurry of the polymeric waste.

[0030] As discussed above, polymeric waste oftentimes contains impurities which are used during the production of the polymer to impart desirable properties to the polymer. Such impurities may include, but are not limited to, nitrogen containing compounds, sulfur containing compounds, and heavy metals, such as aluminum, boron, calcium, chromium cobalt, iron, manganese, magnesium, molybdenum, nickel, potassium, phosphorous, silicon, sodium, titanium, vanadium, and combinations thereof. The polymeric waste may contain metal salts and oxides such as TiCh. talc, CaCOs, SiCh, TiCh, CaCh, and NaCl, for example. In embodiments, the polymeric waste can contain any of the above impurities in an amount of 0.001 wt.% to 15 wt.% by weight of the polymeric waste. Alternatively, the impurities may be present in an amount of 0.001 wt.% to 0.005 wt.%, in an amount of 0.005 wt.% to 0.01 wt.%, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1.0 wt.%, in an amount of 1.0 wt.% to 5.0 wt.%, in an amount of 5.0 wt.% to 10.0 wt.%, in an amount of 10.0 wt.% to 15.0 wt.%, or any ranges therebetween.

[0031] In some aspects, the chlorine-containing polymers can correspond to as 0.001 wt.% to 15 wt.% of the waste feedstock (relative to the weight of the waste feedstock), or 0.1 wt.% to 15 wt.%, or 1.0 wt.% to 15 wt.%, or 0.001 wt.% to 10 wt.%, or 0.1 wt.% to 10 wt.%, or 1.0 wt.% to 10 wt.%, or 0.001 wt.% to 5.0 wt.%, or 0.001 wt.% to 1.0 wt.%. For example, thechlorine-containing polymers may be in the waste feedstock in an amount of 15 wt.% or less, 10 wt.% or less, 5 wt.% or less, 1 wt.% or less, or 0. 1 wt.% or less.

[0032] In embodiments where the waste feedstock is introduced into the coking environment at least partially as solids, having a small particle size can facilitate transport of the solids and / or reduce the likelihood of incomplete conversion. In some embodiments, the waste feedstock includes polymeric w aste having a median particle size to 0.01 mm to 50 mm, 0.01 to 25 mm, 0.01 to 10 mm. 1 mm to 50 mm. 1 mm to 25 mm, 1 mm to 10 mm, 5 mm, or 0. 1 mm to 5 mm, or 0.01 mm to 3 mm, or 0. 1 mm to 3 mm. or 0.01 mm to 3 mm, or 0. 1 mm to 3 mm, or 1 mm to 5 mm, or 1 mm to 3 mm. For determining a median particle size, the particle size is defined as the diameter of the smallest bounding sphere that contains the particle. Additionally, or alternately, the polymeric waste in the waste feedstock can be melted and / or pelletized to improve the uniformity of the particle size of the plastic particles. In some embodiments, the polymeric waste has a maximum particles size of 10 mm or less, or 5 mm or less. Additionally, or alternately, the polymeric waste can be provided in waste bale. In some embodiments, the w aste bale is a composite bale.

[0033] It is noted that some types of polymeric waste can also include bio-derived components. For example, some types of plastic labels can include biogenic waste in the form of paper compounds. In some embodiments, 1 wt.% to 25 wt.% of the waste feedstock can correspond to bio-derived material. Such bio-derived material can also potentially contribute to the nitrogen and / or oxygen content of a waste feedstock.

[0034] Optionally, a carrier fluid can also be included in the waste feedstock to assist with introducing the polymeric waste into the cracking environment. For introduction into a cracking environment, it can be convenient for the feedstock to be in the form of a slurry. If a carrier fluid is used for transporting the waste feedstock, any suitable fluid can be used. Examples of suitable carrier fluids can include (but are not limited to) a wide range of petroleum or petrochemical products. For example, some suitable carrier fluids include crude oil, naphtha, kerosene, diesel, light or heavy cycle oils, catalytic slurry oil, and gas-oils. Other potential carrier fluids can correspond to naphthenic and / or aromatics solvents, such as toluene, benzene, methylnaphthalene, cyclohexane, methylcyclohexane, and mineral oil. Still other carrier fluids can correspond to refinery fractions, such as a gas oil fraction or naphtha fraction from a coker. In another example, a distillate and / or gas oil boiling range fraction can be used that generated by cracking of the w aste feedstock, either alone or with an additional feedstock.

[0035] In various embodiments, coking is used to co-process a combined feedstock corresponding to a mixture of a conventional coking feedstock and a waste feedstock. In someembodiments, the conventional coking feedstock is used as the carrier fluid for the waste feedstock. The conventional coking feedstock can correspond to one or more types of petroleum and / or renewable feeds with a suitable boiling range for cracking, such as processing in a coker. The amount of waste feedstock in the combined feedstock can correspond to 1 wt.% to 50 wt.%, 3 wt.% to 50 wt.%, 10 wt.% to 50 wt.%, 25 wt.% to 50 wt.%, 1 wt.% to 25 wt.%, 1 wt.% to 10 wt.%, 1 wt.% to 5%, 1 wt.% to 3 wt.%, 3 wt.% to 25 wt.%, 10 wt.% to 25 wt.%, 3 wt.% to 15 wt.% by weight of the combined feedstock, or any ranges therebetween. The conventional coking feedstock can correspond to 50% to 99% by weight of the combined feedstock to the coker.

[0036] In some embodiments, the coking feedstock for co-processing with the waste feedstock can correspond to a conventional petroleum feedstock having a relatively high boiling fraction, such as a heavy oil feed. For example, the coking feedstock portion of the feed can have a T10 distillation point of 343°C or more, or 371 °C or more. In some embodiments, the coking feedstock has a T10 distillation point of 343°C to 650°C. Examples of suitable heavy oils for inclusion in the coking feedstock include reduced petroleum crude; petroleum atmospheric distillation bottoms; petroleum vacuum distillation bottoms, or residuum; pitch; asphalt; bitumen; other heavy hydrocarbon residues; tar sand oik shale oik or even a coal slurry or coal liquefaction product such as coal liquefaction bottoms. Such feeds will typically have a Conradson Carbon Residue (ASTM D189-165) of at least 5 wt.%, generally from 5 wt.% to 50 wt.%. In some embodiments, the coking feedstock comprises a petroleum vacuum residuum.

[0037] Some examples of conventional petroleum feedstock suitable for processing in a delayed coker or fluidized bed coker can have a composition and properties within the ranges set forth below7in Table 1.Table 1

[0038] In addition to petroleum feedstocks, renewable feedstocks derived from biomass having a suitable boiling range can also be used as part of the cracking feed. Such renewable feedstocks include feedstocks with a T10 boiling point of 340°C or more and a T90 boiling point of 600°C or less. An example of a suitable renewable feedstock derived from biomass can be a cracking oil feedstock derived at least in part from biomass.

[0039] In some particular embodiments, the waste feedstock and the conventional coking feedstock (e.g., coker feedstock) are mixed to form a combined feedstock prior to entering the coking environment. In other embodiments, the waste feedstock and the conventional coking feedstock are separately introduced into the coking environment. More generally, however, any convenient method for introducing both the waste feedstock and the coking feedstock into the coking environment can be used.

[0040] Prior to being introduced into the coking environment, the feedstocks (optionally in the form of a combined feedstock) are pre-heated in accordance with one or more embodiments. Pre-heating the feedstocks in one or more heating stages can increase the temperature of the feedstocks to a mixing and storage temperature, to a temperature related to the cracking temperature, or to another convenient temperature.

[0041] In some embodiments, a portion of the pre-heating of a waste feedstock can be performed by mixing the waste feedstock with a coking feedstock in a mixing tank and heating the mixture in the mixing tank. For example, a waste feedstock and a coking feedstock can be mixed in a heated stirred tank for storage operating at 200°C to 325°C, or 275°C to 325°C. In some embodiments, tank agitation aids in uniform dispersal of the waste feedstock into resid and maintains slurry suspension. Heating in a mixing tank provides heat to the combined feedstock prior to introducing the combined feedstock into the cracking reaction environment. This can reduce or minimize additional cracking heat duty that would otherwise be required to heat the waste feedstock to thermal cracking temperatures. The mixed feedstock may be further heated and / or physically processed for particle size reduction prior to injection into the cracking reactor. The combined feedstock may be sized to provide particles with a maximum particle size, for example, of 5 mm or less, 2 mm or less, or 1 mm or less. In some embodiments, the particles are sized wi th milling equipment, such as a roller mill. In addition to heating, stripping of the combined waste feedstock and coking feedstock using a stripping gas can be performed in a mixing tank. Passing a stripping gas through the combined feedstock can assist with removing gases that are entrained in the combined feedstock.

[0042] In some embodiments, the waste feedstock is melted, for example, in an extruder. After extruding, the waste feedstock comprising melted polymeric waste can either be directly mixed with a conventional coking feedstock and / or a solvent, or the extruded plastic can be pelletized to form a desired particle size for the waste feedstock.

[0043] Still another option can be to mix the waste feedstock with the coking feedstock after the pre-heater furnace for the coker, in accordance with certain embodiments. In these embodiments, the coking feedstock can be heated to a higher temperature in the pre-heater, and then the waste feedstock can be added to the pre-heated coking feedstock to heat the waste feedstock.Pyrolysis

[0044] In accordance with one or more embodiments, the waste feedstock is pyrolyzed to generate a pyrolysis oil that is then fed to the coking environment. In some embodiments, the waste feedstock is pyrolyzed with one or more additional feedstocks, such as rubber-containing feedstocks. In some embodiments, the pyrolysis oil at least partially derived from polymeric waste is co-processed in the coking environment with a conventional coking feedstock.

[0045] Pyrolysis is a technique of chemical recycling that includes thermal degradation of the pyrolysis feedstock to produce gas and liquid products, referred to as pyrolysis oil and a pyrolysis gas. Waste plastic pyrolysis units are distinct from coker units that have been specially designed to handle heavier feeds. The pyrolysis products may depend on a number of factors, including, but not limited to, pyrolysis reactor temperature, pyrolysis reactor pressure, reactor residence time, feed type, feed quality, and process configuration.

[0046] A specific pyrolysis technique will now be described in more detail. In an example embodiment, a pyrolysis feedstock (e.g., a waste feedstock) may be provided, for example, in a granular, flake, or pellet form, and fed to a pyrolysis unit. In the pyrolysis unit, the waste feedstock may be melted to produce a molten liquid (e.g., molten plastic). For example, the polymeric waste may be melted in an extruder to a temperature of 300°C to 320°C. For example, the molten liquid may be heated in pyrolysis chamber to a higher temperature, such as 390°C to 550°C, while agitating. Long chain hydrocarbons (e.g., approximately 30 carbon atoms or longer) in the produced pyrolysis gases may then be condensed and further pyrolyzed for further thermal degradation while shorter chain hydrocarbons may exit in gaseous form. For example, the produced pyrolysis gases may be directed to a contactor for contact with a bank of condenser elements (e.g., plates) upon which the long chain hydrocarbons may condense. The long chain hydrocarbons may flow' from the condenser back to the pyrolysischamber. The pyrolysis gases including the shorter chain hydrocarbons may be distilled in a distillation column to provide pyrolysis gas and pyrolysis oil.

[0047] FIG. 1 illustrates an example configuration for pyrolyzing a waste feedstock followed by coking. In FIG. 1, a waste feedstock 100 and one or more optional feedstocks 102 are fed into the pyrolysis unit 104. The waste feedstock 100 comprises polymeric waste, such as plastic waste, where the polymeric waste comprises chlorine and / or chloride containing compounds. In the pyrolysis unit 104, the waste feedstock 100 containing the polymeric waste may be pyrolyzed to form at least a pyrolysis gas 106 and a pyrolysis oil 108. The pyrolysis unit 104 can include a variety of different equipment suitable for pyrolysis of polymeric waste, including but not limited to, reactors, extruders, tanks, vessels, valves, sensors, hoppers, conveyance systems, and piping, among others.

[0048] The pyrolysis oil 108 that is at least partially derived from polymeric waste is then passed into coking stage 112. Coking stage 112 corresponds to any suitable coking for coking the pyrolysis oil, including a delayed coker, a fluidized coker, or a combination thereof As illustrated, a conventional coking feedstock 110 can also be fed into the coking stage 112 in accordance with one or more embodiments. In the coking stage 112, the combined feedstock of the pyrolysis oil 108 and the conventional coking feedstock 110 are processed to form at least a coking effluent. In the example shown in FIG. 1, the coking effluent can be separated to form a coker gas fraction 114, a coker naphtha fraction 116, and a coker gas oil fraction 118. A coke product 120 is also shown, but it should be understood that the coke product 120 is typically withdrawn from a coker separately from the coker effluent.Coking

[0049] In accordance with one or more embodiments, the waste feedstock is coked, either alone or with a conventional coking feedstock, to produce more valuable coking products (coking effluent). In various aspects, co-processing can be performed by exposing the combined feedstock of waste feedstock and conventional coking feedstock to coking conditions.

[0050] Coking is a refining process that includes thermal cracking of longer chain molecules into shorter chain molecules with excess carbon left behind in the form of coke. Coking processes in modem refinery settings can typically be categorized as delayed coking or fluidized bed coking. In both processes, the feedstock is cracked to produce gas and liquid products, leaving behind coke. In delayed coking, the feedstock is heated and fed to a coking reactor (commonly referred to as a “coke drum”) where the cracking takes place. To remove the coke, alternating drums can be used. In fluidized coking, the feedstock is head to the cokingreactor where cracking takes place wi th coke transferred from the coking reactor to a heater as a fluidized solid.

[0051] The coking products produced from coking include a cracking effluent, which may include a gas, a liquid, or a mixture thereof. The cracking effluent can be fractionated or otherwise separated to form desirable product streams, such as coker gas (e.g., C4 and lighter hydrocarbons), coker naphtha, and coker gas oil.

[0052] Coker gas is a coker effluent fraction that is formed in the coker with a T90 distillation point of 40°C or less. Coker gas is a mixture of many different hydrocarbons, including paraffins, olefins, and aromatics. Coker gas can comprise hydrocarbons ranging from 1 carbon atom to 5 carbon atoms. Coker gas can additionally comprise trace amounts of higher hydrocarbons (e.g., Ce), including benzene in gas. While coker gas is referred to a gas, it should be understood that the coker gas can be in liquid form, for example, depending on temperature and pressure, so long as the coker gas has a final boiling point of 100°C or less.

[0053] Coker gas oil is a coker effluent fraction that is formed in the coker with a T10 distillation point of 225°C or higher and a T90 distillation point of 650°C or less. Coker gas oil is a mixture of many different hydrocarbons, including paraffins, olefins, and aromatics. Coker gas oil can compnse hydrocarbons ranging from 8 carbon atoms to 70 carbon atoms.

[0054] Coker naphtha is a liquid coker effluent fraction that is formed in the coker with a T10 distillation point of 30°C or higher and a T90 distillation point of 220°C or less. Coker naphtha is a mixture of many different hydrocarbons, including paraffins, napthenes, olefins, and aromatics. Coker naphthas can comprise hydrocarbons ranging from 4 carbon atoms to 12 carbon atoms.

[0055] The hydrocarbon coking products, including coker gas, coker gas oil, and coker naphtha, which at least partially derived from polymeric waste can have desirable reductions in certain components as compared to from a conventional hydrocarbon feedstock, such as decreases in aromatic and sulfur content as well as a decrease in impunties related to processing the polymeric waste. For example, the aromatic content of hydrocarbon coking products derived from a conventional hydrocarbon feedstock can range from roughly 1 wt.% to 25 wt.% while hydrocarbon coking products that are at least partially derived from polymeric waste can have an aromatic content can of 10 wt.% to 20 wt.%. or 10 wt.% to 15 wt.%, or 15 wt.% to 20 wt.%. Hydrocarbon coking products also shows decreases in 2-3 ring aromatics. For example, the hydrocarbon coking products that are at least partially derived from polymeric waste can have a 2-3 ring aromatic content or 0 wt.% to 5 wt.% or 1 wt.% to 3 wt.%. By way of further example, the sulfur content of hydrocarbon coking products derived from aconventional hydrocarbon feedstock can range from 0.5 wt.% to 5 wt.% while hydrocarbon coking products that is at least partially derived from polymeric waste can have a lower sulfur content, for example, 0. 1 wt.% or less.

[0056] In addition to a desirable decrease in aromatics and sulfur, the hydrocarbon coking products that are at least partially derived from polymeric waste can have increased levels of other components that can complicate subsequent chemical processing. Such components include organic halides and basic nitrogen, for example. The specific type and amount of these components depends, for example, on the particular polymeric waste used in forming the coking products. For example, the hydrocarbon coking products at least partially derived from polymeric waste can have a total halide content, such as chlorine, fluorine, and bromine, in amounts, for example, ranging from 1 wppm to 0.5 wt.%, 10 wppm to 0.5 wt.%, or 10 wppm to 0.1 wt.%, while hydrocarbon coking products derived from a conventional hydrocarbon feedstock can include organic contaminants at levels below 1 wppm. By way of further example, the hydrocarbon coking products at least partially derived from polymeric waste can include basic nitrogen at levels of 100 wppm to 5,000 wppm while hydrocarbon coking products from conventional hydrocarbon feedstock can include basic nitrogen at levels from 10 wppm to 50 wppm.

[0057] As used herein, the basic nitrogen content of a feed, fraction, or product can be determined according to the following method by performing measurements on two samples of the feed, fraction, or product. First, the total nitrogen of a sample is characterized according to ASTM D4629. Next, a sample can be acid washed by adding 1 ml of 1 N sulfuric acid to a 10 ml sample. This mixture can be formed in a suitable vessel, such as a 20 ml vial. The mixture of the sample and the sulfur acid is shaken vigorously, and then allowed to settle for 5 minutes. After settling, the sulfuric acid should be at the bottom of the vessel. The acid washed sample is removed from the top of the vessel, such as by using a pipette to remove the acid washed sample while not including any of the sulfuric acid. The acid washed sample can then be characterized according to ASTM D4629. The difference in nitrogen content between the untreated sample and the acid washed sample corresponds to the nitrogen that is removed by acid treatment. In this discussion, the nitrogen removed by acid treatment is defined as the basic nitrogen content. Amides and amines present in a sample correspond to basic nitrogen, so the presence of excess amides and amines in a sample due to decomposition of nitrogencontaining polymers will result in a corresponding increase in the basic nitrogen content of a sample.

[0058] The coking products further include coke. Because many polymeric wastes have relatively low sulfur content (as compared to a conventional coking feedstock), the cracking products have reduced sulfur content, in some embodiments, thus reducing the needed severity’ for any subsequent sulfur removal processes, such as hydroprocessing. Coke produced in a coking process is typically a carbonaceous solid material of which a majority is carbon. In embodiments, the coke can contain from 90 wt.% carbon to 99.99 wt.% carbon. Alternatively, from 90 wt.% carbon to 95 wt.% carbon, from 95 wt.% to 99 wt.%, from 99 wt.% to 99.99 wt.%. or any ranges therebetween. Alternatively, the coke can contain at least 90 wt.% carbon, at least 95 wt.% carbon, at least 99 wt .% carbon, or at least 99.99 wt.% carbon.

[0059] Since the coke is produced from the co-processing of a conventional coking feedstock in the coker, it can also be referred to as petroleum coke or petcoke, in accordance with one or more embodiments. The coke yield typically is 20 wt.% to 40 wt.% of the combined coker feedstock. However, since polymeric wastes can have substantially higher atomic ratio of hydrogen to carbon, coking with a polymeric waste feedstock can produce a reduced or minimized amount of coke. The particular composition of the coke depends on a number of factors, including the particular coking process, such as a delayed coker or fluidized coker.

[0060] In embodiments, the coke can contain contaminants from the polymeric waste. The coking process segregates the contaminants from the polymeric waste into the coke thereby reducing the concentration of contaminants in the other coking products. In some embodiments, the coke may include aluminum in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0061] In some embodiments, the coke may include boron in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0062] In some embodiments, the coke may include calcium in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt .% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0063] In some embodiments, the coke may include chromium in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%. in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0064] In some embodiments, the coke may include cobalt in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0065] In some embodiments, the coke may include iron in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0066] In some embodiments, the coke may include manganese in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0. 1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0067] In some embodiments, the coke may include magnesium in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0. 1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0068] In some embodiments, the coke may include molybdenum in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0069] In some embodiments, the coke may include nickel in an amount of 0.01 wt.% to2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in anamount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0070] In some embodiments, the coke may include potassium in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0. 1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0071] In some embodiments, the coke may include phosphorus in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0072] In some embodiments, the coke may include silicon in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%. or any ranges therebetween.

[0073] In some embodiments, the coke may include sodium in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%. or any ranges therebetween.

[0074] In some embodiments, the coke may include titanium in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0075] In some embodiments, the coke may include vanadium in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%. in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0076] In some embodiments, the coke may include TiCh in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0077] In some embodiments, the coke may include talc (Mg3Si40io(OH)2) in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0078] In some embodiments, the coke may include CaCCh in an amount of 0.01 wt.% to2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%. or any ranges therebetween.

[0079] In some embodiments, the coke may include SiC>2 in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0080] In some embodiments, the coke may include TiCh in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0081] In some embodiments, the coke may include CaCh in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0082] In some embodiments, the coke may include NaCl in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%. in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0083] In some embodiments, the coke may include calcium stearate in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%. in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0084] In some embodiments, the coke may include magnesium stearate in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%. in an amount of 0.1 wt.% to 0.5 wt.%. in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt .% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0085] In some embodiments, the coke may include zinc stearate in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetween.

[0086] Coking polymeric waste containing contaminants mentioned herein may have several advantages over other polymeric recycling techniques such as catalytic recycling where contaminants may accumulate, and catalyst deactivation may occur. Catalytic recycling may require additional unit operations to expel the accumulated contaminants. Using polymeric waste as a co-feed in a coking operation may be advantageous as there is no catalyst deactivation, and the contaminant compounds are at least partially segregated into the coke. Thus, the contaminants such as chlorine and / or chloride containing compounds are removed from the process such that the species do not deactivate catalysts or cause corrosion in downstream units. Contaminants from the polymeric waste which are segregated into the coke may be a minor component of the coke and do not affect the value or properties of the coke. In embodiments, the coke can contain contaminants from polymeric waste, including chlorine and / or chloride containing compounds, in an amount of 0.01 wt.% to 1 wt.%. Alternatively, in an amount of 0.01 wt.% to 2 wt.%. Alternatively, in an amount of 0.01 wt.% to 0.05 wt.%, in an amount of 0.05 wt.% to 0.1 wt.%, in an amount of 0.1 wt.% to 0.5 wt.%, in an amount of 0.5 wt.% to 1 wt.%, in an amount of 1.0 wt.% to 1.5 wt.%, in an amount of 1.5 wt.% to 2 wt.%, or any ranges therebetw een.

[0087] In embodiments, the coke may include a combination of contaminants. For example, a coke composition may include at least 80 wt.% carbon with the balance being chemical species other than carbon with at least a portion of the chemical species being fromthe polymeric waste. Alternatively, the least 85 wt.% carbon with the balance being chemical species other than carbon with at least a portion of the chemical species being from the polymeric waste. Alternatively, the least 90 wt.% carbon with the balance being chemical species other than carbon with at least a portion of the chemical species being from the polymeric waste. Alternatively, the least 95 wt.% carbon with the balance being chemical species other than carbon with at least a portion of the chemical species being from the polymeric waste. Alternatively, the least 99 wt.% carbon with the balance being chemical species other than carbon with at least a portion of the chemical species being from the polymeric w aste. Table 2 illustrates a typical contaminant amount in the coke produced by the processes described herein.Table 2Coking Conditions - Fluidized Coking

[0088] In accordance with one or more embodiments, polymeric waste can be processed in a fluidized coker. In some embodiments, the plastic waste is co-processed with a conventional coking feedstock. In various aspects, co-processing can be performed by exposing the combined feedstock of waste feedstock and conventional coking feedstock to fluidized coking conditions.

[0089] Fluidized coking is a petroleum refining process in which heavy petroleum feeds, typically the non-distillable residues (resids) from the fractionation of heavy oils are converted to lighter, more useful products by thermal decomposition (coking) at elevated reaction temperatures, typically 480°C to 590°C, and in most cases from 500°C to 550°C. Example heavy oils suitable for processing by the fluidized coking process include heavy atmospheric resids. petroleum vacuum distillation bottoms, aromatic extracts, asphalts, and bitumens from tar sands, tar pits and pitch lakes. In accordance with present embodiments, the plastic waste is processed in the fluidized coker either alone or in combination with a conventional coker feedstock.

[0090] Fluidized coking is carried out in a unit with a large reactor containing hot coke particles which are maintained in the fluidized condition at the required reaction temperature with steam injected at the bottom of the vessel with the average direction of movement of the coke particles being downwards through the bed. In particular embodiments, the combined feedstock is heated to a pumpable temperature, typically in the range of 350°C to 400°C, mixed with atomizing steam, and fed through multiple feed nozzles arranged at several successive levels in the reactor. Steam is injected into a stripping section at the bottom of the reactor and passes upwards through the coke particles descending through the dense phase of the fluid bed in the main part of the reactor above the stripping section. Part of the feed liquid coats the coke particles in the fluidized bed and is subsequently cracked into layers of solid coke and lighter products which evolve as gas or vaporized liquid. The residence time of the feed in the coking zone (where temperatures are suitable for thermal cracking) is on the order of 1 second to 30 seconds. Reactor pressure is relatively low in order to favor vaporization of the hydrocarbon vapors which pass upwards from dense phase into dilute phase of the fluid bed in the coking zone and into cyclones at the top of the coking zone where most of the entrained solids are separated from the gas phase by centrifugal force in one or more cyclones and returned to the dense fluidized bed by gravity through the cyclone diplegs. The mixture of steam and hydrocarbon vapors from the reactor is subsequently discharged from the cyclone gas outlets into a scrubber section in a plenum located above the coking zone and separated from it by a partition. It is quenched in the scrubber section by contact with liquid descending over sheds. A pump-around loop circulates condensed liquid to an external cooler and back to the top shed row of the scrubber section to provide cooling for the quench and condensation of the heaviest fraction of the liquid product. This heavy fraction is typically recycled to extinction by feeding back to the coking zone in the reactor.

[0091] During a fluidized coking process, the coking feedstock, pre-heated to a temperature at which it is flowable and pumpable, is introduced into the coking reactor towards the top of the reactor vessel through injection nozzles which are constructed to produce a spray of the feed into the bed of fluidized coke particles in the vessel. Temperatures in the coking zone of the reactor are typically in the range of 450°C to 650°C and pressures are kept at a relatively low level, typically in the range of 0 kPag to 700 kPag, and most usually from 35 kPag to 320 kPag, in order to facilitate fast drying of the coke particles, preventing the formation of sticky, adherent high molecular weight hydrocarbon deposits on the particles which could lead to reactor fouling. In some embodiments, the temperature in the coking zone can be 450°C to 600°C, or 450°C to 550°C. The conditions can be selected so that a desired amount ofconversion of the feedstock occurs in the fluidized bed reactor. For example, the conditions can be selected to achieve at least 10 wt.% conversion relative to 343°C (or 371°C), or at least 20 wt.% conversion relative 343°C (or 371 °C), or at least 40 wt.% conversion relative to 343°C (or 371°C), such as up to 80 wt.% conversion or possibly still higher. The light hydrocarbon products of the coking (thermal cracking) reactions vaporize, mix with the fluidizing steam and pass upwardly through the dense phase of the fluidized bed into a dilute phase zone above the dense fluidized bed of coke particles. This mixture of vaporized hydrocarbon products formed in the coking reactions flows upwardly through the dilute phase with the steam at superficial velocities of roughly 1 to 2 meters per second (~ 3 to 6 feet per second), entraining some fine solid particles of coke which are separated from the cracking vapors in the reactor cyclones as described above. In embodiments where steam is used as the fluidizing agent, the weight of steam introduced into the reactor can be selected relative to the weight of feedstock introduced into the reactor. For example, the mass flow rate of steam into the reactor can correspond to 6.0% of the mass flow rate of feedstock, or 8.0% or more, such as up to 10% or possibly still higher. The amount of steam can potentially be reduced if an activated light hydrocarbon stream is used as part of the stripping and / or fluidizing gas in the reactor. In such embodiments, the mass flow rate of steam can correspond to 6.0% of the mass flow rate of feedstock or less, or 5.0% or less, or 4.0% or less, or 3.0% or less. Optionally, in some embodiments, the mass flow rate of steam can be still lower, such as corresponding to 1.0% of the mass flow rate of feedstock or less, or 0.8% or less, or 0.6% or less, such as down to substantially all of the steam being replaced by the activated light hydrocarbon stream. The cracked hydrocarbon vapors pass out of the cyclones into the scrubbing section of the reactor and then to product fractionation and recovery.

[0092] In a general fluidized coking process, the coke particles formed in the coking zone pass downwards in the reactor and leave the bottom of the reactor vessel through a stripper section where they are exposed to steam in order to remove occluded hydrocarbons. The solid coke from the reactor, consisting mainly of carbon with lesser amounts of hydrogen, sulfur, nitrogen, and traces of vanadium, nickel, iron, and other elements derived from the feed, passes through the stripper and out of the reactor vessel to a burner or heater where it is partly burned in a fluidized bed with air to raise its temperature from 480°C to 700°C to supply the heat required for the endothermic coking reactions, after which a portion of the hot coke particles is recirculated to the fluidized bed reaction zone to transfer the heat to the reactor and to act as nuclei for the coke formation. The balance is withdrawn as coke product. The net coke yield is only 65 percent of that produced by delayed coking.

[0093] For a coking process that includes a gasification zone, the cracking process proceeds in the reactor, the coke particles pass downwardly through the coking zone, through the stripping zone, where occluded hydrocarbons are stripped off by the ascending current of fluidizing gas (steam). They then exit the coking reactor and pass to the gasification reactor (gasifier) which contains a fluidized bed of solid particles, and which operates at a temperature higher than that of the reactor coking zone. In the gasifier, the coke particles are converted by reaction at the elevated temperature with steam and an oxygen-containing gas into a fuel gas comprising carbon monoxide and hydrogen.

[0094] The gasification zone is typically maintained at a high temperature ranging from 850°C to l,000°C and a pressure ranging from 0 kPag to 1000 kPag, preferably from 200 kPag to 400 kPag. Steam and an oxygen-containing gas are introduced to provide fluidization and an oxygen source for gasification. In some embodiments, the oxygen-containing gas can be air. In other embodiments, the oxygen-containing gas can have a low nitrogen content, such as oxygen from an air separation unit or another oxygen stream including 95 vol% or more of oxygen, or 98 vol% or more, are passed into the gasifier for reaction with the solid particles comprising coke deposited on them in the coking zone. In embodiments where the oxygencontaining gas has a low nitrogen content, a separate diluent stream, such as a recycled CO2 or H2S stream derived from the fuel gas produced by the gasifier, can also be passed into the gasifier.

[0095] In the gasification zone the reaction between the coke and the steam and the oxy gencontaining gas produces a hydrogen and carbon monoxi de-containing fuel gas and a partially gasified residual coke product. Conditions in the gasifier are selected accordingly to generate these products. Steam and oxygen rates (as well as any optional CO2 rates) will depend upon the rate at which cold coke enters from the reactor and to a lesser extent upon the composition of the coke which, in turn will vary according to the composition of the heavy oil feed and the severity of the cracking conditions in the reactor with these being selected according to the feed and the range of liquid products which is required. In some embodiments, the fuel gas product from the gasifier contains entrained coke solids and these are removed by cyclones or other separation techniques in the gasifier section of the unit. Suitable cyclones include internal cyclones in the main gasifier vessel itself or external in a separate, smaller vessel as described below. The fuel gas product is taken out as overhead from the gasifier cyclones. The resulting partly gasified solids are removed from the gasifier and introduced directly into the coking zone of the coking reactor at a level in the dilute phase above the lower dense phase.

[0096] In some embodiments, the coking conditions can be selected to provide a desired amount of conversion relative to 343°C. Typically, a desired amount of conversion can correspond to 10 wt.% or more, or 50 wt.% or more, or 80 wt.% or more, such as up to substantially complete conversion of the feedstock relative to 343°C.

[0097] The volatile products from the coke drum are conducted away from the process for further processing. For example, volatiles can be conducted to a coker fractionator for distillation and recovery’ of coker gases, coker naphtha, light gas oil, and heavy gas oil. Such fractions can be used, usually, but not always, following upgrading, in the blending of fuel and lubricating oil products such as motor gasoline, motor diesel oil, fuel oil, and lubricating oil. Upgrading can include separations, heteroatom removal via hydrotreating and nonhydrotreating processes, de-aromatization, solvent extraction, and the like. The process is compatible with processes where at least a portion of the heavy coker gas oil present in the product stream introduced into the coker fractionator is captured for recycle and combined with the fresh feed (coker feed component), thereby forming the coker heater or coker furnace charge. The combined feedstock ratio (“CFR”) is the volumetric ratio of furnace charge (fresh feed plus recycle oil) to fresh feed to the continuous fluidized coker operation. Fluidized coking operations typically employ recycles of 5 vol% to 35% vol% (CFRs of 1.05 to 1.35). In some embodiments, there can be no recycle and sometimes in special applications recycle can be up to 200%.

[0098] The Flexicoking™ process, developed by Exxon Research and Engineering Company, is a type of fluidized coking process that is operated in a unit including a reactor and a heater, but also including a gasifier for gasifying the coke product by reaction with an air / steam mixture to form a low heating value fuel gas. A stream of coke passes from the heater to the gasifier where all but a small fraction of the coke is gasified to a low-BTU gas fl 20 BTU / standard cubic feet) by the addition of steam and air in a fluidized bed in an oxy gendeficient environment to form fuel gas comprising carbon monoxide and hydrogen. In a conventional Flexicoking™ configuration, the fuel gas product from the gasifier, containing entrained coke particles, is returned to the heater to provide most of the heat required for thermal cracking in the reactor with the balance of the reactor heat requirement supplied by combustion in the heater. A small amount of net coke (1 percent of feed) is withdrawn from the heater to purge the system of metals and ash. The liquid yield and properties are comparable to those from fluidized coking. The fuel gas product is withdrawn from the heater following separation in internal cy clones which return coke particles through their diplegs.

[0099] In this description, the term “Flexicoking” (trademark of ExxonMobil) is used to designate a fluidized coking process in which heavy petroleum feeds are subjected to thermal cracking in a fluidized bed of heated solid particles to produce hydrocarbons of lower molecular weight and boiling point along with coke as a by-product which is deposited on the solid particles in the fluidized bed. References to fluidized cokers are intended to include conventional fluidized cokers as well as flexicokers. The resulting coke can then be converted to a fuel gas by contact at elevated temperature with steam and an oxygen-containing gas in a gasification reactor (gasifier). This type of configuration can more generally be referred to as an integration of fluidized bed coking with gasification. FIGS. 3 and 4 provide examples of fluidized coking reactors that include a gasifier.

[0100] FIG. 2 shows an example of a Flexicoker unit (i.e., a system including a gasifier that is thermally integrated with a fluidized bed coker) with three reaction vessels: reactor, heater and gasifier. The coking system 200 comprises coker reactor 202 with the coking zone and its associated stripping and scrubbing sections (not separately indicated), heater 204 and gasifier 206. A coking feedstock, which may be a waste feedstock (or combined feedstock of waste feedstock and conventional coking feedstock) is introduced into the coking system 200 by line 208 and coker effluent withdrawn through line 210. While FIG. 2, shows a combined feedstock, example embodiments also include separate introduction of the conventional coking feedstock and waste feedstock to the coker reactor 202. Fluidizing and stripping steam is supplied by line 212. Cold coke is taken out from the stripping section at the base of coker reactor 202 by means of line 214 and passed to heater 204. The term “cold" as applied to the temperature of the withdrawn coke is, of course, decidedly relative since it is well above ambient at the operating temperature of the stripping section. Hot coke is circulated from heater 204 to coker reactor 202 through line 216. Coke from heater 204 is transferred to gasifier 206 through line 218 and hot, partly gasified particles of coke are circulated from the gasifier back to the heater 204 through hne 220. The excess coke is withdrawn from the heater 204 by way of line 222. In conventional configurations, gasifier 206 is provided with its supply of steam and air by line 224 and hot fuel gas is taken from the gasifier to the heater though line 226. In some alternative embodiments, instead of supplying air via a hne 224 to the gasifier 206, a stream of oxygen with 95 vol% purity or more can be provided, such as an oxygen stream from an air separation unit. In such embodiments, in addition to supplying a stream of oxygen, a stream of an additional diluent gas can be supplied by line 228. The additional diluent gas can correspond to, for example, CO2 separated from the fuel gas generated during the gasification. The fuel gas is taken out from the unit through hne 230 on the heater; coke fines are removedfrom the fuel gas in heater cyclone system 232 comprising serially connected primary7and secondary cyclones with diplegs which return the separated fines to the fluid bed in the heater. The fuel gas from line 230 can then undergo further processing. For example, in some embodiments, the fuel gas from line 230 can be passed into a separation stage for separation of CO2 (and / or H2S). This can result in a stream with an increased concentration of synthesis gas, which can then be passed into a conversion stage for conversion of synthesis gas to methanol.

[0101] It is noted that in some optional embodiments, heater cyclone system 232 can be located in a separate vessel (not shown) rather than in heater 204. In such aspects, line 230 can withdraw the fuel gas from the separate vessel, and the line 222 for purging excess coke can correspond to a line transporting coke fines away from the separate vessel. These coke fines and / or other partially gasified coke particles that are vented from the heater (or the gasifier) can have an increased content of metals relative to the feedstock. For example, the weight percentage of metals in the coke particles vented from the system (relative to the weight of the vented particles) can be greater than the weight percent of metals in the feedstock (relative to the weight of the feedstock). In other words, the metals from the feedstock are concentrated in the vented coke particles. Since the gasifier conditions do not create slag, the vented coke particles correspond to the mechanism for removal of metals from the coker / gasifier environment. In some embodiments, the metals can correspond to a combination of nickel, vanadium, and / or iron. Additionally, or alternately, the gasifier conditions can cause substantially no deposition of metal oxides on the interior walls of the gasifier, such as deposition of less than 0.1% by weight of the metals present in the feedstock introduced into the coker / gasifier system, or less than 0.01% by weight.

[0102] In configurations such as FIG. 2, the system elements shown in the figure can be characterized based on fluid communication between the elements. For example, coker reactor 202 is in direct fluid communication with heater 204. Coker reactor 202 is also in indirect fluid communication with gasifier 206 via heater 204.

[0103] As an alternative, integration of a fluidized bed coker with a gasifier can also be accomplished without the use of an intermediate heater. In such alternative aspects, the cold coke from the reactor can be transferred directly to the gasifier. This transfer, in almost all cases, will be unequivocally direct with one end of the tubular transfer line connected to the coke outlet of the reactor and its other end connected to the coke inlet of the gasifier with no intervening reaction vessel, i.e., heater. The presence of devices other than the heater is not however to be excluded, e.g., inlets for lift gas etc. Similarly, while the hot, partly gasified coke particles from the gasifier are returned directly from the gasifier to the reactor thissignifies only that there is to be no intervening heater as in the conventional three-vessel Flexicoker™ but that other devices may be present between the gasifier and the reactor, e.g., gas lift inlets and outlets.

[0104] FIG. 3 shows an example of integration of a fluidized bed coker with a gasifier but without a separate heater vessel. In the configuration shown in FIG. 3, the cyclones for separating fuel gas from catalyst fines are located in a separate vessel. In other aspects, the cyclones can be included in a main gasifier vessel 304.

[0105] In the configuration shown in FIG. 3, the coker system 300 includes a coker reactor 302, main gasifier vessel 304 and a separator vessel 306. The coking feedstock is introduced into coker reactor 302 through line 308 and fluidizing / stripping gas through line 310; coker effluent is taken out through line 312. The coking feedstocks includes a waste feedstock with optional combination with a conventional coking feedstock (e.g., heavy oil feed). The waste feedstock can be separately introduced to the coker reactor 302 or introduced in combination with a conventional coking feedstock, for example. Cold, stripped coke is routed directly from coker reactor 302 to main gasifier vessel 304 by way of line 314 and hot coke returned to the reactor in line 316. Steam and oxygen are supplied through line 318. The flow of gas containing coke fines is routed to separator vessel 306 through line 320 which is connected to a gas outlet of the main gasifier vessel 304. The fines are separated from the gas flow in cyclone system 322 comprising serially connected primary and secondary' cyclones with diplegs which return the separated fines to the separator vessel. The separated fines are then returned to the main gasifier vessel 304 through return line 324 and the fuel gas product taken out by way of line 326. Coke is purged from the separator through line 328. The fuel gas from line 326 can then undergo further processing for separation of CO2 (and / or H2S) and conversion of synthesis gas to methanol.

[0106] The coker and gasifier can be operated according to the parameters necessary’ for the required coking processes. Thus, the heavy oil feed in the coking feedstock will typically be a heavy (high boiling) reduced petroleum crude; petroleum atmospheric distillation bottoms; petroleum vacuum distillation bottoms, or residuum; pitch; asphalt; bitumen; other heavy hydrocarbon residues; tar sand oil; shale oil; or even a coal slurry or coal liquefaction product such as coal liquefaction bottoms. Such feeds will typically have a Conradson Carbon Residue (ASTM D189-165) of at least 5 wt.%, generally from 5 wt.% to 50 wt.%. In some embodiments, the coking feedstock is a petroleum vacuum residuum.Coking Conditions - Delayed Coking

[0107] In particular embodiments, delayed coking is performed on a waste feedstock optionally combined with a conventional coking feedstock to produce liquid and vapor hydrocarbon products and coke. In various embodiments, the waste feedstock and optional conventional coking feedstock are exposed to delayed coking conditions.

[0108] Delayed coking is another coking process for the thermal conversion of heavy oils such as petroleum residua (also referred to as “resid”) to produce liquid and vapor hydrocarbon products and coke. In some embodiments, the conventional hydrocarbon feedstock includes resids from heavy and / or sour (high sulfur) crude oils. Delayed coking of the feedstock is carried out by converting part of the feedstock to more valuable hydrocarbon products. The resulting coke has value, depending on its grade, as a fuel (fuel grade coke), electrodes for aluminum manufacture (anode grade coke), etc.

[0109] Generally, a feedstock is pumped to a pre-heater where it is pre-heated, such as to a temperature from 480°C to 520°C. The pre-heated feed is conducted to a coking reactor, typically a vertically oriented, insulated coker vessel, e.g., drum, through an inlet at the base of the drum. Pressure in the drum is usually relatively low, such as 100 kPa-g to 550 kPa-g, or 100 kPa-g to 240 kPa-g to allow volatiles to be removed overhead. Typical operating temperatures of the drum will be between roughly 400°C to 445°C, but can be as high as 475°C. The hot feed thermally cracks over a period of time (the “coking time”) in the coke drum, liberating volatiles composed primarily of hydrocarbon products that continuously rise through the coke bed, which consists of channels, pores and pathways, and are collected overhead. The volatile products are conducted to a coker fractionator for distillation and recovery of coker gases, gasoline boiling range material such as coker naphtha, light gas oil, and heavy gas oil. In an embodiment, a portion of the heavy coker gas oil present in the product stream introduced into the coker fractionator can be captured for recycle and combined with the fresh feed (coker feed component), thereby forming the coker heater or coker furnace charge. In addition to the volatile products, the process also results in the accumulation of coke in the drum. When the coke drum is full of coke, the heated feed is switched to another dram and hydrocarbon vapors are purged from the coke drum with steam. The drum is then quenched with water to lower the temperature down to 95°C to 150°C, after which the water is drained. When the draining step is complete, the drum is opened, and the coke is removed by drilling and / or cutting using high velocity waterjets (“hydraulic decoking”).

[0110] FIG. 4 illustrates an example delayed coking system 400. In the illustrated embodiment, a feedstock 402 comprising a waste feedstock, which may be preheated, is fedinto a coker fractionator 404. In some embodiments, the feedstock 402 further includes a conventional coking feedstock, which may alternatively be separately feed to the coker fractionator 404. In the illustrated embodiment, a fractionator effluent 406 comprising at least a portion of the waste feedstock and / or conventional coking feedstock is withdrawn from the coker fractionator 404 and fed to a coker furnace 408. From the coker furnace 408, the preheated effluent 410 comprising a preheated waste feedstock and / or preheated conventional coking feedstock is passed to a coking reactor 412, which includes, for example, a coking vessel or coking drum. The preheated effluent 410 also includes, for example, tower bottoms (or recycle). The coking reactor 412 is operated at coking conditions such that the preheated waste feedstock / conventional coking feedstock thermally cracks over a period of time (the “coking time”) in the coking reactor 412, liberating volatiles composed primarily of hydrocarbon products that continuously rise through the coke bed, which consists of channels, pores and pathways, and are collected overhead as a coker effluent 414, which is passed to the coker fractionator 404. In the illustrated embodiment, the coker effluent 414 is separated in the coker fractionator 404 into various fractions, including, but not limited to, one or more of a coker gas fraction 418, a coker naphtha fraction 420, and a coker gas oil fraction 422. It should be understood that separation of the coking products into various fractions can occur in one or more vessels and / or one or more different operations. As previously mentioned, coke is accumulated in the coking reactor 412 (e.g., coking vessel). A coke product 416 comprising coke is withdrawn from the coking reactor 412.Chemical Production

[0111] In accordance with one or more embodiments, the processing of the polymeric waste results in the production or recover}' of chemical products. For example, one or more fractions of hydrocarbon coking products from coking of polymeric waste can be processed to form chemical products. Example hydrocarbon coking products include coker gas, coker naphtha, and / or coker gas oil. By way of further example, the one or more fractions from the coker effluent from coking of pyrolysis oil that is at least partially derived from polymeric waste can be processed to form chemical products.

[0112] In some embodiments, the fractions of hydrocarbon coking products includes one or more components that need to be removed and / or reduced in concentration prior to subsequent processing. For example, embodiments include treating the fractions of hydrocarbon coking products to remove at least a portion of contaminants, including halides, acids, and sulfur species. Any of a variety of techniques may be used for treatment of the fractions of hydrocarbon coking products, including absorption, adsorption, hydroprocessing,filtration, and fractionation. Adsorption can be used for removal of specific contaminants, such as mercury. Examples of specific adsorption techniques include treatment beds, such as mercury beds. Absorption includes solid and liquid contacting methods such as water washing, amine gas treating, caustic treatment. Water washing includes, for example, contacting the fractions of hydrocarbon coking products with a water stream. Example hydroprocessing techniques include hydrogenation and hydrotreating. Embodiments of hydroprocessing also may convert organic halides in the fractions of hydrocarbon coking products to inorganic acid. Neutralizing additives can then be added to the hydroprocessing effluent for neutralization of the produced inorganic acids. Mercury is removed, in some embodiments, for example, with mercaptan oxidation. Filtration is used, for example, to remove solid particulates.

[0113] The chemical products produced from integration of co-processing of polymeric waste includes a variety of chemical products, including olefins e.g.. alpha-olefins), aromatics, oligomers, and polymers. A '‘polymer’’ has one or more repeating units that are the same or different. The term '‘polymer” as used herein includes oligomers (up to 75 repeating units) and larger polymers (greater than 75 repeating units). “Homopolymer” is a polymer having the same repeating unit. A “copolymer” is a polymer having two or more repeating units different from each other. A “terpolymer” is a polymer having three repeating units different from each other. “Different” is used to mean that the repeating units differ from each other by at least one atom or isomer. Therefore, the definition of the copolymer used herein includes a terpolymer and the like. The chemical products include or can be processed to form a number of desirable products, including: olefins, such as ethylene, propylene, butylene, butadiene, pentenes, Cs olefins, and CT di-olefins, as well as longer olefins, such as hexene, nonene, and tetramer; aromatics, such as benzene, styrene, and toluene; cyclohexane; polymers, such as polyethylene, polypropylene, polystyrene, polyesters, poly-vinyl chloride; and di-vinyl chloride; synthetic elastomers and rubbers, such as styrene-butadiene rubber, ethylene- propylene-diene-rubbers, butyl rubbers, and halobutyl rubbers; plastic additives and modifiers, such as plasticizers; epoxies resins; and fluids with multiple applications, such as isopropyl alcohol, oxo-alcohols, glycols, detergents, and lubricants.

[0114] At least a portion of these chemical products may be circular chemical products that are attributable to the polymeric waste, such as determined by crediting, allocating, and / or offsetting or substituting for other hydrocarbons in a mass or energy balance for a system, such as in accordance with a third-party certification relating to circularity. At least a portion of these chemical products may be certified circular chemical products that are certified for their circularity by third party certification may be referred to as certified circular.

[0115] Various processes may be employed to integrate chemical production with coking. For example, a fraction of hydrocarbon coking products received from coking may be converted in one or more of the following units: hydroprocessing units, such as hydrocracking and hydrotreating units; fluid catalytic cracking units; steam cracking units; catalytic reforming units; partial oxidation to synthetic gas; and / or isomerization. The chemical products may be directly produced by such processes or may be obtained by further processing, such as separation, treating, and / or cracking of an effluent of such processes. As an example, the chemical products may be obtained by processing of fractions of hydrocarbon coking products at least partially derived from polymeric waste. In addition, co-processing of polymeric waste as a feed or co-feed into delayed or fluidized coking units (including FLEXICOKING™ units), may result in the attribution of the polymeric waste to chemical products (including olefins, polymers, or aromatics), such as determined by crediting, allocating, and / or offsetting or substituting for other hydrocarbons in a mass or energy balance for a system, such as in accordance with a third-parly certification relating to circularity.

[0116] Accordingly, processes per various embodiments herein may further include obtaining olefins that have been produced or recovered from the processing of polymeric waste or olefins to which the processing of polymeric waste has been attributed, e.g., for employment in polymerization processes; and polymers of various embodiments described herein may comprise olefins that have been produced or recovered from the processing of polymeric waste or olefins to which the processing of polymeric waste has been attributed. As an example, at least a portion of the olefin content (e.g.. employed in processes and / or included in compositions as described herein) may be from olefins that are produced or recovered directly from the processing of polymeric waste. Similarly, the processing of polymeric waste may be attributed to at least a portion the olefins (e.g., employed in processes and / or included in compositions as described herein).Additional Embodiments

[0117] Accordingly, the present disclosure may provide for the integration of polymeric waste co-processing in cokers to produce circular chemical products from coker naphtha. The methods and systems may include any of the various features disclosed herein, including one or more of the following embodiments.

[0118] Embodiment 1. A method of sequestering contaminant compounds from polymeric waste comprising thermally cracking at least, a feedstock comprising a polymeric waste and a coker feedstock to produce at least coke and a coking effluent comprising hydrocarbons, wherein the polymeric waste comprises chlorine and / or chloride compounds, wherein at leasta portion of the chlorine and / or chloride compounds are segregated into the coke, and wherein the coke comprises 0.01 wt.% to 1 wt.% of the chlorine and / or chloride compounds; and separating at least a portion of the coking effluent to form a coker naphtha.

[0119] Embodiment 2. The method of embodiment 1, wherein the coker naphtha has a concentration of the chlorine and / or chloride compounds in an amount of about 1 wppm to about 0.5 wt.%, a 2-3 ring aromatic content of about 0 wt.% to about 5 wt.%, and a sulfur content of about 750 ppm to about 2 wt.%.

[0120] Embodiment 3. The method of any of embodiments 1-2. wherein the polymeric waste further comprises at least one contaminant selected from the group consisting of nitrogen, sulfur, aluminum, boron, calcium, chromium cobalt, iron, manganese, magnesium, molybdenum, nickel, potassium, phosphorous, silicon, sodium, titanium, vanadium, and combinations thereof.

[0121] Embodiment 4. The method of embodiment 3, wherein the coke further comprises each of the at least one contaminant in an amount of about 0.01 wt.% to about 1 wt.%.

[0122] Embodiment 5. The method of any of embodiments 1-4, wherein coker feedstock comprises a heavy oil with a T10 distillation point of about 343°C to about 575°C.

[0123] Embodiment 6. The method of embodiment 5, wherein the heavy oil comprises petroleum vacuum resid.

[0124] Embodiment 7. The method of any of embodiments 1-6, wherein the feedstock comprises the polymeric waste in an amount of about 0. 1 wt.% to about 25 wt.%.

[0125] Embodiment 8. The method of any of embodiments 1-7, further comprising converting the coker naphtha into at least a polymer.

[0126] Embodiment 9. The method of embodiment 8, wherein at least a portion of the polymer is attributable to one or more polymers in the polymeric waste.

[0127] Embodiment 10. The method of any of embodiments 8-9, wherein the polymer comprises a circular polymer.

[0128] Embodiment 11. The method of any of embodiments 8-10, wherein at least a portion of the polymer is certified circular in accordance with International Sustainability' and Carbon Certification.

[0129] Embodiment 12. The method of any of embodiments 8-11. wherein the coker naphtha is further converted into at least one chemical product selected from the group consisting of a monomer, an aromatic, a synthetic elastomer, a synthetic rubber, an epoxy, a resin, isopropyl alcohol, an oxo-alcohol, and combinations thereof.

[0130] Embodiment 13. The method of any of embodiments 8-12, wherein converting the coker naphtha into at least the polymer comprises cracking at least a portion of the coker naphtha to fonn at least a cracking effluent, recovering olefins from the cracking effluent; and polymerizing at least a portion of the olefins to form at least a polyolefin.

[0131] Embodiment 14. The method of any of embodiments 1-13, wherein the coking effluent further comprises coker gas and wherein the coker gas comprises chlorine and / or chloride compounds in an amount of about 0 wt.% to about 0.001 wt.%.

[0132] Embodiment 15. The method of any of embodiments 1-14, wherein the coking effluent further comprises coker gas oil and wherein the coker gas oil comprises chlorine and / or chloride compounds in an amount of about 0 wt.% to about 0.001 wt.%.

[0133] Embodiment 16. A method of sequestering contaminant compounds from polymeric waste comprising: thermally cracking at least, a feedstock comprising a polymeric waste and a coker feedstock to produce at least coke and a coking effluent comprising hydrocarbons, wherein the polymeric waste comprises a metal comprising at least titanium, wherein at least a portion of the metal is segregated into the coke, and wherein the coke comprises 0.01 wt.% to 2 wt.%. of the metal; and separating at least a portion of the coking effluent to form a coker naphtha.

[0134] Embodiment 17. The method of embodiment 16 wherein the metal further comprises at least one additional metal selected from the group consisting of aluminum, calcium, magnesium, zinc, and combinations thereof.

[0135] Embodiment 18. The method of any of embodiments 16-17 wherein the coke further comprises the additional metal in an amount of about 0.01 wt.% to about 1 wt.%.

[0136] Embodiment 19. A petroleum coke composition comprising at least 95 wt.% carbon; chlorine and / or chloride compounds in an amount of about 0.01 wt.% to about 1 wt.%', titanium in an amount of about 0.01 wt.% to about 1 wt.%; aluminum in an amount of about 0.01 wt.% to about 1 wt.%; and vanadium in an amount of about 0.01 wt.% to about 1 wt.%.

[0137] Embodiment 20. The petroleum coke composition of embodiment 19, wherein at least a portion of the carbon is attributable to one or more polymers from thermally cracked polymeric waste.

[0138] Embodiment 21. The petroleum coke composition of embodiment 20, wherein the polymeric waste comprises plastic waste.

[0139] Embodiment 22. The petroleum coke composition of embodiment 19, further comprising at least one contaminant selected from the group consisting of nitrogen, sulfur, boron, calcium, chromium cobalt, iron, manganese, magnesium, molybdenum, nickel,potassium, phosphorous, silicon, sodium, and combinations thereof, in an amount of about 0.01 wt.% to about 1 wt.%.

[0140] T o facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the entire scope of the disclosure.EXAMPLE 1

[0141] In this example, a plastic feedstock containing chloride compounds and a petroleum vacuum resid were co-processed in a refining coking unit. Coke balls were collected from the coking unit and analyzed by scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS). The coke samples were embedded in a cold mount epoxy resin, mechanically cross sectioned, and polished prior to analysis by SEM and EDS.

[0142] FIG. 5 is an x-ray image of a cross section of a coke ball. FIG. 6 is extracted spectra data from the EDS of the coke ball. It was observed that in the analyzed section of the coke ball the local concentration of chlorine was 0.1 wt.%, indicating that chloride compounds from the plastic feedstock were segregated into the coke ball. It was further observed that the analyzed section of the coke ball contained a local concentration of titanium and aluminum in an amount of 0. 1 wt.%.EXAMPLE 2

[0143] In this example, the hydrolysis of sodium chloride (NaCl) and calcium chloride (CaCh) was compared to the hydrolysis of comparative compounds of magnesium chloride (MgCh) and iron(III) chloride (FeCE) in a simulated coking environment. In coker conditions, inorganic chlorides may pose a corrosion risk because the inorganic chlorides may hydrolyze to for hydrochloric acid (HC1). In this example, humidified argon was used as a moisture source. Two reactor temperatures were chosen, 432°C and 551 °C to simulate coker conditions. The tested inorganic chloride was placed in the humidified argon which was heated by 10°C / min until the desired reactor temperature was reached, followed by a 1-hour hold time. The hydrolysis reaction of the inorganic chloride was monitored by thermogravimetric analysis (TGA) coupled with Fourier-transform infrared spectroscopy (FTIR). FIG. 7 is a graph of the thermogravimetric analysis profile and FIG. 8 is a graph of the Fourier-transform infrared spectroscopy of iron (III) chloride hydrolysis.

[0144] Table 3 shows the results of the hydrolysis experiment. It was observed that magnesium chloride and iron (III) chloride completely hydrolyzed a both the selected temperatures. It was further observed that the sodium chloride and calcium chloride werepartially hydrolyzed at both temperatures, but the higher temperature resulted in a greater extent of hydrolysis.

[0145] The result from these experiments were extrapolated to estimate hydrolysis at thermal dechlorination temperature. It is worth noting that these estimates are higher than actual expectation since the experiments were completed with single component (salt only) and does not capture the mass transfer impact. In reality, a few of these inorganic chlorides can be in the polymer matrix and in coker co-processing case, the inorganic chlorides will be in the bulk of coker hydrocarbon and parameters such as mixing, viscosity, residence time, moisture content, etc. will impact % hydrolysis.Table 3

[0146] While the disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the disclosure as disclosed herein. Although individual embodiments are discussed, the present disclosure covers all combinations of all those embodiments.

[0147] While compositions, methods, and processes are described herein in terms of “comprising,” “containing,” “having,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. The phrases, unless otherwise specified, “consists essentially of’ and “consisting essentially of’ do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0148] All numerical values within the detailed description are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0149] Many alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of thepresent disclosure and that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

Claims

CLAIMS:

1. A method of sequestering contaminant compounds from polymeric waste comprising: thermally cracking at least, a feedstock comprising a polymeric waste and a coker feedstock to produce at least coke and a coking effluent comprising hydrocarbons, wherein the polymeric waste comprises chlorine and / or chloride compounds, wherein at least a portion of the chlorine and / or chloride compounds are segregated into the coke, and wherein the coke comprises 0.01 wt.% to 1 wt.% of the chlorine and / or chloride compounds; and separating at least a portion of the coking effluent to form a coker naphtha.

2. The method of claim 1, wherein the coker naphtha has a concentration of the chlorine and / or chloride compounds in an amount of about 1 wppm to about 0.5 wt.%, a 2-3 ring aromatic content of about 0 wt.% to about 5 wt.%, and a sulfur content of about 750 ppm to about 2 wt.%.

3. The method of any of claims 1-2. wherein the polymeric waste further comprises at least one contaminant selected from the group consisting of nitrogen, sulfur, aluminum, boron, calcium, chromium cobalt, iron, manganese, magnesium, molybdenum, nickel, potassium, phosphorous, silicon, sodium, titanium, vanadium, and combinations thereof.

4. The method of claim 3, wherein the coke further comprises each of the at least one contaminant in an amount of about 0.01 wt.% to about 1 wt.%.

5. The method of any of claims 1-4, wherein coker feedstock comprises a heavy oil with a T10 distillation point of about 343°C to about 575°C.

6. The method of any of claims 1 -5, wherein the feedstock comprises the polymeric waste in an amount of about 0. 1 wt.% to about 25 wt.%.

7. The method of any of claims 1-6, further comprising converting the coker naphtha into at least a polymer.

8. The method of claim 7, wherein at least a portion of the polymer is attributable to one or more polymers in the polymeric waste wherein the polymer comprises a circular polymer.

9. The method of claim 8, wherein at least a portion of the polymer is certified circular in accordance with International Sustainability and Carbon Certification.

10. The method of any of claim 1-9, wherein the coking effluent further comprises coker gas and wherein the coker gas comprises chlorine and / or chloride compounds in an amount of about 0 wt.% to about 0.001 wt.% and / or wherein the coking effluent further comprises coker gas oil and wherein the coker gas oil comprises chlorine and / or chloride compounds in an amount of about 0 wt.% to about 0.001 wt.%.

11. A method of sequestering contaminant compounds from polymeric waste comprising: thermally cracking at least, a feedstock comprising a polymeric waste and a coker feedstock to produce at least coke and a coking effluent comprising hydrocarbons, wherein the polymeric waste comprises a metal comprising at least titanium, wherein at least a portion of the metal is segregated into the coke, and wherein the coke comprises 0.01 wt.% to 2 wt.% of the metal; and separating at least a portion of the coking effluent to form a coker naphtha.

12. The method of claim 11 wherein the metal further comprises at least one additional metal selected from the group consisting of aluminum, calcium, magnesium, zinc, and combinations thereof, wherein the coke further comprises the additional metal in an amount of about 0.01 wt.% to about 1 wt .%.

13. A petroleum coke composition comprising: at least 95 wt .% carbon; chlorine and / or chloride compounds in an amount of about 0.01 wt.% to about 1 wt.%; titanium in an amount of about 0.01 wt.% to about 1 wt.%; aluminum in an amount of about 0.01 wt.% to about 1 wt.%; and vanadium in an amount of about 0.01 wt.% to about 1 wt.%.

14. The petroleum coke composition of claim 13, wherein at least a portion of the carbon is attributable to one or more polymers from thermally cracked polymeric waste.

15. The petroleum coke composition of claim 13, further comprising at least one contaminant selected from the group consisting of nitrogen, sulfur, boron, calcium, chromium cobalt, iron, manganese, magnesium, molybdenum, nickel, potassium, phosphorous, silicon, sodium, and combinations thereof, in an amount of about 0.01 wt.% to about 1 wt.%.

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