Catalytic cracking process for true circular solution for converting pyrolysis oil produced from recycled waste plastic into virgin olefins and petrochemical intermediates

Abstract

To provide a true circular solution for recycled waste plastics.SOLUTION: There are provided processes and systems for producing raw materials and for producing truly circular polymers. The systems and processes may include processing a waste-derived hydrocarbon stream, such as a waste plastic pyrolysis oil, in a first reactor system with a catalyst mixture, and processing a fossil-based feedstock in a second reactor system with the catalyst mixture. The catalyst mixture may be supplied to each of the first and second reactor systems from a common catalyst regenerator. An effluent comprising fossil-based hydrocarbon products may be recovered from the second reactor system, and an effluent comprising waste-derived hydrocarbon products may be recovered from the first reactor system. Following separations, spent catalyst from each of the first and second reactor systems may be returned to the common catalyst regenerator.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to recycling waste materials, such as plastic waste. More particularly, embodiments herein relate to systems and methods that provide a true circular solution for converting end-of-life plastic materials back into olefins and chemical intermediates that may be useful in producing new plastic materials and compositions. [Background technology]

[0002] Thermal pyrolysis of plastic waste reclaims valuable carbon and hydrogen elements from used plastics by converting them into valuable molecules that can be upgraded to new chemical intermediates, which can then be converted into entirely new consumer goods. Because this process potentially allows post-consumer plastics to be repeatedly recycled into new materials, the polymers produced through this process are called circular polymers. This reduces plastic waste in landfills and the environment, replacing the consumption of an equivalent amount of fossil-derived raw materials. However, several factors affect the economic feasibility of this recycling pathway.

[0003] The liquid oil product derived from the pyrolysis of plastic waste may not be feedable to a liquid steam cracker or may require treatment or conditioning before being fed to a liquid steam cracker. High levels of nitrogen, chlorine, and contaminants such as mono- and di-olefins, as well as iron and calcium, may require further consideration or adjustment before being added directly as feed to the steam cracking furnace. To make this feedstock steam crackable, one possible solution may require a hydrotreating step, such as first saturating the di-olefins, then saturating the mono-olefins, and then hydrotreating. However, such a step requires a hydrogen supply, the addition of multiple high-pressure reactors, and the associated investment (if vessels are not available), and operating costs.

[0004] Another option to this approach would be to blend the pyrolysis oil with conventional naphtha feedstock and send it to the cracking unit to dilute the negative impact of its properties. However, the olefins and petrochemical intermediates obtained from cracking the pyrolysis oil would be blended with those from conventional naphtha, contributing a small amount to the final olefin product and would require certification of a specific recycled content based on mass balance methodology. However, dilution / blending with fresh hydrocarbon feed is only a transitional solution and not a viable long-term solution for a circular plastics economy.

[0005] Another factor affecting the feasibility of plastic recycling is the limited amount of plastic waste feedstock available through cost-effective channels. Due to infrastructure and logistical limitations, the amount of plastic accessible for recycling is limited in each geographic location. Most currently available plastic pyrolysis process technologies are designed to process no more than 50 tonnes of plastic per day per train. This is dictated not only by limitations on scale-up but also by the availability of plastic waste. At this scale, the pyrolysis oil produced from one of these units would be equivalent to 13,000 metric tons per year. If this were fed to a global-scale naphtha cracker, it would constitute only 2 wt% of the total feed to a single steam cracker. Plastic waste pyrolysis unit capacities are expected to increase to even larger sizes in the future, ranging from 1,000 to 2,000 tonnes per day of plastic feed. However, even at these higher capacities, the resulting feedstock contribution to the naphtha cracker would likely only represent a fraction of the total feed to the steam cracker. Therefore, the resulting product will not be 100% recycled; it is believed that the resulting product will have a very small percentage of recycled components.

[0006] The cost of acquiring plastic waste and the costs associated with sorting and cleaning it into a feedstock suitable for pyrolysis are also high. Many proposed processes are not flexible to feed variability and contaminant content and require significant sorting and cleaning to produce usable feedstock. To address issues related to the quality and contamination of pyrolysis oil feedstocks to liquid naphtha cracking units, many companies use expensive clean, pure recycled plastic feedstocks, such as pure PE or PP, in their pyrolysis units, hydrotreating and hydrotreating, or using the dilution effect of blending pyrolysis oil with much larger amounts of fossil-derived naphtha. However, even at larger capacities, such as approximately 3,800 barrels per day, it can still be uneconomical to hydrotreat and hydrotreat pyrolysis oil to make the feed suitable for a typical steam cracking unit.

[0007] Yet another factor affecting plastics recycling is that plastic pyrolysis units are typically designed with small processing capacities, not taking advantage of economies of scale, and the required product processing levels result in high associated operating and capital costs. The quantity and quality of the pyrolysis oil product sent, the preparation required for further processing, and the impact on existing operations make integration with existing downstream facilities difficult. Furthermore, revenues from the sale of pyrolysis products when combined with fossil-based products often compare unfavorably with processing costs and can fluctuate depending on the available markets and prices for various plastic pyrolysis-derived products. Summary of the Invention [Problem to be solved by the invention]

[0008] Embodiments herein relate to systems and methods that address one or more of the challenges of converting pyrolysis oil produced from the thermal pyrolysis of waste materials, such as plastics, back into useful virgin olefins and petrochemical intermediates. In one or more embodiments, the systems and methods may provide a true circular solution to plastic waste recycling. [Means for solving the problem]

[0009] In one aspect, embodiments disclosed herein relate to a method for producing a feedstock for producing truly circular polymers. The method may include treating a waste-derived hydrocarbon stream, such as plastic waste pyrolysis oil, with a catalyst mixture in a first reactor system and treating a fossil-based feedstock with the catalyst mixture in a second reactor system. The catalyst mixture may be supplied to each of the first and second reactor systems from a common catalyst regenerator. The method may also include recovering an effluent containing fossil-based hydrocarbon products from the second reactor system and recovering an effluent containing waste-derived hydrocarbon products from the first reactor system. After separating the hydrocarbons from the catalyst in the effluent, the method may include returning spent catalyst from each of the first and second reactor systems to the common catalyst regenerator.

[0010] In various embodiments, the method may include maintaining the fossil-based hydrocarbon product recovered from the first reactor system separately from the waste-derived hydrocarbon product recovered from the second reactor system. Further embodiments may include feeding an olefin fraction recovered from the waste-derived hydrocarbon product to a polymerization system to produce a recycled polymer. Additionally, the method may include pyrolyzing a waste stream containing plastic, tires, or other polymeric materials to produce the plastic waste pyrolysis oil. In yet other embodiments, the method may include feeding one or more of the waste-derived hydrocarbon products, or waste-derived monomers obtained from processing the waste-derived hydrocarbon products, directly or indirectly to a polymerization process to produce a recycled polymer.

[0011] In another aspect, embodiments herein are directed to a method for converting plastic waste into a feedstock for producing plastics. The method may include pyrolyzing a polymeric waste feedstock to produce a plastic waste pyrolysis oil. A catalyst mixture including a first catalyst and a second catalyst may be regenerated in a catalyst regenerator. A portion of the catalyst mixture may be fed to a first reactor system, and another portion of the catalyst mixture may be fed to a second reactor system. In the first reactor system, a fossil-based feedstock may be contacted with the catalyst mixture to crack a portion of the fossil-based feedstock, thereby producing a first effluent including fossil-derived olefins, the first catalyst, and the second catalyst. In the second reactor system, the plastic waste pyrolysis oil may be contacted in a reactor with a high-concentration catalyst mixture to crack a portion of the plastic waste pyrolysis oil, the high-concentration catalyst mixture including a portion of the catalyst mixture fed to the second reactor system and an additional second catalyst, such that the catalyst mixture in the second reactor system has a higher concentration of the second catalyst than in the catalyst regenerator or the first reactor system. The contacting in the second reactor system produces a second reactor effluent containing waste-derived olefins and other hydrocarbons, the first catalyst, and the second catalyst. The second reactor effluent may then be separated to produce a first stream containing the first catalyst and the waste-derived olefins and other hydrocarbons, and a second stream containing the second catalyst. The second stream may be fed to the second reactor as the additional second catalyst, thereby enriching the second catalyst in the second reactor system. The first effluent may be separated to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a first reactor system product stream containing the fossil-derived olefins. The first stream (the effluent from the second reactor and spent first catalyst) may be separated to recover (i) spent first catalyst, and (ii) a second reactor system product stream containing the waste-derived olefins and other waste-derived hydrocarbons.The method may include providing each of (i) a mixture of the spent first catalyst and the spent second catalyst, and (ii) the spent first catalyst to the catalyst regenerator.

[0012] In some embodiments, the first catalyst comprises one or more selected from the group consisting of amorphous silica alumina, Y-type zeolite, X-type zeolite, zeolite beta, zeolite MOR, mordenite, faujasite, nanocrystalline zeolite, and MCM mesoporous material.

[0013] In various embodiments, the second catalyst comprises one or both of an additive-type cracking catalyst or a mixture of additive-type cracking catalysts selected from the group consisting of medium pore zeolites and pentasil-based zeolites; or a pollutant-trapping additive or a mixture of pollutant-trapping additives selected from the group consisting of MgO, CaO, CeO2, MgTiO3, CaTiO3, Li2Ti2O7, and ZnTiO3, Ca / Mg, boron, rare earth-based scavenging additives, or low chlorine FCC catalysts.

[0014] Methods according to some embodiments may include feeding the first reactor system product stream to a first fractionation system to separate the first reactor system product stream to recover two or more fossil-derived hydrocarbon fractions. Methods according to embodiments herein may further include feeding the second reactor system product stream to a second fractionation system to separate the second reactor system product stream to recover two or more waste-derived hydrocarbon fractions. The method may include feeding one or more of the two or more waste-derived hydrocarbon fractions to a polymerization process to produce a recycled polymer.

[0015] In another aspect, embodiments herein relate to a method for converting plastic waste into a feedstock for producing plastics. The method may include pyrolyzing a polymeric waste feedstock to produce a plastic waste pyrolysis oil having a concentration of one or more contaminants. The contaminants may include, for example, one or more of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine. The method may include regenerating a catalyst mixture in a catalyst regenerator, the catalyst mixture including a first catalyst and a second catalyst, the second catalyst configured to capture the one or more contaminants. A portion of the catalyst mixture may be fed to a first reactor system, and another portion of the catalyst mixture may be fed to a second reactor system. In the first reactor system, a fossil-based feedstock may be contacted with the catalyst mixture to crack a portion of the fossil-based feedstock, thereby producing a first effluent including fossil-derived olefins, the first catalyst, and the second catalyst. In the second reactor system, the plastic waste pyrolysis oil may be contacted with a concentrated catalyst mixture in a first-stage reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil, the concentrated catalyst mixture comprising a portion of the catalyst mixture supplied to the second reactor system and an additional second catalyst, such that the catalyst mixture in the first-stage reactor has a higher concentration of second catalyst than in the catalyst regenerator, and the contact produces a first-stage reactor effluent comprising treated plastic waste pyrolysis oil with reduced contaminant concentrations, the first catalyst, and the second catalyst containing captured contaminants. The first-stage reactor effluent may be separated to produce a first stream comprising the first catalyst and treated plastic waste pyrolysis oil with reduced contaminant concentrations, and a second stream comprising the second catalyst. The second stream may be supplied to the first-stage reactor as the additional second catalyst, thereby enriching the second catalyst in the first-stage reactor.The first stream may be fed to a second-stage reactor to crack the treated plastic waste pyrolysis oil, thereby recovering a second-stage reactor effluent containing spent catalyst and waste-derived olefins and other waste-derived hydrocarbons. The first effluent may be separated to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a first reactor system product stream containing the fossil-derived olefins. The second-stage reactor effluent may further be separated to recover (i) spent catalyst, and (ii) a second-stage reactor system product stream containing the waste-derived olefins and other waste-derived hydrocarbons. The method may include feeding each of (i) the mixture of spent first catalyst and spent second catalyst, and (ii) the spent catalyst, to the catalyst regenerator.

[0016] In some embodiments, the method may further include feeding the first reactor system product stream to a first fractionation system to separate the first reactor system product stream to recover two or more fossil-derived hydrocarbon fractions; and feeding the second stage reactor system product stream to a second fractionation system to separate the second stage reactor system product stream to recover two or more waste-derived hydrocarbon fractions.

[0017] In various embodiments, the method may further include maintaining the fossil-based hydrocarbon fraction recovered from the first reactor system separate from the waste-derived hydrocarbon product recovered from the second reactor system.

[0018] To produce recycled polymer, embodiments herein may further include feeding the olefin fraction recovered from the waste-derived hydrocarbon product to a polymerization system to produce recycled polymer.

[0019] After separation of the waste-derived hydrocarbon product, the method herein may include feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the first reactor of the second reactor system. In this manner, additional waste-derived olefins may be produced from the waste-based feedstock. In other embodiments, the method may include feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the second reactor of the second reactor system.

[0020] In yet another aspect, embodiments herein relate to a method for converting plastic waste materials into recycled polymers. The method may include pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil having a concentration of one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine. The method may also include regenerating a catalyst mixture in a catalyst regenerator, the catalyst mixture including a first catalyst and a second catalyst, wherein the second catalyst is configured to capture the one or more contaminants. A portion of the catalyst mixture may be fed to a first reactor system, and a portion of the catalyst mixture may be fed to a second reactor system. In the first reactor system, the plastic waste pyrolysis oil may be contacted with a high-concentration catalyst mixture in a first reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil, the high-concentration catalyst mixture comprising a portion of the catalyst mixture supplied to the first reactor system and an additional second catalyst, such that the catalyst mixture in the first reactor system has a higher concentration of second catalyst than in the catalyst regenerator. The contact in the first reactor system may produce a first reactor effluent comprising treated plastic waste pyrolysis oil having a reduced contaminant concentration, the first catalyst, and the second catalyst containing captured contaminants. The first reactor effluent may then be separated to produce a first stream comprising the first catalyst and treated plastic waste pyrolysis oil having the reduced contaminant concentration, and a second stream comprising the second catalyst. The second stream may be supplied to the first reactor as the additional second catalyst, thereby enriching the second catalyst in the first reactor system. The first stream may be fed to a separation system to recover a first separation effluent containing the spent first catalyst and a second separation effluent containing the treated plastic waste pyrolysis oil, and the second separation effluent may be fed to a fractionation system to fractionate the treated plastic waste pyrolysis oil into three or more hydrocarbon fractions including a light olefin fraction, a naphtha fraction, and a treated pyrolysis oil fraction.At least one of the naphtha fraction and the treated pyrolysis oil fraction may be supplied to a second reactor system, where the naphtha fraction and at least one of the heavy oil fraction are contacted with the catalyst mixture to crack a portion of the hydrocarbons contained therein, thereby producing a second reactor system effluent comprising waste-derived olefins, the first catalyst, and the second catalyst. The second reactor system effluent may then be separated to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a second reactor system product stream comprising the waste-derived olefins. The method may further comprise supplying each of (i) the mixture of spent first catalyst and spent second catalyst, and (ii) the first separated effluent comprising the spent first catalyst, to the catalyst regenerator.

[0021] In yet a further aspect, embodiments herein are directed to a method for producing a feedstock for producing truly recycled polymers. The method may include processing a polymer waste mixture in a first reactor system including a first-stage reactor and a second-stage reactor. The processing of the polymer waste mixture may include supplying the polymer waste mixture to the first-stage reactor to pyrolyze the polymers contained therein and recovering a pyrolysis effluent. The processing of the polymer waste mixture may include supplying a waste-derived plastic pyrolysis oil and a catalyst mixture to the second-stage reactor to crack the hydrocarbons contained therein and recovering an effluent containing the cracked hydrocarbons. The pyrolysis effluent from the first-stage reactor and the effluent from the second-stage reactor may be supplied to a first fractionation system to separate the effluent into two or more waste-derived hydrocarbon streams including the waste-derived plastic pyrolysis oil and one or more waste-derived olefin fractions. A fossil-based feedstock may be processed with the catalyst mixture in a second reactor system. The method may further include feeding the catalyst mixture to each of the first and second reactor systems from a common catalyst regenerator. An effluent containing fossil-based hydrocarbon products may be recovered from the second reactor system, and the effluent containing fossil-based hydrocarbon products may be fed to a second fractionation system. The method may include returning spent catalyst from each of the first and second reactor systems to the common catalyst regenerator.

[0022] In some embodiments of the method, the catalyst mixture includes a first catalyst and a second catalyst, and the second-stage reactor is a catalyst-enriched reactor system. The method may include recovering a second-stage reactor effluent comprising the catalyst mixture and the cracked hydrocarbons. The second-stage reactor effluent may be separated to produce a first stream comprising the first catalyst and the cracked hydrocarbons and a second stream comprising the second catalyst. The first stream may be separated to recover (i) spent catalyst and (ii) the second-stage reactor effluent that was fed to the first fractionation system. The method may include feeding the second stream to the second-stage reactor, thereby enriching the second catalyst circulating in the second reactor to a higher concentration than the catalyst mixture as received from the regenerator.

[0023] In any of the above-described methods, the polymer waste pyrolysis oil may be derived from, or the polymer waste feed or polymer waste mixture may comprise, one or more thermoplastic resins selected from the group consisting of polystyrene, polypropylene, polyphenylene sulfide, polyphenylene oxide, polyethylene, polyetherimide, polyetheretherketone, polyoxymethylene, polyethersulfone, polycarbonate, polybenzimidazole, polylactic acid, nylon, acrylonitrile-butadiene-styrene (ABS) polymer, polymethyl methacrylic acid (PMMA); one or more thermoset resins formed from monomers including one or more of acrylic, polyester, vinyl ester, epoxy, urethane, urea, and isocyanate; and one or more unsaturated or saturated elastomers selected from the group consisting of polybutadiene, isoprene, chloroprene, styrene-butadiene, nitrile, and ethylene vinyl acetate.

[0024] In another aspect, embodiments disclosed herein relate to apparatus and process schemes for producing recycled virgin light olefins and petrochemical intermediates. In another aspect, embodiments disclosed herein relate to methods and apparatus for treating pyrolysis oil contaminants and further producing recycled virgin light olefins and petrochemical intermediates. In yet another aspect, embodiments herein are directed to systems for carrying out the methods outlined above.

[0025] In some aspects, embodiments herein are directed to a system for producing feedstock for producing truly circular polymers. The system may include a first reactor system configured to process plastic waste pyrolysis oil and containing a catalyst mixture, and a second reactor system configured to process a fossil-based feedstock with the catalyst mixture. A feed line may be configured to supply the catalyst mixture to each of the first and second reactor systems from a common catalyst regenerator. A flow line may be configured to recover an effluent containing fossil-based hydrocarbon products from the second reactor system. Another flow line may be configured to recover an effluent containing waste-derived hydrocarbon products from the first reactor system. A further flow line may be configured to return spent catalyst from each of the first and second reactor systems to the common catalyst regenerator. In some embodiments, the system further includes a plastic waste pyrolysis system configured to pyrolyze a waste stream containing plastic, tires, or other polymeric materials to produce the plastic waste pyrolysis oil.

[0026] In another aspect, embodiments herein are directed to a system for converting plastic waste into a feedstock for producing recycled plastics. The system includes a plastic waste pyrolysis reactor system configured to pyrolyze a polymeric waste feedstock to produce a plastic waste pyrolysis oil. A catalyst regenerator is provided for regenerating a catalyst mixture comprising a first catalyst and a second catalyst. A first flow line is provided for supplying a portion of the catalyst mixture from the catalyst regenerator to a first reactor system. Similarly, a second flow line is provided for supplying a portion of the catalyst mixture from the catalyst regenerator to a second reactor system. The first reactor system is configured to contact a fossil-based feedstock with the catalyst mixture to crack a portion of the fossil-based feedstock, thereby producing a first effluent comprising fossil-derived olefins, the first catalyst, and the second catalyst. The second reactor system is configured for contacting the plastic waste pyrolysis oil with a concentrated catalyst mixture in a reactor to crack a portion of the plastic waste pyrolysis oil, the concentrated catalyst mixture comprising a portion of the catalyst mixture supplied to the second reactor system and an additional second catalyst, such that the catalyst mixture in the second reactor system has a higher concentration of second catalyst than in the catalyst regenerator or the first reactor, and the contacting produces a second reactor effluent comprising waste-derived olefins and other hydrocarbons, the first catalyst, and the second catalyst; separating the second reactor effluent to produce a first stream comprising the first catalyst and the waste-derived olefins and other hydrocarbons, and a second stream comprising the second catalyst; and supplying the second stream to the second reactor as the additional second catalyst, thereby enriching the second catalyst in the second reactor system. The system further includes a first separation system for separating the first effluent to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a first reactor system product stream comprising the fossil-derived olefins.Another separation system is provided for separating the first stream to recover (i) the spent first catalyst and (ii) a second reactor system product stream containing the waste-derived olefins and other hydrocarbons. Flow lines are also provided for supplying (i) a mixture of the spent first catalyst and the spent second catalyst and (ii) the spent first catalyst to the catalyst regenerator, respectively. In some embodiments, the system includes a first fractionation system and a second fractionation system. The first separation system is configured to separate the first reactor system product stream to recover two or more fossil-derived hydrocarbon fractions. The second fractionation system is configured to separate the second reactor system product stream to recover two or more waste-derived hydrocarbon fractions. Other embodiments of the system may include a polymerization system configured to directly or indirectly receive one or more of the two or more waste-derived hydrocarbon fractions or monomers obtained from processing one or more of the two or more waste-derived hydrocarbon fractions to produce recycled polymers.

[0027] In some aspects, embodiments herein are directed to a system for converting plastic waste into a feedstock for producing plastics. The system may include a pyrolysis reactor system for pyrolyzing a polymer waste feedstock to produce a polymer waste pyrolysis oil having a concentration of one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine. A catalyst regenerator regenerates a catalyst mixture including a first catalyst and a second catalyst, the second catalyst being configured to capture the one or more contaminants. A flow line supplies a portion of the catalyst mixture from the catalyst regenerator to a first reactor system. Another flow line supplies a portion of the catalyst mixture from the catalyst regenerator to a second reactor system. The first reactor system is configured to contact a fossil-based feedstock with the catalyst mixture to crack a portion of the fossil-based feedstock and produce a first effluent including fossil-derived olefins, the first catalyst, and the second catalyst. The second reactor system is configured to contact the plastic waste pyrolysis oil with a high-concentration catalyst mixture in a first-stage reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil. The high-concentration catalyst mixture includes a portion of the catalyst mixture supplied to the second reactor system and an additional second catalyst. Thus, the catalyst mixture in the first-stage reactor has a higher concentration of the second catalyst than in the catalyst regenerator. Furthermore, the contact produces a first-stage reactor effluent containing treated plastic waste pyrolysis oil with reduced contaminant concentrations, the first catalyst, and the second catalyst containing captured contaminants. The first reactor system may also include a separator for separating the first-stage reactor effluent to produce a first stream containing the first catalyst and treated plastic waste pyrolysis oil with reduced contaminant concentrations, and a second stream containing the second catalyst. A flow line may be provided for supplying the second stream to the first stage reactor as the additional second catalyst, thereby enriching the second catalyst in the first stage reactor.The reactor system may further include a flow line for supplying the first stream to a second-stage reactor to crack the treated plastic waste pyrolysis oil and recovering a second-stage reactor effluent containing spent catalyst and waste-derived olefins and other waste-derived hydrocarbons. A first separation system is configured to separate the first effluent to recover (i) a mixture of spent first catalyst and spent second catalyst and (ii) a first reactor system product stream containing the fossil-derived olefins. A second separation system is configured to separate the second-stage reactor effluent to recover (i) the spent catalyst and (ii) a second-stage reactor system product stream containing the waste-derived olefins and other waste-derived hydrocarbons, and flow lines are provided to supply (i) the mixture of spent first catalyst and spent second catalyst and (ii) the spent catalyst to the catalyst regenerator, respectively. In some embodiments, the system further includes a first fractionation system and a second fractionation system. The first fractionation system is configured to separate the first reactor system product stream to recover two or more fossil-based hydrocarbon fractions. The second fractionation system is configured to separate the second stage reactor system product stream and recover two or more waste-derived hydrocarbon fractions. In some embodiments, the system may be configured to maintain the fossil-based hydrocarbon fraction recovered from the first reactor system separately from the waste-derived hydrocarbon product recovered from the second reactor system. Various embodiments also include a polymerization system configured to directly or indirectly receive monomers recovered from or derived from the waste-derived hydrocarbon product to produce a cyclic polymer. Some embodiments of the system include a flow line for feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the first reactor of the second reactor system, while others include a flow line for feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the second reactor of the second reactor system. A flow line may be provided for withdrawing a portion of the second catalyst from the first reactor.

[0028] In another aspect, embodiments herein are directed to a system for converting plastic waste materials into recycled polymers. The system may include a plastic waste pyrolysis reactor for pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil having a concentration of one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine. A catalyst regenerator is provided for regenerating a catalyst mixture including a first catalyst and a second catalyst, the second catalyst configured to capture the one or more contaminants. The system includes a flow line for supplying a portion of the catalyst mixture to a first reactor system and a flow line for supplying a portion of the catalyst mixture to a second reactor system. The first reactor system contacts the plastic waste pyrolysis oil with a high-concentration catalyst mixture in a first reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil, the high-concentration catalyst mixture comprising a portion of the catalyst mixture supplied to the first reactor system and an additional second catalyst, such that the catalyst mixture in the first reactor system has a higher concentration of second catalyst than in the catalyst regenerator, and the contacting produces treated plastic waste pyrolysis oil having reduced contaminant concentrations, the first catalyst, and a separation system configured to supply the second stream to the first reactor as the additional second catalyst, thereby enriching the second catalyst in the first reactor system, and recovering a first separated effluent containing the spent first catalyst and a second separated effluent containing the treated plastic waste pyrolysis oil. A fractionation system is used to fractionate the treated waste pyrolysis oil into three or more hydrocarbon fractions, including a light olefin fraction, a naphtha fraction, and a treated pyrolysis oil fraction.The system includes a flow line for supplying at least one of the naphtha fraction and the treated pyrolysis oil fraction to a second reactor system. The second reactor system is configured to contact at least one of the naphtha fraction and the heavy oil fraction with the catalyst mixture to crack a portion of the hydrocarbons contained therein, thereby producing a second reactor system effluent comprising waste-derived olefins, a first catalyst, and a second catalyst. A separation system is provided for separating the second reactor system effluent to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a second reactor system product stream comprising the waste-derived olefins. The system further includes flow lines for supplying each of (i) the mixture of spent first catalyst and spent second catalyst, and (ii) a first separation effluent comprising the spent first catalyst, to the catalyst regenerator.

[0029] In yet another aspect, embodiments herein are directed to a system for producing a feedstock for producing truly recycled polymers. The system may include a first reactor system including a first-stage reactor and a second-stage reactor. A polymer waste mixture is fed to the first-stage reactor to pyrolyze the contained polymers and recover a pyrolysis effluent. A waste-derived plastic pyrolysis oil and a catalyst mixture are fed to the second-stage reactor to crack the contained hydrocarbons and recover an effluent containing the cracked hydrocarbons. The pyrolysis effluent from the first-stage reactor and the effluent from the second-stage reactor are fed via flow lines to a first fractionation system to separate the effluent into two or more waste-derived hydrocarbon streams containing the waste-derived plastic pyrolysis oil and one or more waste-derived olefin fractions. The system further includes a second reactor system configured to process a fossil-based feedstock with the catalyst mixture. A common catalyst regenerator is provided and configured to feed the catalyst mixture to each of the first and second reactor systems. A flow line is configured for recovering an effluent containing fossil-based hydrocarbon products from the second reactor system. A second fractionation system is provided and configured for separating the effluent containing fossil-based hydrocarbon products. The system further includes a flow line for returning spent catalyst from each of the first and second reactor systems to the common catalyst regenerator. In some embodiments, the catalyst mixture includes a first catalyst and a second catalyst, and the second stage reactor is a catalyst concentration reactor system.

[0030] Other aspects and advantages will become apparent from the following description and appended claims. [Brief explanation of the drawings]

[0031] [Figure 1] 1 shows a simplified process flow diagram of a system and method according to one or more embodiments disclosed herein. [Figure 1A]1 shows a simplified process flow diagram of a system and method according to one or more embodiments disclosed herein. [Figure 2] 1 shows a simplified process flow diagram of a system and method according to one or more embodiments disclosed herein. [Figure 3] 1 shows a simplified process flow diagram of a system and method according to one or more embodiments disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0032] Embodiments herein are generally directed to processing waste materials to form virgin feedstocks, such as light olefins and petrochemical intermediates. For example, waste materials, such as plastics, elastomers, and other polymeric materials, are subjected to pyrolysis to break down the polymeric materials and form pyrolysis oil. Methods and systems herein can advantageously process such waste-derived pyrolysis oil to form olefins and petrochemical intermediates. Such olefins and petrochemical intermediates can then be used to reform polymeric materials, including thermoplastics and elastomeric polymers, providing true circular polymers in some embodiments.

[0033] As used herein, the terms "circulated polymer," "circulated plastic," "circulated elastomer," and other similar "circulated" or "recycled" refer to a circular process of producing a polymer from monomer components such as ethylene or propylene, producing and using consumer goods formed from the polymer to obtain waste (post-consumer) polymeric material, and then converting the waste polymeric material back into its monomer components, which are then converted back into polymers and converted into consumer goods. Embodiments herein are largely directed to the conversion of waste polymeric material back into its monomer components.

[0034] Embodiments herein for converting waste materials may include stand-alone systems that are particularly directed to methods for producing feedstocks that can be used to produce truly circular polymers. Other embodiments herein for converting waste materials may include systems integrated with processes for converting fossil-based materials into products such as olefins, fuels, and the like, typically produced in refineries. In some embodiments, systems for converting fossil-based materials may be adapted to further process the waste-based materials described herein.

[0035] Starting with an integrated system and process, embodiments herein may include a first reactor system for catalytically converting waste-based materials, a second reactor system for catalytically converting fossil-based materials, and a common catalyst regeneration system for regenerating the catalyst mixture used in each of the first and second reactor systems. A waste-derived hydrocarbon stream, such as plastic waste pyrolysis oil, may be fed to the first reactor system and contacted with the catalyst mixture to crack the contained hydrocarbons into lighter waste-derived hydrocarbons. A fossil-based feedstock, such as a fuel oil fraction or other various hydrocarbon cuts derived directly or indirectly from crude oil, may be fed to the second reactor system and contacted with the catalyst mixture to crack the contained hydrocarbons into lighter fossil-derived hydrocarbons. The catalyst mixture fed to each of the first and second reactor systems may be provided from a common catalyst regenerator. An effluent containing fossil-based hydrocarbon products and spent catalyst may be recovered from the second reactor system. Similarly, an effluent containing waste-derived hydrocarbon products and spent catalyst may be recovered from the first reactor system. After separation of the respective effluents, the spent catalyst from each of the first and second reactor systems may be returned to a common catalyst regenerator for regeneration and reuse within the reactor.

[0036] In some embodiments, the reactor effluent may be fed to a common fractionation system for processing the hydrocarbon products, however, such embodiments may result in the commingling of waste-derived and fossil-derived hydrocarbons.

[0037] In other embodiments, the fossil-based hydrocarbon product recovered from the first reactor system may be maintained and processed separately from the waste-derived hydrocarbon product recovered from the second reactor system. In this manner, the waste-derived hydrocarbon product may be provided as a purely recycled product, and the consumer goods derived therefrom may be provided as a truly recycled product. For example, the olefin fraction recovered from the waste-derived hydrocarbon product may be fed to a polymerization system to produce recycled polymer.

[0038] Waste-derived hydrocarbon streams useful in embodiments herein may be obtained from any number of sources. In some embodiments, for example, the waste-derived hydrocarbon stream may be formed by pyrolyzing a waste stream containing polymeric materials, such as thermoplastics, tires, or other polymeric materials, to produce plastic waste pyrolysis oil.

[0039] Polymers that can be pyrolyzed to form plastic waste pyrolysis oil can include thermoplastics, thermosetting resins, and elastomers. For example, waste materials that undergo pyrolysis to form plastic waste pyrolysis oil can include polystyrene, polypropylene, polyphenylene sulfide, polyphenylene oxide, polyethylene, polyetherimide, polyetheretherketone, polyoxymethylene, polyethersulfone, polycarbonate, polybenzimidazole, polylactic acid, nylon, and acrylic polymers such as polymethyl methacrylic acid (PMMA), among many other thermoplastics. Plastic waste pyrolysis oil useful herein can be formed from a variety of unsaturated or saturated elastomers and rubbers known in the art, such as polybutadiene, isoprene, styrene-butadiene, ethylene vinyl acetate, and many others. While embodiments herein may be robust enough to process some amounts of heteroatom-containing polymers, including those listed above and others known in the art, the heteroatom content of the resulting plastic waste pyrolysis oil should typically be less than 2 wt%, e.g., less than 1 wt% or less than 0.5 wt%.

[0040] The pyrolysis of the polymer waste material described above may be carried out by thermal or catalytic pyrolysis of the polymer waste material. For example, thermal pyrolysis of plastic feedstock may be carried out by contacting the plastic feedstock at an elevated temperature, for example, a temperature in the range of 300°C to 850°C, for example, from about 350°C to about 600°C. The pyrolysis of plastics can produce a variety of hydrocarbons, including light gaseous hydrocarbon products and liquid hydrocarbon products, all or a portion of which may be used as the plastic waste pyrolysis oil herein.

[0041] Polymeric materials are typically processed to produce end products, where polymerization catalysts and various additives, such as metal colorants and crosslinkers, are retained in the resulting polymer, but these introduce various contaminants, such as iron, calcium, and sulfur, among others, into the pyrolysis process. The polymer itself may also contain various atoms, such as oxygen, nitrogen, chlorine, and fluorine, that may be considered contaminants in typical cracking processes. Embodiments herein may pretreat plastic waste pyrolysis liquid to remove some or most of these contaminants. In other embodiments, the methods herein may be robust enough to advantageously convert plastic waste pyrolysis liquid without such costly pretreatment.

[0042] Converting waste materials into olefins and petrochemicals and then into finished consumer goods may provide truly recycled product generation, with the resulting waste and waste products then being converted back into valuable light olefins and petrochemicals using the resulting waste products as feedstocks. Embodiments herein also contemplate "green" production, where the feedstock to the waste reactor may include bio-based oils, biomass, biowaste materials, and other renewable feedstocks that can be cracked to produce olefins, such as propylene and ethylene, among others, and / or other petrochemical intermediates. The use of such materials may allow the produced olefins and other petrochemicals, and the consumer goods made therefrom, to be classified as non-fossil-derived products, while providing feedstock flexibility.

[0043] The integrated methods herein may process separate waste-derived and fossil-derived feeds using a common catalyst regenerator, as described above. Fossil-derived feeds that may be processed by embodiments herein may include crude oil or any number of hydrocarbon fractions produced directly or indirectly therefrom. For example, embodiments herein may crack fossil-derived hydrocarbons, including those having a boiling point of about 200° C. or 250° C. or less, or any fraction thereof, such as one or more light hydrocarbon fractions, e.g., naphtha fractions, and / or those having a boiling point in the range of about 200° C. or 250° C. to about 600° C. or 700° C., or any fraction thereof, such as one or more heavy hydrocarbon fractions, e.g., atmospheric gas oil, vacuum gas oil, diesel, and atmospheric or vacuum resid, among others.

[0044] Catalysts useful in embodiments herein may include various fluid catalytic cracking (FCC) catalysts. Suitable FCC catalysts may include Y-type zeolites, X-type zeolites, mordenite, faujasite, nanocrystalline zeolites, and MCM mesoporous materials, among others known in the art. Typically, such catalysts are selected for cracking heavier hydrocarbons.

[0045] Additive-type cracking catalysts may include various medium pore zeolites, such as the pentasil family of zeolites (e.g., ZSM-5 or ZSM-11). Typically, such catalysts are selected for cracking lighter hydrocarbons, such as C4 and naphtha range hydrocarbons, for the production of light olefins, such as ethylene, propylene, and butenes.

[0046] Embodiments herein may also employ pollutant-trapping additives (scavenging catalysts, passivators, etc.). Useful pollutant-trapping additives are compounds and structures that have a higher affinity for pollutants than FCC or additive-type cracking catalysts under reaction conditions. Thus, pollutants may be preferentially absorbed or retained on the pollutant-trapping additive. Pollutant-trapping additives may include MgO, CaO, CeO2, MgTiO3, CaTiO3, Li2Ti2O7, and ZnTiO3, Ca / Mg, boron, and other rare earth-based scavenging additives. Useful pollutant-trapping additives may include low-chlorine FCC catalysts, among others.

[0047] As mentioned above, various contaminants may be found in the plastic waste pyrolysis oil used. Contaminants that may be found in various plastic waste pyrolysis oil feedstocks may include one or more of iron, copper, calcium, phosphorus, vanadium, nickel, sodium, and chlorine, among others. Such contaminants may adversely affect the performance of catalysts, such as cracking catalysts, including FCC catalysts, used to convert heavier hydrocarbons to lighter hydrocarbons. Various contaminants may poison the cracking catalyst, reducing its activity and / or necessitating increased daily additions of fresh catalyst to the process. Contaminants may also clog pores or reduce the diffusivity of the catalyst pores, inhibiting the effectiveness of the catalyst.

[0048] The pollutant-trapping additive should have a higher affinity for the pollutants than the catalyst, as discussed above. Therefore, the specific type of pollutant-trapping additive used may depend on the specific pollutants being targeted. Pollutant-trapping additives useful in some embodiments disclosed herein may include commercially available vanadium / nickel / iron scavengers (additives) manufactured by FCC catalyst vendors.

[0049] Embodiments herein may utilize a mixture of an FCC catalyst and an additive cracking catalyst. Other embodiments herein may utilize a mixture of an FCC catalyst and a metal / pollutant trap catalyst. Still other embodiments may utilize a mixture of an FCC catalyst, an additive cracking catalyst, and a trap catalyst.

[0050] Although a homogeneous mixture of the various catalysts used is recycled from the catalyst regenerator, embodiments herein may desirably enrich one or more of the catalysts in the reactor. For example, it may be desirable to increase the concentration of additive cracking catalyst or scavenging catalyst in a reactor vessel so that the reactions occurring in that vessel are enhanced relative to the enriched catalyst, thereby taking advantage of the enriched catalyst to improve reactor dynamics.

[0051] Embodiments herein may advantageously thicken the catalyst within the reactor by taking advantage of size and / or density differences between each catalyst type. For example, a first catalyst, such as a Y-based zeolite, may have a particle size in the range of 20 to 200 microns and an apparent bulk density in the range of 0.60 to 1.0 g / ml. A second catalyst, such as ZSM-5 or ZSM-11, may have a particle size in the range of 20 to 350 microns and an apparent bulk density in the range of 0.7 to 1.2 g / ml. Such catalysts may be separated based on one or both of size and density, and the heavier or denser catalyst may be advantageously recycled to the reactor and thickened therein. Such catalyst separation and concentration within the reactor may, in some embodiments, be carried out using methods and systems described, for example, in U.S. Pat. Nos. 10,450,514, 10,758,883, 10,351,786, or 9,452,404 (each of which is incorporated by reference herein to the extent consistent with embodiments herein).

[0052] The waste-based feedstock reactor system and the fossil-based feedstock reactor system may each receive the same catalyst mixture from the regenerator. For example, the catalyst mixture may include FCC catalyst and ZSM-5 catalyst in a ratio (weight, volume, particle count, etc.) of 9:1 to 4:1, respectively. By concentrating the larger, denser ZSM-5 catalyst in the waste-based feedstock reactor system according to embodiments herein, the catalyst mixture may circulate through the waste-based feedstock reactor system to achieve an FCC to ZSM-5 ratio of 0.2:1 to 9.5:1, e.g., 1:4. These ratios are merely exemplary, as the catalyst ratio in the regenerator may vary depending on, among other variables, the fossil-based feedstock being processed, the configuration of the fossil-based feedstock reactor system, the respective fresh catalyst feed rates and spent catalyst withdrawal rates, and the fluidization conditions and catalyst separation / recycle variables associated with the waste-based feedstock reactor system (e.g., separation efficiency, recycle rate, fresh catalyst make-up feed rate, spent catalyst withdrawal rate, etc.).

[0053] In certain embodiments, the catalyst mixture contained within and circulated from the regenerator may have a weight ratio of first catalyst to second catalyst ranging from 2:1 to 9:1, where the first catalyst is lighter and / or less dense than the second catalyst. Thus, a riser reactor for converting fossil-based hydrocarbon feedstocks may operate with a similar ratio of first catalyst to second catalyst contained within the regenerator. A reactor for converting waste-based hydrocarbon feedstocks may receive catalysts in a similar ratio to that contained within the regenerator, but operate with a lower ratio of circulating first catalyst to second catalyst than within the regenerator, for example, a ratio ranging from 1:1 to 1:9.

[0054] Referring now to Figure 1, a simplified process flow diagram of a system 1 for converting plastic waste into a feedstock for producing plastics is illustrated. System 1 may include a first reactor system 3 and a second reactor system 5, each of which receives regenerated catalyst 6, 7 from a catalyst regenerator 9 and returns spent catalyst 11, 12 to the catalyst regenerator 9. The catalyst mixture recycled between the regenerator 9 and the reactor systems 3, 5 may be a homogeneous mixture of the first and second catalysts, such as a mixture of an FCC catalyst and an additive catalyst, e.g., a mixture of Y-zeolite and ZSM-5. For example, the regenerator 9 may operate at a temperature ranging from about 600°C to about 750°C and a pressure ranging from about 1 barg to about 5 barg.

[0055] A fossil-derived hydrocarbon feed stream 13 may be fed to the first reactor system 3. The fossil-derived hydrocarbon feed may be one or more hydrocarbon fractions, such as a naphtha fraction, a gas oil fraction, or other hydrocarbon fraction derived from crude oil, as described above.

[0056] The waste-derived hydrocarbon feed stream 15 may be fed to a second reactor system 5 for conversion (cracking) to lighter hydrocarbons. The system may include a pyrolysis reactor (not shown) for pyrolyzing a waste stream, such as a polymer waste feedstock, to produce a waste-derived hydrocarbon feed stream 15, such as a plastic waste pyrolysis oil. For example, a catalytic or non-catalytic plastic pyrolysis unit (not shown) may be used to pyrolyze the polymer waste to produce, among other products (not shown), a plastic waste pyrolysis oil stream 15. Alternatively, the plastic waste pyrolysis oil feedstock 15 may be supplied from a remote source (not shown) and may be fed to the conversion unit of FIG. 1 via, for example, a truck or pipeline.

[0057] Within the first reactor system 3, a fossil-based hydrocarbon feedstock 13 may be contacted with a catalyst mixture to crack a portion of the fossil-based feedstock. The heat required for vaporizing the fossil-based feedstock and / or raising the temperature of the feedstock to a desired reactor temperature, e.g., in the range of 500°C to about 750°C, as well as the heat required for endothermic heating (heat of reaction), may be provided by high-temperature regenerated catalyst from the regenerator 9. The pressure within the first reactor system 3, which may include a riser reactor, is typically in the range of about 1 barg to about 5 barg. Because the heat of reaction reduces the temperature along the length of the reactor, the reactor may start at a temperature that may be favorable for cracking hydrocarbons in the C4, C5, and naphtha ranges, e.g., 600°C to 750°C, and may be reduced to a lower reactor temperature that may be favorable for cracking heavier hydrocarbon feedstocks, e.g., 475°C to 520°C. Thus, various feeds to the reactor may be introduced along the length of the reactor where conditions are favorable for their processing.

[0058] An effluent 17 may be recovered from reactor system 3, this effluent containing fossil-derived olefins (cracked hydrocarbon products), the first catalyst, and the second catalyst. The effluent 17 may then be quenched, if desired, and forwarded to separation system 19 to separate the first effluent to recover (i) a mixture of spent first catalyst and spent second catalyst 11 and (ii) a first reactor system product stream 21 containing fossil-derived olefins and other fossil-derived hydrocarbon products resulting from processing the fossil-based hydrocarbon feedstock 13. The spent catalyst mixture 11 may then be returned to catalyst regenerator 9 for regeneration and reuse in the reactor. When quenching is used, a hydrocarbon feed, such as heavy vacuum gas oil, atmospheric bottoms, heavy hydrocarbon resid feed, light cycle oil (LCO), and / or steam may be injected as a quenching medium.

[0059] After separation of the spent catalyst 11 from the fossil-derived hydrocarbon product 21, the fossil-derived hydrocarbon product may be advanced to fractionation system 23, where the fossil-derived hydrocarbons may be fractionated into any number of separate fossil-derived hydrocarbon fractions based on boiling point. As shown, fossil-derived hydrocarbon product stream 21 may be fractionated in fractionation system 23 to recover an ethylene-containing fraction 25, a propylene-containing fraction 27, a butene-containing fraction 29, a C5 fraction 31, a naphtha fraction 33, a light cycle oil fraction 35, and a slurry oil fraction 37. Each of these fractions may be further processed or recovered for sale as a product fraction. For example, the naphtha fraction may be processed to recover aromatics for use in the gasoline pool and / or recycled to reactor system 3 to convert naphtha-range hydrocarbons to additional ethylene and propylene. As another example, the C5 fraction may be used for the gasoline pool and / or fed to an olefin conversion unit (not shown) or recycled back to reactor system 3 to convert the contained C5s into additional ethylene and propylene.

[0060] Within the second reactor system 5, a waste-derived hydrocarbon stream 15, such as plastic waste pyrolysis oil, may be contacted with a rich catalyst mixture formed from the regenerated catalyst mixture 6 provided from the regenerator 9. Contact with the rich catalyst mixture within the reactor system 5 may crack a portion of the waste-derived hydrocarbons to produce a second reactor system effluent containing waste-derived olefins and other waste-derived hydrocarbons, the first catalyst, and the second catalyst. The heat required for vaporizing the waste-based feedstock and / or raising the temperature of the feed to a desired reactor temperature, e.g., in the range of 500°C to about 750°C, as well as the heat required for endothermic heat (heat of reaction), may be provided by the high-temperature regenerated catalyst from the regenerator 9. The pressure within the second reactor system 5, which may include, for example, a riser reactor, is typically in the range of about 1 barg to about 5 barg. The heat of reaction reduces the temperature along the length of the reactor, so the reactor may start at a temperature that may be favorable for cracking hydrocarbons in the C4, C5, and naphtha ranges, e.g., 600° C. to 750° C., and decrease to a lower reactor temperature that may be favorable for cracking heavier hydrocarbon feedstocks, e.g., 475° C. to 520° C. Thus, various waste-based feeds to the reactor may be introduced along the length of the reactor where conditions are favorable for their processing.

[0061] The catalyst-rich mixture in the second reactor system comprises a portion of the catalyst mixture fed to the second reactor system from the regenerator and additional second catalyst, such that the catalyst mixture in the second reactor system has a higher concentration of second catalyst than in the catalyst regenerator or the first reactor. After conversion in the second reactor system and effluent recovery, the second reactor effluent may be quenched as needed, if desired, and then separated to produce a first stream comprising the first catalyst and waste-derived olefins and other hydrocarbons, and a second stream comprising the second catalyst. The second stream may then be returned to the second reactor system as additional second catalyst, thereby enriching the second catalyst in the second reactor system.

[0062] The second catalyst-depleted first stream may be quenched, if desired, and fed to a catalyst separator to recover (i) a spent first catalyst fraction 12 and (ii) a second reactor system product stream 49 comprising waste-derived olefins and other waste-derived hydrocarbons. The spent catalyst 12 may then be returned to the catalyst regenerator 9 for regeneration and reuse in the reactor. When quenching is used, a waste-based hydrocarbon feed, such as heavy vacuum gas oil, atmospheric bottoms, heavy hydrocarbon resid feed, light cycle oil (LCO), and / or steam may be injected as the quenching medium, such as when the waste-based hydrocarbon quenching is provided by fractionation system 51.

[0063] After separating the spent catalyst 12 from the waste-derived hydrocarbon product 49, the waste-derived hydrocarbon product may be advanced to a fractionation system 51, where the waste-derived hydrocarbons may be fractionated into any number of separate waste-derived hydrocarbon fractions based on boiling point. As shown, the waste-derived hydrocarbon product stream 49 may be fractionated in the fractionation system 51 to recover an ethylene-containing fraction 53, a propylene-containing fraction 55, a butene-containing fraction 57, a C5 fraction 59, a naphtha fraction 61, a light cycle oil fraction 63, and a treated pyrolysis oil fraction 65. Each of these fractions may be further processed or recovered for sale as a waste-derived product fraction. For example, the ethylene and propylene streams, among other hydrocarbon fractions that may be recovered, may be further refined, if necessary, to provide a polymer-grade waste-derived olefin fraction having a purity greater than 99.8%, for example. Such waste-derived olefin fraction may then be provided to a polymerization unit to produce recycled polymer. As another example, the butene-containing fraction 57 or the C4-containing fraction may be further separated and / or processed to produce waste-derived propylene and ethylene, which may then be provided to a polymerization unit to produce recycled polymers. As yet another example, the naphtha fraction 61 may be further purified and / or processed to recover recycled aromatic fractions. The waste-derived aromatics may then be provided to produce aromatic-containing recycled polymers, such as polystyrene, styrene-butadiene rubber (SBR), and many other types of aromatic-containing polymers known in the art. Various product fractions, or portions thereof, may be further processed to provide feedstocks suitable for the production of polyethers, polyesters, and other recycled polymers.

[0064] As can be readily imagined, any of numerous types of recycled polymers can be made from the waste-derived fraction obtained from the pyrolysis and processing of plastic waste according to embodiments herein. Generally, embodiments herein may include directly or indirectly feeding one or more monomers recovered from or derived from the waste-derived hydrocarbon product fraction into a polymerization system to produce a recycled polymer. Among possible recycled polymers, embodiments herein contemplate the production of recycled polymers, including polymers that can be pyrolyzed to form the plastic waste pyrolysis oil described above.

[0065] In some embodiments, the second reactor system 5 may be similar to that illustrated in Figure 1A. The regenerated and mixed first and second catalysts 6 may be fed from a common catalyst regenerator 9 via flow line 71 through control valve 72 to the bottom of a riser reactor 73. At the bottom of the riser reactor 73, the regenerated mixed catalyst is mixed with additional second catalyst fed via flow line 74. The catalyst in flow line 74 may have a higher concentration of a larger and / or heavier second catalyst, such as ZSM-5.

[0066] The mixed catalyst in riser reactor 73, having a higher concentration of larger and / or heavier second catalyst than that supplied in mixture 6 from regenerator 9, may then be contacted with hydrocarbons in secondary riser reactor 73. For example, plastic waste pyrolysis oil feed 5 may be introduced into a lower section of riser reactor 73, and upflow steam, if used, may be supplied to riser reactor 73 via flow line 75. Plastic waste pyrolysis oil may also be supplied to various locations along riser reactor 73 not shown in FIG. 1A, if desired.

[0067] As the cracking reaction occurs in the riser reactor 73, the plastic waste pyrolysis oil feed and steam feed are maintained at flow rates sufficient to entrain both the first and second catalysts along with the cracked hydrocarbon products. The reactor effluent stream containing the catalyst mixture then enters a solids separator (SSD) 77, which may be used to facilitate concentration of a denser and / or larger second catalyst. The SSD 77 may separate the effluent from the riser reactor 73 into a vapor / first catalyst stream 79 and a second catalyst stream 81. The second catalyst recovered from the separator may be recycled back to the riser reactor 73 via flow line 74 to continue reacting and provide an even higher concentration of the second catalyst in the riser reactor 73, as described above.

[0068] The cracked hydrocarbons and first catalyst in flow line 79 may then be fed to a stripper 83 to separate the first catalyst from the cracked hydrocarbon products. The cracked waste-derived hydrocarbon products, including light olefins, C4 hydrocarbons, naphtha range hydrocarbons and heavier hydrocarbons, may be recovered via flow line 49 and then separated to recover the desired waste-derived products or product fractions. The first catalyst 12 may then be recovered from the stripper 83 and returned to the catalyst regenerator.

[0069] In addition to the upwelling steam 75, there may be provision for injecting additional waste-derived feed streams, such as C4 olefins or paraffins, naphtha, or other external streams, as upwelling media / reactants. The locations of such feed streams may be such that they provide preferential conditions for cracking the hydrocarbons contained in the respective streams.

[0070] Although the second reactor system 5 is illustrated in FIG. 1A as including a riser reactor, a solids separator, and a stripper vessel, other configurations for separating and enriching the second catalyst within the reactor may be used. Furthermore, the reactor of the second reactor system is not limited to a riser reactor. In some embodiments, the second reactor system may include a reactor such as a bubbling bed or moving bed reactor, where fluidization is sufficient to carry only the lighter or less dense of the two catalysts out of the reactor, thereby enriching the second catalyst within the reactor and removing the first catalyst along with the hydrocarbon effluent. The enriched second catalyst within the reactor vessel may be withdrawn for regeneration, if necessary.

[0071] In yet other embodiments, the second reactor system 5 may include two or more reactors or reactor systems, such as those shown in Figure 2, where like numbers represent like parts. Multiple reactor systems 5 may be used, for example, to advantageously pretreat contaminated waste-derived pyrolysis oil in a first-stage reactor or reactor system 5A, and then further crack the treated waste-derived pyrolysis oil in a second-stage reactor or reactor system 5B. Additionally, the use of the solids separation concepts discussed above may be used to concentrate additive catalysts, cracking catalysts, and / or capture catalysts in either or both of the first and second stage reactors or reactor systems.

[0072] For example, the regenerated catalyst mixture from the catalyst regenerator 9 may be fed to the mixed-flow turbulent bed / moving bed reactor 5A. A trapped catalyst 89 may be fed to the mixed-flow turbulent bed / moving bed reactor 5A. The trapped catalyst may be formed from particles larger and / or denser than any of the catalysts in the mixed catalyst fed from the regenerator. The flow regime within the reactor 5A may be maintained such that the trapped catalyst forms a turbulent or bubbling bed, while the regenerated mixed catalyst forms a moving bed and flows with the hydrocarbons and other fluidizing gases, with the mixed catalyst and hydrocarbons being recovered as effluent 91 from the first-stage reactor 5A. If desired, the trapped catalyst may be recovered from the reactor system 5A via flow line 93, disposed of, or further processed to recover metals.

[0073] The second-stage reactor system 5B may be similar to that described with respect to Figure 1A and receives a feed mixture 91 comprising the mixed catalyst and treated hydrocarbons. The converted products and catalyst recovered as the second reactor effluent may then be fed to an initial separator to recycle the larger / denser catalyst of the mixed catalyst, allowing for a higher concentration of the larger / denser catalyst in reactor 5B. The converted hydrocarbons and lighter / less dense catalyst may then be separated, the spent catalyst 12 returned to the regenerator 9, and the waste-derived hydrocarbon product may be advanced to fractionation system 51 for processing as described above with respect to Figure 1.

[0074] As shown in Figure 2, a processing scheme integrates the removal of pyrolysis oil feed contaminants with catalytic processing for the production of light olefins and aromatics from waste-derived hydrocarbon streams. This can advantageously enable the treatment and processing of contaminated waste-derived feedstocks, and the ability to increase the concentration of various catalysts, including capture catalysts, can provide a more efficient and cost-effective means of processing waste-derived feedstocks than previously proposed hydroprocessing systems.

[0075] While Figure 2 is described above as including a three-particle system (mixed cracking catalyst + trap catalyst from the regenerator), embodiments herein further contemplate a two-particle, two-stage reactor system in which additive-rich FCC catalyst and trap catalyst are recycled from the regenerator. The resulting contaminant-laden catalyst may be recovered from the first-stage reactor 5A, while the additive-rich FCC catalyst may proceed to the second-stage reactor 5B along with the treated feed steam. The flexibility of the reactor system herein to operate in multiple flow regimes (turbulence, mixing, and transport) allows for various other combinations of particles / catalysts and enrichment of select particles within the reactor stages.

[0076] 2 , a polymer waste feedstock may be pyrolyzed to produce a plastic waste pyrolysis oil 15 having a concentration of one or more contaminants, such as iron, calcium, chlorine, or other contaminants. A catalyst mixture including a first catalyst and a second catalyst may be regenerated in a catalyst regenerator 9, where the second catalyst is configured to capture the one or more contaminants. A first portion of the catalyst mixture may be fed to a first reactor system 3, and a second portion of the catalyst mixture may be fed to a second reactor system 5.

[0077] Within the first reactor system 3, the fossil-based feedstock may be contacted with the catalyst mixture to crack a portion of the fossil-based feedstock to produce a first effluent 17 comprising fossil-derived olefins, the first catalyst, and the second catalyst. The first effluent may then be treated similarly to that described with respect to Figure 1 to separate the first effluent and recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a first reactor system product stream comprising fossil-derived olefins and other fossil-derived hydrocarbon products 21.

[0078] In the second reactor system, the contaminated plastic waste pyrolysis oil may be contacted with a high-concentration catalyst mixture in the first-stage reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil. The high-concentration catalyst mixture may include a portion of the catalyst mixture supplied from the regenerator to the second reactor system and an additional second catalyst. Thus, the catalyst mixture in the first-stage reactor may have a higher concentration of the second catalyst than in the catalyst regenerator 9. Contact of the mixed catalysts in the first-stage reactor 5A may produce a first-stage reactor effluent containing treated plastic waste pyrolysis oil having reduced contaminant concentrations, the first catalyst, and the second catalyst containing the captured contaminants. The first-stage reactor effluent may then be separated to produce a first stream 91 containing the first catalyst and treated plastic waste pyrolysis oil having reduced contaminant concentrations, and a second stream containing the second catalyst. The second stream may then be fed to a second reactor as additional second catalyst, thereby enriching the second catalyst (the capture catalyst) in the first-stage reactor system. The first stream may then be fed to a second-stage reactor to crack the treated plastic waste pyrolysis oil and recover a second-stage reactor effluent containing spent catalyst and waste-derived olefins and other waste-derived hydrocarbons. The second-stage reactor effluent may then be separated to recover (i) the spent catalyst and (ii) a second reactor system product stream 49 containing waste-derived olefins and other waste-derived hydrocarbons.

[0079] Each of (i) the mixture of spent first catalyst and spent second catalyst 11 recovered from reactor system 3 and (ii) the spent catalyst 12 recovered from reactor system 5 may then be fed to a catalyst regenerator to be regenerated and continuously used in the conversion of hydrocarbons.

[0080] 1, it may be desirable to keep the fossil-based hydrocarbon fraction recovered from the first reactor system 3 separate from the waste-derived hydrocarbon products recovered from the second reactor system 5. In this manner, all products from the separation system 51 may be certified and properly accountable as waste-derived products, which may be used, for example, to produce recycled polymers.

[0081] 2, the methods and systems herein may include feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to first stage reactor 5A of second reactor system 5. For example, a light naphtha fraction of C4, C5 or full range naphtha may be fed to first stage reactor 5A, which may operate at conditions preferential for cracking of lighter hydrocarbons.

[0082] Additionally, the methods and systems herein contemplate feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to second-stage reactor 5B of the second reactor system. For example, a heavy naphtha fraction or other heavier hydrocarbon fraction may be fed to second-stage reactor 5B, which may operate under conditions that favor cracking of the heavier hydrocarbons.

[0083] The reaction conditions in each of the reactor systems described with respect to Figure 2 and Figure 3 described below may be similar to those described with respect to Figure 1. For example, regenerator 9 may operate at a temperature in the range of about 600°C to about 750°C and a pressure in the range of about 1 barg to about 5 barg. Reactors for converting fossil-based and waste-based hydrocarbon feedstocks may operate at a temperature in the range of about 450°C to about 750°C. Similarly, the reactor effluent recovered in the embodiments of Figures 2 and 3 may be quenched, if desired.

[0084] As described above with respect to Figure 2, the common regenerator may be configured to supply regenerated catalyst only to the first stage reactor of a two-stage reactor system for processing a waste-derived hydrocarbon feedstock. Other embodiments herein contemplate supplying regenerated catalyst to each of the first stage reactor and the second stage reactor of a two-stage reactor system for processing a waste-derived hydrocarbon feedstock. In yet other embodiments, the second stage reactor system of a two-stage reactor system for processing a waste-derived hydrocarbon feedstock may indirectly receive treated feed from the first stage, such as that shown in Figure 3.

[0085] Referring now to Figure 3, a simplified process flow diagram of a system for processing waste-derived hydrocarbon feed is illustrated, with like numbers representing like parts. In some embodiments, the system of Figure 3 may be used in conjunction with processing fossil-derived hydrocarbons similar to those illustrated in Figures 1 and 2, with reactor system 3 not illustrated in Figure 3. In other embodiments, the system of Figure 3 may be used as a stand-alone system for processing waste-derived hydrocarbons (i.e., not integrated with processing fossil-derived hydrocarbons).

[0086] The embodiment of Figure 3 includes a two-stage reactor system including a first stage reactor system 5A and a second stage reactor system 5B, each of which receives a mixed catalyst (6, 100) from a catalyst regenerator 9. The embodiment of Figure 3 also provides treated waste-derived hydrocarbons indirectly from the first stage reactor system 5A to the second stage reactor system 5B.

[0087] As shown in FIG. 3 , a waste-derived hydrocarbon feed stream 15 may be fed to a first-stage reactor system 5A to convert (crack) the contained hydrocarbons into lighter hydrocarbons through contact with a mixed catalyst system including a first catalyst and a second catalyst. The system may include a pyrolysis reactor (not shown) for pyrolyzing a waste stream, such as a polymer waste feedstock, to produce a waste-derived hydrocarbon feed stream 15, such as a plastic waste pyrolysis oil. For example, a catalytic or non-catalytic plastic pyrolysis unit (not shown) may be used to pyrolyze the polymer waste to produce, among other products (not shown), a plastic waste pyrolysis oil stream 15. Alternatively, the plastic waste pyrolysis oil feedstock 15 may be supplied from a remote source (not shown), for example, via a truck or pipeline, to the conversion unit of FIG. 3 . If the waste-derived hydrocarbon stream 15 is a contaminated waste-derived hydrocarbon stream, in addition to cracking the hydrocarbons in the first-stage reactor 5A, contaminants may be removed from the waste-derived hydrocarbons, such as by being captured by a second catalyst, which may be a capture catalyst.

[0088] Within the first stage reactor system 5A, a waste-derived hydrocarbon stream 15, such as plastic waste pyrolysis oil, may be contacted with a rich catalyst mixture formed from the regenerated catalyst mixture 6 provided from the regenerator 9. Contact with the rich catalyst mixture within the reactor system 5 may crack a portion of the waste-derived hydrocarbons and remove contaminants to produce a first stage reactor system effluent comprising waste-derived olefins and other waste-derived hydrocarbons, the first catalyst, and the second catalyst.

[0089] The enriched catalyst mixture in the first stage reactor system comprises a portion 6 of the catalyst mixture fed to the first stage reactor system 5A from regenerator 9 and additional second catalyst, such that the catalyst mixture in the first stage reactor system 5A has a higher concentration of the second catalyst than in catalyst regenerator 9. After conversion in the first stage reactor system 5A and effluent recovery, the first stage reactor effluent may be separated to produce a first stream comprising the first catalyst and treated waste-derived olefins and other hydrocarbons, and a second stream comprising the second catalyst. The second stream may then be returned to the first stage reactor system 5A as additional second catalyst, thereby enriching the first stage reactor system with the second catalyst.

[0090] The second catalyst-depleted first stream may be fed to a catalyst separator to recover (i) a spent first catalyst fraction 12 and (ii) a first stage reactor system product stream 49 comprising waste-derived olefins and other waste-derived hydrocarbons. The spent catalyst 12 may then be returned to the catalyst regenerator 9 for regeneration and reuse in the reactor.

[0091] After separation of the spent catalyst 12 from the waste-derived hydrocarbon product 49, the waste-derived hydrocarbon product may be advanced to a fractionation system 51, where the waste-derived hydrocarbons may be fractionated into any number of separate waste-derived hydrocarbon fractions based on boiling point. As shown, the waste-derived hydrocarbon product stream 49 may be fractionated in fractionation system 51 to recover an ethylene-containing fraction 53, a propylene-containing fraction 55, a butene-containing fraction 57, a C5 fraction 59, a naphtha fraction 61, a light cycle oil fraction 63, and a treated pyrolysis oil fraction 65.

[0092] The treated waste-derived hydrocarbons may be provided from fractionation system 51 to a second stage reactor system 5B, which may include, for example, a riser reactor. The treated waste-derived fractions that may be fed to second stage reactor system 5B may include, for example, C4 hydrocarbons 57, C5 hydrocarbons 59, naphtha range hydrocarbons 61A, and / or treated pyrolysis oil 65, among others.

[0093] The illustrated treated waste-derived hydrocarbon feedstock or naphtha / unconverted oil 61A and 65 may then be contacted with catalyst mixture 100 in second-stage reactor system 5B to crack a portion of the treated waste-based feedstock. An effluent containing additional waste-derived olefins (cracked hydrocarbon products), the first catalyst, and the second catalyst may be recovered from second-stage reactor system 5B. The effluent from second-stage reactor system 5B may then be forwarded to separation system 109 to separate the effluent and recover (i) a mixture of spent first catalyst and spent second catalyst 111 and (ii) a second-stage reactor system product stream 113 containing additional waste-derived olefins and other waste-derived hydrocarbon products obtained from the processing of the treated waste-based hydrocarbon feedstocks 61A, 65. The spent catalyst mixture 111 may then be returned to catalyst regenerator 9 for regeneration and reuse in the reactor.

[0094] After separation of the spent catalyst 111 from the treated waste-derived hydrocarbon product 113, the treated waste-derived hydrocarbon product 113 may be advanced to fractionation system 51 for separation along with the vapor product 49 recovered from first stage reactor system 5A.

[0095] In some embodiments of the process shown in FIG. 3, the first-stage reactor system 5A may be a catalytic pyrolysis reactor for converting polymeric waste materials into plastic waste pyrolysis oil. For example, catalytic pyrolysis of plastic feedstocks may be carried out by contacting the plastic feedstock with a suitable plastic pyrolysis catalyst at elevated temperatures, such as temperatures ranging from 350°C to 850°C, e.g., from about 400°C to about 750°C. In some embodiments, the pyrolysis catalyst may include individual components or mixtures of spent FCC and / or ZSM-5 catalysts. These catalysts / additives may be modified to provide desired objectives, such as reactivity and / or adsorption capacity for selected reactants, metals, or contaminants. The pyrolysis of plastics may produce various hydrocarbons, including light gaseous and liquid hydrocarbon products. The pyrolysis products may then be fed to a fractionation system 51 to separate various hydrocarbon fractions, including portions used as plastic waste pyrolysis oil and other waste-based feeds, which may be fed to one or more second-stage reactor systems 5B, which may include a catalyst enrichment reactor according to embodiments herein. As mentioned above, the regenerator that provides catalyst to second reactor system 5B may also provide catalyst to a fossil-based reactor system (not shown), which may be similar to that described with respect to reactor system 3 of FIG. 1, for example.

[0096] Example 1 This example illustrates the catalytic cracking performance of the reaction system described herein. Experiments were conducted in a circulating fluidized bed (CFB) pilot plant using a combination of ultrastable Y zeolite (USY) catalyst and ZSM-5 additive to convert pyrolysis oil. The basic properties of the feedstock obtained from the conversion of plastic waste processed in the pyrolysis unit are shown in Table 1. Feed A is a naphtha range feed, while Feed B is a blend of naphtha and heavy oil.

[0097] The potential of various feedstocks from recycling plastic waste to maximize light olefins was investigated. The first performance data set from the pilot plant experiments reported in Table 2 corresponds to the naphtha feed, Feed A, as defined in Table 1, while the second set corresponds to Feed B. As can be seen in Table 2, catalytic cracking of the pyrolysis oil feed resulted in very high yields of ethylene, propylene, and butylenes. Both types of feedstocks showed similar results, demonstrating the potential of these feedstocks to produce truly recyclable petrochemical building blocks using the processes disclosed herein.

[0098] The experimental data also demonstrates distinct features of embodiments herein, where catalysts, methods, and hardware may be tailored to favor catalytic reactions to maximize light olefins (ethylene, propylene, and butylenes) while simultaneously reducing the ecological and environmental impacts from plastic waste. This example clearly demonstrates the catalyst, reactor conditions, and mechanism for cracking these unconventional feeds into light olefins using the system described herein.

[0099] [Table 1]

[0100] [Table 2]

[0101] Example 2 In these experiments, a blend of liquid oil (naphtha range and heavy oil) products from a thermal cracking process unit was subjected to catalytic cracking in the presence of a USY and ZSM-5 catalyst blend in a CFB pilot plant at the conditions set forth in Table 3 below. From the data presented in Table 3, it is clear that increased reactor temperatures of 1050°F to 1100°F, coupled with a relatively high C / O ratio, resulted in higher yields of light olefins (propylene, ethylene, and butylenes). Also, at the conditions provided for Cases C and D, the thermal cracking-derived oil exhibited higher olefin production potential, reflecting conditions favorable for maximizing light olefins.

[0102] [Table 3]

[0103] As described above, embodiments herein provide systems and methods that can provide a truly circular solution for plastics recycling. By utilizing a single regenerator-dual catalyst (SRDC) reaction system associated with an FCC unit but with its own separate product section, or a stand-alone destination production unit integrated with a pyrolysis unit, the resulting product may be 100% circular. Furthermore, due to the characteristics of the fluidized-bed catalytic reactor, it can be economically sized to receive product from pyrolysis units of essentially any capacity, such as pyrolysis units with smaller capacities of 600 tons / day or more.

[0104] Embodiments herein also help address the economic feasibility factor of feedstock acquisition and processing costs. Because of the FCC platform, and more importantly the SRDC platform, systems according to embodiments herein have inherent flexibility with respect to feed variability and contaminant content, thus lowering costs associated with sorting and cleaning.

[0105] Therefore, selecting an FCC and / or SRDC platform as the pyrolysis oil conversion step in a downstream facility addresses the factors listed above regarding pyrolysis oil quantity and quality requirements. Embodiments herein using these platforms can also eliminate the need for hydrotreating and hydroprocessing, minimizing the impact on existing operations. The ability of the systems herein to achieve high concentrations of selected catalysts within the reactor system while using a single regenerator allows for the processing of contaminated feedstocks and waste-derived hydrocarbons of various compositions, far different from typical fossil-based hydrocarbon streams, offering significant advantages over fossil-based hydrocarbon dilution and steam cracking, as well as advantages over FCC systems that may include a parallel plastic pyrolysis oil riser reactor.

[0106] A further advantage of embodiments herein relates to the revenue factor from product sales. By utilizing an SRDC unit bolted to an FCC unit but with its own separate product section, or a stand-alone end-production unit integrated with a thermal cracking unit, the products could be 100% recycled. The olefins and other valuable products obtained from embodiments herein can be 100% recycled and highly concentrated, and such products can command a premium, thus supporting the economic viability of this recycle route.

[0107] Overall, embodiments herein provide the ability to convert plastic waste pyrolysis oil into valuable products by applying an FCC / SRDC platform, whether integrated with existing facilities or in dedicated facilities for purpose-built production. The benefits stem from (1) feedstock quality flexibility, (2) the ability to handle a wider range of compositions and potential contaminants without the need for dilution or blending with fossil-derived naphtha, (3) the ability to produce 100% recycled, premium-priced separated products, (4) good integration and low impact on the operation of existing downstream facilities, and (5) the ability to process both the relatively small amount of pyrolysis oil (650 t / day) produced from currently planned pyrolysis facilities and future, larger-sized pyrolysis oil (over 3,000 t / day) with economies of scale in SRDC or FCC units while maintaining all of the above benefits.

[0108] Unless otherwise defined, all technical and scientific terms used have the same meaning as commonly understood by one of ordinary skill in the art to which these systems, devices, methods, processes and compositions belong.

[0109] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0110] As used in this specification and the appended claims, the words "comprise," "have," and "include," and all grammatical variations thereof, are each intended to have an open, non-limiting meaning that does not exclude additional elements or steps.

[0111] "Optionally" means that the subsequently described event or circumstance may or may not occur. The description includes cases where the event or circumstance occurs and cases where it does not occur.

[0112] When the word "approximately" or "about" is used, this term may mean that the value may vary by up to ±10%, up to 5%, up to 2%, up to 1%, up to 0.5%, up to 0.1%, or up to 0.01%.

[0113] Ranges may be expressed as from about one particular value to about another particular value, inclusive of those values. When such a range is expressed, it is to be understood that another embodiment is from the one particular value to the other particular value, along with all particular values and combinations thereof within that range.

[0114] While the present disclosure includes a limited number of embodiments, those skilled in the art, having the benefit of this disclosure, will recognize that other embodiments may be devised that do not depart from the scope of the present disclosure, which scope, therefore, should be limited only by the appended claims.

Claims

1. 1. A method for producing a feedstock for producing truly circular polymers, comprising: treating the plastic waste pyrolysis oil with a catalyst mixture in a first reactor system; treating a fossil-based feedstock with said catalyst mixture in a second reactor system; supplying the catalyst mixture to each of the first and second reactor systems from a common catalyst regenerator; recovering an effluent from said second reactor system comprising fossil-based hydrocarbon products; recovering an effluent from the first reactor system comprising waste-derived hydrocarbon products; and returning spent catalyst from each of said first and second reactor systems to said common catalyst regenerator. A method comprising:

2. 10. The method of claim 1, further comprising maintaining the fossil-based hydrocarbon products recovered from the first reactor system separate from the waste-derived hydrocarbon products recovered from the second reactor system.

3. 3. The method of claim 2, further comprising feeding the olefin fraction recovered from said waste-derived hydrocarbon product into a polymerization system to produce recycled polymer.

4. 4. The method of any one of claims 1 to 3, further comprising pyrolyzing a waste stream comprising plastic, tires or other polymeric materials to produce said plastic waste pyrolysis oil.

5. 5. The method of any one of claims 1 to 4, further comprising feeding one or more of said waste-derived hydrocarbon products, or waste-derived monomers obtained from processing said waste-derived hydrocarbon products, directly or indirectly to a polymerization process to produce a recycled polymer.

6. 1. A method for converting plastic waste into a feedstock for producing plastics, comprising: pyrolysis of the polymer waste feedstock to produce plastic waste pyrolysis oil; regenerating a catalyst mixture comprising the first catalyst and the second catalyst in a catalyst regenerator; feeding a portion of said catalyst mixture into a first reactor system; feeding a portion of the catalyst mixture into a second reactor system; contacting a fossil-based feedstock with the catalyst mixture in the first reactor system to crack a portion of the fossil-based feedstock to produce a first effluent comprising fossil-derived olefins, a first catalyst, and a second catalyst; In the second reactor system, contacting the plastic waste pyrolysis oil with a concentrated catalyst mixture in a reactor to crack a portion of the plastic waste pyrolysis oil, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture provided to the second reactor system and an additional second catalyst, such that the catalyst mixture in the second reactor system has a higher concentration of second catalyst than in the catalyst regenerator or the first reactor system, and wherein the contacting produces a second reactor effluent comprising waste-derived olefins and other hydrocarbons, the first catalyst, and the second catalyst; separating the second reactor effluent to produce a first stream comprising the first catalyst and the waste-derived olefins and other hydrocarbons, and a second stream comprising the second catalyst; feeding the second stream to the second reactor as the additional second catalyst, thereby enriching the second catalyst in the second reactor system; separating the first effluent to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a first reactor system product stream comprising the fossil-derived olefins; separating the first stream to recover (i) spent first catalyst and (ii) a second reactor system product stream comprising the waste-derived olefins and other waste-derived hydrocarbons; and (i) feeding a mixture of the spent first catalyst and the spent second catalyst, and (ii) feeding the spent first catalyst to the catalyst regenerator. A method comprising:

7. 7. The method of claim 6, wherein the first catalyst comprises one or more selected from the group consisting of amorphous silica alumina, Y-type zeolite, X-type zeolite, zeolite beta, zeolite MOR, mordenite, faujasite, nanocrystalline zeolite, and MCM mesoporous material.

8. The second catalyst is an additive cracking catalyst or a mixture of additive cracking catalysts selected from the group consisting of medium pore zeolites and pentasil zeolites; or MgO, CaO, CeO ２ , MgTiO ３ , CaTiO ３ , Li ２ Ti ２ O ７ and ZnTiO ３ , Ca / Mg, boron, rare earth based scavenging additives or mixtures of pollutant scavenging additives selected from the group consisting of low chlorine FCC catalysts.

8. The method of claim 6 or claim 7, comprising one or both of:

9. feeding the first reactor system product stream to a first fractionation system to separate the first reactor system product stream to recover two or more fossil-derived hydrocarbon fractions; and feeding said second reactor system product stream to a second fractionation system to separate said second reactor system product stream to recover two or more waste-derived hydrocarbon fractions. The method of any one of claims 6 to 8, further comprising:

10. 10. The method of claim 9, further comprising feeding one or more of the two or more waste-derived hydrocarbon fractions, or monomers obtained from processing one or more of the two or more waste-derived hydrocarbon fractions, directly or indirectly to a polymerization process to produce a recycled polymer.

11. the pyrolysis comprising pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil having a concentration of one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine; a catalyst mixture comprising the first catalyst and the second catalyst, the second catalyst being configured to capture the one or more pollutants; The contacting in the second reactor system comprises: contacting the plastic waste pyrolysis oil with a concentrated catalyst mixture in a first stage reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture provided to the second reactor system and an additional second catalyst, such that the catalyst mixture in the first stage reactor has a higher concentration of second catalyst than in the catalyst regenerator, and the contacting produces a first stage reactor effluent comprising treated plastic waste pyrolysis oil having reduced contaminant concentrations, the first catalyst, and the second catalyst containing captured contaminants; separating the first-stage reactor effluent to produce a first stream comprising the first catalyst and a treated plastic waste pyrolysis oil having the reduced contaminant concentration, and a second stream comprising the second catalyst; feeding the second stream to the first-stage reactor as the additional second catalyst, thereby enriching the second catalyst in the first-stage reactor; and feeding the first stream to a second-stage reactor to crack the treated plastic waste pyrolysis oil and recovering a second-stage reactor effluent containing spent catalyst and waste-derived olefins and other waste-derived hydrocarbons; Including, 11. The method for converting plastic waste into a feedstock for producing plastics according to any one of claims 6 to 10, wherein separating the first stream comprises separating the second-stage reactor effluent to recover (i) spent catalyst and (ii) a second-stage reactor system product stream comprising the waste-derived olefins and other waste-derived hydrocarbons.

12. 12. The method of claim 11, further comprising maintaining the fossil-based hydrocarbon fraction recovered from the first reactor system separate from the waste-derived hydrocarbon product recovered from the second reactor system.

13. 12. The method of claim 11, further comprising feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the first reactor of the second reactor system.

14. 12. The method of claim 11, further comprising feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the second reactor of the second reactor system.

15. 12. The method of claim 11, further comprising withdrawing a portion of the second catalyst from the first reactor.

16. 1. A method for converting plastic waste materials into monomers for producing circular polymers, comprising: Pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil having a concentration of one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine; regenerating a catalyst mixture in a catalyst regenerator, the catalyst mixture including a first catalyst and a second catalyst, the second catalyst configured to capture the one or more pollutants; feeding a portion of said catalyst mixture into a first reactor system; feeding a portion of the catalyst mixture into a second reactor system; in the first reactor system, contacting the plastic waste pyrolysis oil with a concentrated catalyst mixture in a first reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture provided to the first reactor system and an additional second catalyst, such that the catalyst mixture in the first reactor system has a higher concentration of second catalyst than in the catalyst regenerator, and the contacting produces a first reactor effluent comprising treated plastic waste pyrolysis oil having reduced contaminant concentrations, the first catalyst, and the second catalyst containing captured contaminants; separating the first reactor effluent to produce a first stream comprising the first catalyst and a treated plastic waste pyrolysis oil having the reduced contaminant concentration, and a second stream comprising the second catalyst; feeding the second stream to the first reactor as the additional second catalyst, thereby enriching the second catalyst in the first reactor system; and feeding the first stream to a separation system to recover a first separated effluent containing a spent first catalyst and a second separated effluent containing the treated plastic waste pyrolysis oil; feeding the second separation effluent to a fractionation system to fractionate the treated waste pyrolysis oil into three or more hydrocarbon fractions, including a light olefin fraction, a naphtha fraction, and a treated pyrolysis oil fraction; feeding at least one of the naphtha fraction and the treated pyrolysis oil fraction into a second reactor system; contacting at least one of the naphtha fraction and the heavy oil fraction with the catalyst mixture in the second reactor system to crack a portion of the hydrocarbons contained therein, thereby producing a second reactor system effluent comprising waste-derived olefins, a first catalyst, and a second catalyst; separating the second reactor system effluent to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a second reactor system product stream comprising the waste-derived olefins; and (i) supplying a mixture of the spent first catalyst and the spent second catalyst, and (ii) a first separation effluent containing the spent first catalyst, to the catalyst regenerator. A method comprising:

17. 1. A method for producing a feedstock for producing truly circular polymers, comprising: treating a polymer waste mixture in a first reactor system comprising a first stage reactor and a second stage reactor, said treating said polymer waste mixture comprising: feeding said polymer waste mixture to said first stage reactor to pyrolyze the contained polymers and recovering a pyrolysis effluent; Supplying the waste-derived plastic pyrolysis oil and catalyst mixture to the second-stage reactor to crack the contained hydrocarbons, and recovering an effluent containing the cracked hydrocarbons. including, feeding the pyrolyzed effluent from the first-stage reactor and the effluent from the second-stage reactor to a first fractionation system to separate the effluents into two or more waste-derived hydrocarbon streams comprising the waste-derived plastic pyrolysis oil and one or more waste-derived olefin fractions; treating a fossil-based feedstock with said catalyst mixture in a second reactor system; supplying the catalyst mixture to each of the first and second reactor systems from a common catalyst regenerator; recovering an effluent comprising fossil-based hydrocarbon products from said second reactor system; feeding the effluent containing the fossil-based hydrocarbon product into a second fractionation system; and returning spent catalyst from each of said first and second reactor systems to said common catalyst regenerator. A method comprising:

18. the catalyst mixture comprises a first catalyst and a second catalyst, the second stage reactor is a catalyst enrichment reactor system, and the method comprises: recovering a second-stage reactor effluent comprising said catalyst mixture and said cracked hydrocarbons; separating the second-stage reactor effluent to produce a first stream comprising the first catalyst and the cracked hydrocarbons and a second stream comprising the second catalyst; separating the first stream to recover (i) spent catalyst and (ii) the second-stage reactor effluent that is fed to the first fractionation system; and feeding said second stream to said second stage reactor, thereby concentrating said second catalyst circulating in said second reactor to a higher concentration than said catalyst mixture as received from said regenerator; 18. The method of claim 17, comprising:

19. 19. The method of any one of claims 1 to 18, wherein the polymer waste pyrolysis oil is derived from, or the polymer waste feed or polymer waste mixture comprises, one or more thermoplastic resins selected from the group consisting of polystyrene, polypropylene, polyphenylene sulfide, polyphenylene oxide, polyethylene, polyetherimide, polyetheretherketone, polyoxymethylene, polyethersulfone, polycarbonate, polybenzimidazole, polylactic acid, nylon, acrylonitrile-butadiene-styrene (ABS) polymer, polymethyl methacrylic acid (PMMA); one or more thermosetting resins formed from monomers comprising one or more of acrylic, polyester, vinyl ester, epoxy, urethane, urea, and isocyanate; and one or more unsaturated or saturated elastomers selected from the group consisting of polybutadiene, isoprene, chloroprene, styrene-butadiene, nitrile, and ethylene vinyl acetate.

20. 1. A system for producing raw materials for producing truly circular polymers, comprising: a first reactor system configured for treating plastic waste pyrolysis oil and containing a catalyst mixture; a second reactor system configured to process a fossil-based feedstock with said catalyst mixture; a feed line for feeding the catalyst mixture from a common catalyst regenerator to each of the first and second reactor systems; a flow line for recovering an effluent comprising fossil-based hydrocarbon products from said second reactor system; a flow line for recovering an effluent comprising waste-derived hydrocarbon products from the first reactor system; and a flow line for returning spent catalyst from each of said first and second reactor systems to said common catalyst regenerator; Including, the system.

21. 22. The system of claim 21, further comprising a plastic waste pyrolysis system configured to pyrolyze a waste stream comprising plastic, tires or other polymeric materials to produce said plastic waste pyrolysis oil.

22. 1. A system for converting plastic waste into a feedstock for producing plastics, comprising: a plastic waste pyrolysis reactor system configured for pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil; a catalyst regenerator for regenerating a catalyst mixture comprising the first catalyst and the second catalyst; a first flow line for supplying a portion of the catalyst mixture from the catalyst regenerator to a first reactor system; a second flow line for supplying a portion of the catalyst mixture from the catalyst regenerator to a second reactor system; a first reactor system configured to contact a fossil-based feedstock with the catalyst mixture to crack a portion of the fossil-based feedstock, thereby producing a first effluent comprising fossil-derived olefins, a first catalyst, and a second catalyst; contacting the plastic waste pyrolysis oil with a concentrated catalyst mixture in a reactor to crack a portion of the plastic waste pyrolysis oil, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture provided to the second reactor system and an additional second catalyst, such that the catalyst mixture in the second reactor system has a higher concentration of second catalyst than in the catalyst regenerator or the first reactor, and wherein the contacting produces a second reactor effluent comprising waste-derived olefins and other hydrocarbons, the first catalyst, and the second catalyst; separating the second reactor effluent to produce a first stream comprising the first catalyst and the waste-derived olefins and other hydrocarbons, and a second stream comprising the second catalyst; feeding said second stream to said second reactor as said additional second catalyst, thereby enriching said second catalyst within said second reactor system; the second reactor system configured for a first separation system for separating the first effluent to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a first reactor system product stream comprising the fossil-derived olefins; a separation system for separating the first stream to recover (i) spent first catalyst and (ii) a second reactor system product stream comprising the waste-derived olefins and other hydrocarbons; and a flow line configured to supply each of (i) the mixture of the spent first catalyst and the spent second catalyst and (ii) the spent first catalyst to the catalyst regenerator; Including, the system.

23. a first fractionation system configured to separate the first reactor system product stream to recover two or more fossil-derived hydrocarbon fractions; and a second fractionation system configured to separate the second reactor system product stream to recover two or more waste-derived hydrocarbon fractions; 24. The system of claim 23, further comprising:

24. 25. The system of claim 24, further comprising a polymerization system configured to directly or indirectly receive one or more of the two or more waste-derived hydrocarbon fractions or monomers obtained from processing one or more of the two or more waste-derived hydrocarbon fractions to produce a recycled polymer.

25. 1. A system for converting plastic waste into a feedstock for producing plastics, comprising: a pyrolysis reactor system for pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil having a concentration of one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine; a catalyst regenerator for regenerating a catalyst mixture comprising a first catalyst and a second catalyst, said second catalyst being configured to capture said one or more pollutants; a flow line for supplying a portion of the catalyst mixture from the catalyst regenerator to a first reactor system; a flow line for supplying a portion of the catalyst mixture from the catalyst regenerator to a second reactor system; a first reactor system configured to contact a fossil-based feedstock with the catalyst mixture to crack a portion of the fossil-based feedstock, thereby producing a first effluent comprising fossil-derived olefins, a first catalyst, and a second catalyst; contacting the plastic waste pyrolysis oil with a concentrated catalyst mixture in a first stage reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture provided to the second reactor system and an additional second catalyst, such that the catalyst mixture in the first stage reactor has a higher concentration of second catalyst than in the catalyst regenerator, and the contacting produces a first stage reactor effluent comprising treated plastic waste pyrolysis oil having reduced contaminant concentrations, the first catalyst, and the second catalyst containing captured contaminants; separating the first-stage reactor effluent to produce a first stream comprising the first catalyst and a treated plastic waste pyrolysis oil having the reduced contaminant concentration, and a second stream comprising the second catalyst; feeding the second stream to the first-stage reactor as the additional second catalyst, thereby enriching the second catalyst in the first-stage reactor; and feeding the first stream to a second-stage reactor to crack the treated plastic waste pyrolysis oil and recovering a second-stage reactor effluent containing spent catalyst and waste-derived olefins and other waste-derived hydrocarbons; the second reactor system configured for a first separation system configured to separate the first effluent to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a first reactor system product stream comprising the fossil-derived olefins; a second separation system configured to separate the second-stage reactor effluent to recover (i) spent catalyst and (ii) a second-stage reactor system product stream comprising the waste-derived olefins and other waste-derived hydrocarbons; and a flow line for supplying each of (i) the mixture of the spent first catalyst and the spent second catalyst and (ii) the spent catalyst to the catalyst regenerator; Including, the system.

26. a first fractionation system for separating the first reactor system product stream to recover two or more fossil-derived hydrocarbon fractions; and a second fractionation system for separating the second-stage reactor system product stream and recovering two or more waste-derived hydrocarbon fractions; 26. The system of claim 25, further comprising:

27. 27. The system of claim 26, configured to maintain the fossil-based hydrocarbon fraction recovered from the first reactor system separate from the waste-derived hydrocarbon product recovered from the second reactor system.

28. 28. The system of claim 26 or claim 27, further comprising a polymerization configured to directly or indirectly receive monomers recovered from or derived from the waste-derived hydrocarbon product to produce a recycled polymer.

29. 27. The system of claim 26, further comprising a flow line for supplying one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the first reactor of the second reactor system.

30. 27. The system of claim 26, further comprising a flow line for supplying one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the second reactor of the second reactor system.

31. 27. The method of claim 26, further comprising a flow line for withdrawing a portion of the second catalyst from the first reactor.

32. 1. A system for converting plastic waste materials into circular polymers, comprising: a plastic waste pyrolysis reactor for pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil having a concentration of one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine; a catalyst regenerator for regenerating a catalyst mixture comprising a first catalyst and a second catalyst, said second catalyst being configured to capture said one or more pollutants; a flow line for supplying a portion of the catalyst mixture to a first reactor system; a flow line for supplying a portion of the catalyst mixture to a second reactor system; contacting the plastic waste pyrolysis oil with a concentrated catalyst mixture in a first reactor to remove contaminants from the plastic waste pyrolysis oil and crack a portion of the plastic waste pyrolysis oil, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture provided to the first reactor system and an additional second catalyst, such that the catalyst mixture in the first reactor system has a higher concentration of second catalyst than in the catalyst regenerator, and the contacting produces a first reactor effluent comprising treated plastic waste pyrolysis oil having reduced contaminant concentrations, the first catalyst, and the second catalyst containing captured contaminants; separating the first reactor effluent to produce a first stream comprising the first catalyst and a treated plastic waste pyrolysis oil having the reduced contaminant concentration, and a second stream comprising the second catalyst; the first reactor system configured to supply the second stream to the first reactor as the additional second catalyst, thereby enriching the second catalyst within the first reactor system; and a separation system for recovering a first separated effluent containing a used first catalyst and a second separated effluent containing the treated plastic waste pyrolysis oil; a fractionation system for fractionating the treated waste pyrolysis oil into three or more hydrocarbon fractions, including a light olefin fraction, a naphtha fraction, and a treated pyrolysis oil fraction; a flow line for supplying at least one of the naphtha fraction and the treated pyrolysis oil fraction to a second reactor system; a second reactor system configured to contact at least one of the naphtha fraction and the heavy oil fraction with the catalyst mixture to crack a portion of the hydrocarbons contained therein, thereby producing a second reactor system effluent comprising waste-derived olefins, a first catalyst, and a second catalyst; a separation system configured to separate the second reactor system effluent to recover (i) a mixture of spent first catalyst and spent second catalyst, and (ii) a second reactor system product stream comprising the waste-derived olefins; and a flow line for supplying each of (i) the mixture of the spent first catalyst and the spent second catalyst and (ii) the first separated effluent containing the spent first catalyst to the catalyst regenerator; Including, the system.

33. 1. A system for producing raw materials for producing truly circular polymers, comprising: A first reactor system comprising a first stage reactor and a second stage reactor, feeding said polymer waste mixture to said first stage reactor to pyrolyze the contained polymers and recovering a pyrolysis effluent; supplying the waste-derived plastic pyrolysis oil and catalyst mixture to the second-stage reactor to crack the contained hydrocarbons, and recovering an effluent containing the cracked hydrocarbons; feeding the pyrolyzed effluent from the first stage reactor and the effluent from the second stage reactor to a first fractionation system to separate the effluents into two or more waste-derived hydrocarbon streams comprising the waste-derived plastic pyrolysis oil and one or more waste-derived olefin fractions; a first reactor system configured for a second reactor system configured to process a fossil-based feedstock with said catalyst mixture; a common catalyst regenerator configured to supply said catalyst mixture to each of said first and second reactor systems; a flow line for recovering an effluent comprising fossil-based hydrocarbon products from said second reactor system; a second fractionation system for separating the effluent containing the fossil-based hydrocarbon product; and a flow line for returning spent catalyst from each of said first and second reactor systems to said common catalyst regenerator; Including, the system.

34. 34. The system of claim 33, wherein the catalyst mixture comprises a first catalyst and a second catalyst, and the second stage reactor is a catalyst concentration reactor system.

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