A catalytic cracking method for a true circular solution for converting pyrolysis oil produced from recycled waste plastics into virgin olefins and petrochemical intermediates

Abstract

A method and system for producing a feedstock and for producing a truly circular polymer. The system and method may include treating a waste-derived hydrocarbon stream, such as plastic waste pyrolysis oil, with a catalytic mixture in a first reactor system, and treating a fossil-based feedstock with the catalytic mixture in a second reactor system. The catalytic mixture may be fed 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 an effluent containing waste-derived hydrocarbon products may be recovered from the first reactor system. After separation, the spent catalyst from each of the first and second reactor systems may be returned to the common catalyst regenerator.

Description

Technical Field

[0001] Embodiments of the present disclosure generally relate to recycling waste materials such as plastic waste. More particularly, embodiments herein provide systems and methods for a true circular solution to convert end-of-life plastic materials back into olefins and chemical intermediates that can be useful in generating new plastic materials and compositions.

Background Art

[0002] Thermal pyrolysis of plastic waste regenerates valuable carbon and hydrogen elements from used plastics by converting the used plastics into valuable molecules, which can be upgraded to new chemical intermediates and converted into entirely new consumer goods. Since this process has the potential to repeatedly recycle post-use plastics into new materials, the polymers produced through this process are called circular polymers. This reduces plastic waste in landfills and the environment and replaces the consumption of an equivalent amount of raw materials produced from fossil fuels. However, there are several factors that affect the economic viability of this recycling route.

[0003] Liquid oil products derived from the pyrolysis of plastic waste may not be suitable for feeding into a liquid steam cracking unit or may require treatment or conditioning before being fed into the liquid steam cracking unit. High levels of nitrogen, chlorine, and mono- and diolefins, as well as contaminants such as iron and calcium, may require further consideration or adjustment before being directly added as feedstock to a steam cracking furnace. To make this feedstock suitable for steam cracking, one possible solution may require a hydrogenation treatment step, such as saturating the diolefins first and then the monoolefins, followed by hydrogenation. However, such steps require hydrogen supply, the addition of multiple high-pressure reactors, associated investment (if tanks are not available), and operating costs.

[0004] As an alternative to such an approach, it is conceivable to dilute the negative impact of the properties of the pyrolysis oil by mixing it with a conventional naphtha feedstock and sending it to the cracking unit. However, the olefins and petrochemical intermediates obtained from the cracking of the pyrolysis oil will be mixed with those from the conventional naphtha and will contribute, albeit in small amounts, to the final olefin product, requiring proof that they have a specific recycle content based on a mass balance methodology. However, dilution / mixing with a new hydrocarbon feedstock is only a transitional solution and not a viable long-term solution for a circular plastic economy.

[0005] Another factor affecting the viability of plastic recycling is the limited amount of plastic waste feedstock available through cost-effective channels. Due to infrastructure and logistics limitations, the amount of plastic accessible for recycling is restricted in each geographical location. Most of the current plastic pyrolysis process technologies available are designed to process less than 50 T / day of plastic per train. This is determined not only by the limitations on scaling up but also by the availability of plastic waste. At this scale, the pyrolysis oil produced from one of these units is equal to an amount of 13,000 metric tons per year, but if this were fed into a global-scale naphtha cracking unit, it would constitute only 2 wt% of the total feed to one steam cracking heater. The plastic waste pyrolysis unit capacity is expected to increase in the future to even larger sizes in the range of 1,000 - 2,000 tons / day of plastic feedstock. However, even at these higher capacities, the contribution of the resulting feedstock to the naphtha cracking unit is thought to be only a fraction of the total feed to the steam cracking unit. Therefore, the resulting products will not be 100% circular, and the resulting products are thought to have a very small proportion of recycled components.

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

[0007] Still other factors affecting plastic recycling are that the design throughput of plastic pyrolysis units is typically small, the economies of scale are not exploited, and the associated operating and capital costs are high due to the required product throughput levels. The amount and quality of pyrolysis oil product sent, the preparation required for further processing, and the impact on existing operations make integration with existing downstream facilities difficult. Furthermore, the revenue from the sale of pyrolysis products when blended with fossil-based products is often unfavorable compared to the processing costs and can vary depending on the available markets and prices for various products derived from plastic pyrolysis.

Summary of the Invention

Problems to be Solved by the Invention

[0008] Embodiments of this specification relate to systems and methods for addressing one or more of the problems 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 for plastic waste recycling.

Means for Solving the Problems

[0009] In one aspect, embodiments disclosed herein relate to a method for producing raw materials for generating true 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 a fossil-based hydrocarbon product from the second reactor system, and recovering an effluent containing a waste-derived hydrocarbon product from the first reactor system. After separating the hydrocarbons from the catalyst in the effluent, the method may include returning the 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, separate 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 comprising plastic, tire, or other polymeric material to produce the plastic waste pyrolysis oil. In yet other embodiments, the method may include directly or indirectly feeding one or more of the waste-derived hydrocarbon products, or waste-derived monomers obtained from the treatment of the waste-derived hydrocarbon products, to a polymerization process to produce a recycled polymer.

[0011] In another aspect, embodiments of the present specification are directed to a method for converting plastic waste into a raw material for producing plastics. The method may include pyrolyzing a polymer waste raw material 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 supplied to a first reactor system, and another portion of the catalyst mixture may be supplied to a second reactor system. In the first reactor system, a fossil-based raw material may be contacted with the catalyst mixture to crack a portion of the fossil-based raw material, thereby producing a first effluent including a fossil-derived olefin, the first catalyst, and the second catalyst. In the second reactor system, the plastic waste pyrolysis oil may be contacted with a high-concentration catalyst mixture in the reactor to crack a portion of the plastic waste pyrolysis oil, and 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 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 including a waste-derived olefin and other hydrocarbons, the first catalyst, and the second catalyst. Then, the second reactor effluent may be separated to produce a first stream including the first catalyst and the waste-derived olefin and other hydrocarbons, and a second stream including the second catalyst. The second stream may be supplied to the second reactor as the additional second catalyst, thereby increasing the concentration of the second catalyst in the second reactor system. The first effluent may be separated to recover (i) a mixture of the used first catalyst and the used second catalyst, and (ii) a first reactor system product stream including the fossil-derived olefin. The first stream (the effluent from the second reactor and the used first catalyst) may be separated to recover (i) the used first catalyst, and (ii) a second reactor system product stream including the waste-derived olefin and other waste-derived hydrocarbons.The method may include supplying (i) a mixture of the used first catalyst and the used second catalyst, and (ii) the used first catalyst to the catalyst regenerator, respectively.

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

[0013] In various embodiments, the second catalyst is 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 one or both of a pollutant capture additive or a mixture of pollutant capture additives selected from the group consisting of MgO, CaO, CeO2, MgTiO3, CaTiO3, Li2Ti2O7, and ZnTiO3, Ca / Mg, boron, rare earth-based capture additives, or low-chlorine FCC catalysts.

[0014] The method according to some embodiments may include supplying 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. The method according to the embodiments herein may further include supplying 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 supplying one or more of the two or more waste-derived hydrocarbon fractions to a polymerization process to produce a cyclic polymer.

[0015] In another aspect, embodiments of the present specification relate to a method for converting plastic waste into a raw material for producing plastics. The method may include pyrolyzing a polymer waste raw material to produce a plastic waste pyrolysis oil having one or more contaminants at a certain concentration. 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 including a first catalyst and a second catalyst in a catalyst regenerator, wherein the second catalyst is configured to capture the one or more contaminants. A portion of the catalyst mixture may be supplied to a first reactor system, and another portion of the catalyst mixture may be supplied to a second reactor system. In the first reactor system, a fossil-based raw material may be contacted with the catalyst mixture to crack a portion of the fossil-based raw material, thereby producing a first effluent including a fossil-derived olefin, the first catalyst, and the second catalyst. In the second reactor system, the plastic waste pyrolysis oil may be contacted 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, wherein the high-concentration catalyst mixture includes a portion of the catalyst mixture supplied to the second reactor system and an additional second catalyst, and thus the catalyst mixture in the first-stage reactor has a higher concentration of the second catalyst than in the catalyst regenerator, and the contacting produces a first-stage reactor effluent including a treated plastic waste pyrolysis oil having a reduced contaminant concentration, the first catalyst, and the second catalyst containing the captured contaminants. The first-stage reactor effluent may be separated to produce a first stream including the first catalyst and the treated plastic waste pyrolysis oil having a reduced contaminant concentration, and a second stream including the second catalyst. The second stream may be supplied to the first-stage reactor as the additional second catalyst, thereby increasing the concentration of the second catalyst in the first-stage reactor.The above-mentioned first stream may be fed into a second-stage reactor, and the treated plastic waste pyrolysis oil may be cracked to recover a second-stage reactor effluent containing spent catalysts as well as waste-derived olefins and other waste-derived hydrocarbons. The above-mentioned first effluent may be separated to recover (i) a mixture of the spent first catalyst and the spent second catalyst, and (ii) a first reactor system product stream containing the above-mentioned fossil-derived olefins. Further, the above-mentioned second-stage reactor effluent may be separated to recover (i) the spent catalyst, and (ii) a second-stage reactor system product stream containing the above-mentioned waste-derived olefins and other waste-derived hydrocarbons. The method may include feeding (i) the mixture of the spent first catalyst and the spent second catalyst, and (ii) the spent catalyst respectively into the catalyst regenerator.

[0016] In some embodiments, the method may further include feeding the first reactor system product stream into 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 into 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 separately from the waste-derived hydrocarbon product recovered from the second reactor system.

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

[0019] After separation of the waste-derived hydrocarbon product, the method of the present specification may include feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the first reactor of the second reactor system. Thus, 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 circular polymers. The method may include pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil having one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine at a certain concentration. The method may include regenerating a catalyst mixture including a first catalyst and a second catalyst in a catalyst regenerator, 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, wherein the high-concentration catalyst mixture includes a portion of the catalyst mixture fed to the first reactor system and an additional second catalyst, and thus the catalyst mixture in the first reactor system has a higher concentration of the second catalyst than in the catalyst regenerator. The contacting in the first reactor system may produce a first reactor effluent including a treated plastic waste pyrolysis oil having a reduced contaminant concentration, the first catalyst, and the second catalyst containing the captured contaminants. The first reactor effluent may then be separated to produce a first stream including the first catalyst and the treated plastic waste pyrolysis oil having a reduced contaminant concentration, and a second stream including the second catalyst. The second stream may be fed to the first reactor as the additional second catalyst, thereby increasing the concentration of the second catalyst in the first reactor system. The first stream may be fed to a separation system to recover a first separation effluent including the spent first catalyst and a second separation effluent including the treated plastic waste pyrolysis oil. The second separation effluent may be fed 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.At least one of the naphtha fraction and the treated pyrolysis oil fraction is supplied to a second reactor system, and at least one of the naphtha fraction and the heavy oil fraction is brought into contact with the catalyst mixture to crack a part of the hydrocarbons contained therein, thereby generating a second reactor system effluent containing waste-derived olefins, a first catalyst, and a second catalyst. Next, the second reactor system effluent may be separated to recover (i) a mixture of the used first catalyst and the used second catalyst, and (ii) a second reactor system product stream containing the waste-derived olefins. The method may further include supplying (i) the mixture of the used first catalyst and the used second catalyst and (ii) the first separation effluent containing the used first catalyst to the catalyst regenerator.

[0021] In a further aspect, embodiments of the present specification are directed to a method for producing raw materials for producing true cyclic polymers. The method may include treating a polymer waste mixture in a first reactor system including a first-stage reactor and a second-stage reactor. The treatment of the polymer waste mixture may include feeding the polymer waste mixture to the first-stage reactor to pyrolyze the contained polymer and recovering the pyrolyzed effluent. The treatment of the polymer waste mixture may include feeding a waste-derived plastic pyrolysis oil and a catalyst mixture to the second-stage reactor to crack the contained hydrocarbons 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 fed 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 raw material may be treated with the catalyst mixture in a second reactor system. Further, the method may include supplying the catalyst mixture from a common catalyst regenerator to each of the first and second reactor systems. An effluent containing a fossil-based hydrocarbon product may be recovered from the second reactor system and the effluent containing the fossil-based hydrocarbon product 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 intensification reactor system. The method may include recovering a second stage reactor effluent including the catalyst mixture and the cracked hydrocarbon. The second stage reactor effluent may be separated to produce a first stream including the first catalyst and the cracked hydrocarbon and a second stream including the second catalyst. The first stream may be separated to recover (i) the spent catalyst and (ii) the second stage reactor effluent fed to the first fractionation system. The method may include feeding the second stream to the second stage reactor, thereby intensifying the second catalyst circulating within the second reactor to a higher concentration than the catalyst mixture when received from the regenerator.

[0023] In any of the above methods, the polymeric waste pyrolysis oil may be 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 methacrylate (PMMA); one or more thermosetting resins formed from one or more monomers including one or more of acrylic, polyester, vinyl ester, epoxy, urethane, ureas and isocyanates; and one or more unsaturated or saturated elastomers selected from the group consisting of polybutadiene, isoprene, chloroprene, styrene-butadiene, nitrile and ethylene vinyl acetate, or the polymeric waste feed or polymeric waste mixture may include these.

[0024] In another aspect, the embodiments disclosed herein relate to an apparatus and a process scheme for producing recycled virgin light olefins and petrochemical intermediates. In another aspect, the embodiments disclosed herein relate to a method and an apparatus for treating pyrolysis oil contaminants and further producing recycled virgin light olefins and petrochemical intermediates. In yet another aspect, the embodiments herein are directed to a system for performing the method outlined above.

[0025] In some aspects, the embodiments herein are directed to a system for producing a raw material for producing a true cyclic polymer. The system may include a first reactor system including a catalyst mixture configured to treat plastic waste pyrolysis oil, and a second reactor system configured to treat a fossil-based feedstock with the catalyst mixture. A supply line may be configured to supply the catalyst mixture from a common catalyst regenerator to each of the first and second reactor systems. A flow line may be configured to recover an effluent containing a fossil-based hydrocarbon product from the second reactor system. Another flow line may be configured to recover an effluent containing a waste-derived hydrocarbon product 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 including plastic, tire or other polymeric materials to produce the plastic waste pyrolysis oil.

[0026] In another aspect, embodiments of the present specification are directed to a system for converting plastic waste into a raw material for producing recycled plastics. The system includes a plastic waste pyrolysis reactor system configured to pyrolyze a polymer waste raw material to produce plastic waste pyrolysis oil. A catalyst regenerator is provided to regenerate a catalyst mixture including a first catalyst and a second catalyst. A first flow line is provided to supply a portion of the catalyst mixture from the catalyst regenerator to a first reactor system. Similarly, a second flow line is provided to supply 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 raw material with the catalyst mixture to crack a portion of the fossil-based raw material to produce a first effluent including a fossil-derived olefin, 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 the reactor to crack a portion of the plastic waste pyrolysis oil, wherein the high-concentration catalyst mixture includes a portion of the catalyst mixture supplied to the second reactor system and an additional second catalyst, and thus 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, and the contacting produces a second reactor effluent including a waste-derived olefin and other hydrocarbons, the first catalyst, and the second catalyst; separating the second reactor effluent to produce a first stream including the first catalyst and the waste-derived olefin and other hydrocarbons, and a second stream including the second catalyst; and supplying the second stream to the second reactor as the additional second catalyst to thereby increase the concentration of 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 a spent first catalyst and a spent second catalyst, and (ii) a first reactor system product stream including the fossil-derived olefin.Another separation system is provided to separate the first stream above and recover (i) the spent first catalyst and (ii) the second reactor system product stream containing the waste-derived olefins and other hydrocarbons. Also, flow lines are provided 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. 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 and recover two or more fossil-derived hydrocarbon fractions. The second fractionation system is configured to separate the second reactor system product stream and 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 the treatment of one or more of the two or more waste-derived hydrocarbon fractions and produce a cyclic polymer.

[0027] In one aspect, embodiments of the present specification are directed to a system for converting plastic waste into a raw material for producing plastics. The system may include a pyrolysis reactor system for pyrolyzing a polymer waste raw material to produce a polymer waste pyrolysis oil having one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine at a certain concentration. A catalyst regenerator regenerates a catalyst mixture including a first catalyst and a second catalyst, wherein the second catalyst is 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 raw material with the catalyst mixture to crack a portion of the fossil-based raw material to produce a first effluent including a fossil-derived olefin, 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. Further, the contacting produces a first-stage reactor effluent including a treated plastic waste pyrolysis oil having a reduced contaminant concentration, the first catalyst, and the second catalyst containing the captured contaminants. The first reactor system may include a separator for separating the first-stage reactor effluent to produce a first stream including the first catalyst and the treated plastic waste pyrolysis oil having a reduced contaminant concentration, and a second stream including the second catalyst. A flow line may be provided to supply the second stream to the first-stage reactor as the additional second catalyst, thereby increasing the concentration of the second catalyst in the first-stage reactor.The reactor system may further include a flow line for supplying the first stream to the second-stage reactor and recovering a second-stage reactor effluent containing the used catalyst and waste-derived olefins and other waste-derived hydrocarbons by cracking the treated plastic waste pyrolysis oil. The first separation system is configured to separate the first effluent and recover (i) a mixture of the used first catalyst and the used second catalyst and (ii) a first reactor system product stream containing the fossil-derived olefins. The second separation system is configured to separate the second-stage reactor effluent and recover (i) the used catalyst and (ii) a second-stage reactor system product stream containing the waste-derived olefins and other waste-derived hydrocarbons, and the flow line is provided to supply each of (i) the mixture of the used first catalyst and the used second catalyst and (ii) the used catalyst to the catalyst regenerator. 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 and recover two or more fossil-derived 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 polymerization 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 supplying 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 supplying one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the second reactor of the second reactor system. The flow line may be provided to withdraw a portion of the second catalyst from the first reactor.

[0028] In another aspect, embodiments of the present specification are directed to a system for converting plastic waste materials into circular polymers. The system may include a plastic waste pyrolysis reactor for pyrolyzing a polymer waste raw material to produce plastic waste pyrolysis oil having one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine at a certain concentration. A catalyst regenerator is provided to regenerate a catalyst mixture including a first catalyst and a second catalyst, wherein the second catalyst is 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 is configured to contact 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, wherein the high-concentration catalyst mixture includes a portion of the catalyst mixture supplied to the first reactor system and an additional second catalyst, and thus the catalyst mixture in the first reactor system has a higher concentration of the second catalyst than in the catalyst regenerator, and the contacting produces a first reactor effluent including a treated plastic waste pyrolysis oil having a reduced contaminant concentration, the first catalyst, and the second catalyst containing the captured contaminants; separating the first reactor effluent to produce a first stream including the first catalyst and the treated plastic waste pyrolysis oil having a reduced contaminant concentration and a second stream including the second catalyst; supplying the second stream to the first reactor as the additional second catalyst to thereby increase the concentration of the second catalyst in the first reactor system, and a separation system for recovering a first separated effluent including the used first catalyst and a second separated effluent including 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 containing waste-derived olefins, a first catalyst, and a second catalyst. A separation system is provided that is configured to separate the second reactor system effluent to recover (i) a mixture of the spent first catalyst and the spent second catalyst and (ii) a second reactor system product stream containing the waste-derived olefins. The system further includes flow lines for supplying (i) the 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, respectively.

[0029] In yet other aspects, embodiments herein are directed to a system for producing raw materials for producing true cyclic 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 polymers contained therein and recover the pyrolyzed effluent. A waste-derived plastic pyrolysis oil and a catalyst mixture are fed to the second stage reactor to crack the hydrocarbons contained therein and recover an effluent containing the cracked hydrocarbons. The pyrolyzed effluent from the first stage reactor and the effluent from the second stage reactor are fed to a first fractionation system via a flow line 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. 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 supply the catalyst mixture to each of the first and second reactor systems. A flow line is configured to recover an effluent containing a fossil-based hydrocarbon product from the second reactor system. A second fractionation system is provided and configured to separate the effluent containing the fossil-based hydrocarbon product. 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 intensification reactor system.

[0030] Other aspects and advantages will be apparent from the following description and the appended claims.

Brief Description of the Drawings

[0031]

Figure 1

Figure 1A

Figure 2

Figure 3

[0032] Embodiments herein generally relate to treating waste materials to form virgin materials such as light olefins and petrochemical intermediates. For example, waste materials such as plastics, elastomers, and other polymeric materials are subjected to pyrolysis, where the polymeric material is broken down and pyrolysis oil is formed. The 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 thermoplastic resins and elastomeric polymers, providing in some embodiments a true circular polymer.

[0033] As used herein, the terms circular polymer, circular plastic, circular elastomer, and other similar "circular" or "recycled" refer to a circular process of generating a polymer from monomer components such as ethylene or propylene, producing and using consumer goods made of the polymer to obtain waste (used) polymeric materials, and then converting the waste polymeric materials back to monomer components and then back to a polymer and into consumer goods. Embodiments herein are mostly directed to the conversion of waste polymeric materials back to monomer components.

[0034] Embodiments of the present specification for the conversion of waste materials may include a stand-alone system specifically targeted at methods for generating raw materials that can be used to produce true circular polymers. Other embodiments of the present specification for converting waste materials may include a system integrated with a process for converting fossil-based materials into products such as olefins and fuels typically produced in an oil refinery. In some embodiments, the system for converting fossil-based materials may be retrofitted to further process the waste-based materials described herein.

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

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

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

[0038] The waste-derived hydrocarbon streams useful in the 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 a polymeric material, such as a thermoplastic resin, a tire, or other polymeric material, to produce a plastic waste pyrolysis oil.

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

[0040] Pyrolysis of the polymer waste materials described above may be carried out by thermal or catalytic pyrolysis of the polymer waste materials. For example, thermal pyrolysis of plastic feedstocks may be carried out by contacting the plastic feedstock at a high temperature, such as in the range of 300 °C to 850 °C, such as about 350 °C to about 600 °C. Pyrolysis of plastics can produce various hydrocarbons, including light gas hydrocarbon products and liquid hydrocarbon products, all or some of which may be used as the plastic waste pyrolysis oil herein.

[0041] Polymer materials are generally processed to produce a final product, in which case polymerization catalysts and various additives such as metal colorants and crosslinking agents are retained in the resulting polymer, but these introduce various contaminants such as iron, calcium, and sulfur into the pyrolysis process. The polymer itself may also contain various atoms such as oxygen, nitrogen, chlorine, and fluorine that can be considered contaminants in a typical cracking process. Embodiments herein may pretreat the 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 the plastic waste pyrolysis liquid without such costly pretreatment.

[0042] The generation of truly recyclable products may be provided by converting waste materials into olefins and petrochemicals, then into finished consumer goods, and then using the resulting discarded / waste products as raw materials to convert them back into valuable light olefins and petrochemicals. Embodiments herein contemplate "green" products, in which case the feedstock to the waste reactor may include bio-derived oils, biomass, bio-waste materials, and other renewable feedstocks that can be cracked to produce olefins such as propylene and ethylene and / or other petrochemical intermediates. The use of such materials may provide flexibility in the feedstock while allowing the olefins and other petrochemicals produced, as well as the consumer goods made from them, to be classified as not being fossil-derived products.

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

[0044] Catalysts useful in embodiments of this specification may include various fluid catalytic cracking (FCC) catalysts. Suitable FCC catalysts may include, among those known in the art, Y-type zeolite, X-type zeolite, mordenite, faujasite, nanocrystalline zeolite, and MCM mesoporous materials. Typically, such catalysts are selected to crack heavier hydrocarbons.

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

[0046] Embodiments of this specification may use pollutant capture additives (such as capture catalysts, passivators, etc.). Useful pollutant capture additives are compounds and structures that have a higher affinity for pollutants than FCC or additive-type cracking catalysts under reaction conditions. Thus, pollutants can be preferentially absorbed or retained on the pollutant capture additives. The pollutant capture additives may include MgO, CaO, CeO2, MgTiO3, CaTiO3, Li2Ti2O7, and ZnTiO3, Ca / Mg, boron, and other rare earth-based capture additives. Useful pollutant capture additives may include, among other things, low-chlorine FCC catalysts.

[0047] As described above, various pollutants can be found in the plastic waste pyrolysis oil used. Pollutants that can be found in various plastic waste pyrolysis oil raw materials may include, among other things, one or more of iron, copper, calcium, phosphorus, vanadium, nickel, sodium, and chlorine. Such pollutants can have an adverse effect on the performance of catalysts such as cracking catalysts including FCC catalysts used to convert heavier hydrocarbons to lighter hydrocarbons. Various pollutants can poison the cracking catalyst and reduce its activity and / or may require increasing the daily replenishment rate of fresh catalyst to the process. Pollutants can also clog pores or reduce the diffusivity of catalyst pores, inhibiting the effectiveness of the catalyst.

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

[0049] Embodiments of this specification may utilize a mixture of an FCC catalyst and an additive-type cracking catalyst. Other embodiments of this specification may utilize a mixture of an FCC catalyst and a metal / contaminant capture catalyst. Still other embodiments may utilize a mixture of an FCC catalyst, an additive-type cracking catalyst, and a capture catalyst.

[0050] It is circulated from the catalyst regenerator as a homogeneous mixture of the various catalysts used, but embodiments of this specification may desirably increase the concentration of one or more of the catalysts within the reactor. For example, it may be desirable to increase the concentration of the additive-type cracking catalyst or the capture catalyst within the reactor tank so that the reaction occurring within the reactor tank is enhanced with respect to the high-concentration catalyst, and to take advantage of the high-concentration catalyst to improve the dynamics of the reactor.

[0051] Embodiments of this specification may advantageously increase the concentration of the catalyst within the reactor by taking advantage of the difference in size and / or density between each catalyst type. For example, the first catalyst, such as a Y-type 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. The 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 concentrated within the reactor. Such catalyst separation and concentration within the reactor may, in some embodiments, be performed using the methods and systems described, for example, in U.S. Patent Nos. 10450514, 10758883, 10351786, or 9452404 (each of which is incorporated herein by reference to the extent not inconsistent with the embodiments of this specification).

[0052] Each of the reactor system for waste-based raw materials and the reactor system for fossil-based raw materials may receive the same catalyst mixture from the regenerator. For example, the catalyst mixture may contain an FCC catalyst and a ZSM-5 catalyst in a ratio (by weight, volume, number of particles, etc.) of 9:1 to 4:1, respectively. By increasing the concentration of the larger and denser ZSM-5 catalyst in the reactor system for waste-based raw materials according to the embodiments herein, the catalyst mixture circulates within the reactor system for waste-based raw materials, and the FCC to ZSM-5 ratio can be 0.2:1 to 9.5:1, for example 1:4. These ratios are merely illustrative. Because the ratio of the catalysts in the regenerator depends on, among other variables, the fossil-based raw material to be processed, the configuration of the reactor system for the fossil-based raw material, the supply rate of each fresh catalyst and the withdrawal rate of the spent catalyst, as well as the fluidization conditions and catalyst separation / recycle variables (separation efficiency, recycle rate, supply rate of fresh catalyst replenishment, spent catalyst withdrawal rate, etc.) related to the reactor system for waste-based raw materials, and can vary accordingly.

[0053] In certain embodiments, the catalyst mixture contained in the regenerator and circulated from the regenerator may have a weight ratio of the first catalyst to the second catalyst in the range of 2:1 to 9:1. In this case, the first catalyst is lighter and / or less dense than the second catalyst. Thus, the riser reactor for converting the fossil-based hydrocarbon raw material may operate at a ratio of the first catalyst to the second catalyst similar to that contained in the regenerator. The reactor for converting the waste-based hydrocarbon raw material may operate at a ratio of the circulating first catalyst to the second catalyst lower than that in the regenerator, for example in the range of 1:1 to 1:9, while receiving the catalyst at a ratio similar to that contained in the regenerator.

[0054] Next, referring to FIG. 1, a simplified process flow diagram of a system 1 for converting plastic waste into raw materials for producing plastics is illustrated. System 1 may include a first reactor system 3 and a second reactor system 5, each receiving regenerated catalysts 6, 7 from a catalyst regenerator 9 and returning spent catalysts 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 a first catalyst and a second catalyst, such as a mixture of an FCC catalyst and an additive catalyst, for example, a mixture of Y-zeolite and ZSM-5. For example, the 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.

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

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

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

[0058] The effluent 17 may be recovered from the reactor system 3, and this effluent contains fossil-derived olefins (cracked hydrocarbon products), the first catalyst, and the second catalyst. The effluent 17 may then be quenched, if desired, and advanced to a separation system 19 to separate the first effluent to recover (i) a mixture 11 of the spent first catalyst and the spent second catalyst and (ii) a first reactor system product stream 21 containing fossil-derived olefins and other fossil-derived hydrocarbon products obtained from the treatment of the fossil-based hydrocarbon feedstock 13. The mixture 11 of the spent catalysts may then be returned to the catalyst regenerator 9 for regeneration and reused in the reactor. When using a quench treatment, a hydrocarbon feed such as heavy vacuum gas oil, atmospheric tower bottom oil, heavy hydrocarbon residue feed, light cycle oil (LCO), and / or steam may be injected as the quench treatment 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 a 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, the fossil-derived hydrocarbon product stream 21 may be fractionated within the 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 used in a gasoline pool and / or recycled to a reactor system 3 to convert naphtha-range hydrocarbons to additional ethylene and propylene. As another example, the C5 fraction may be used for a gasoline pool and / or supplied to an olefin conversion unit (not shown) or recycled back to the reactor system 3 to convert the contained C5 to additional ethylene and propylene.

[0060] In the second reactor system 5, a waste-derived hydrocarbon stream 15, such as pyrolysis oil of plastic waste, may be contacted with a high-concentration catalyst mixture formed from the regenerated catalyst mixture 6 provided from the regenerator 9. By contacting with the high-concentration catalyst mixture in the reactor system 5, a portion of the waste-derived hydrocarbons can be cracked to produce a second reactor system effluent containing waste-derived olefins and other waste-derived hydrocarbons, a first catalyst, and a second catalyst. The heat required for vaporization of the waste-based feedstock and / or for 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 endothermic heat (reaction heat) may be provided by the high-temperature regenerated catalyst from the regenerator 9. The pressure in 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. Since the reaction heat decreases the temperature along the length of the reactor, the reactor may start at a temperature favorable for cracking hydrocarbons in the C4, C5, and naphtha ranges, e.g., 600°C to 750°C, and may decrease to a lower reactor temperature, e.g., 475°C to 520°C, which may be favorable for cracking heavier hydrocarbon feeds. Thus, various waste-based feeds to the reactor may be introduced along the length of the reactor where the conditions are favorable for their processing.

[0061] The high-concentration catalyst mixture in the second reactor system includes a portion of the catalyst mixture supplied from the regenerator to the second reactor system and additional second catalyst, and thus 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. After conversion and effluent recovery in the second reactor system, the second reactor effluent may be quenched as needed if desired and then separated to produce a first stream containing the first catalyst and waste-derived olefins and other hydrocarbons, and a second stream containing the second catalyst. The second stream may then be returned to the second reactor system as additional second catalyst, thereby increasing the concentration of the second catalyst in the second reactor system.

[0062] The first stream with the second catalyst depleted, if desired, is quenched and fed to a catalyst separator to recover (i) the spent first catalyst fraction 12 and (ii) the second reactor system product stream 49 containing 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 using quenching, waste-based hydrocarbon feeds such as heavy vacuum gas oil, atmospheric tower bottom oil, heavy hydrocarbon residue feed, light cycle oil (LCO), and / or steam may be injected as a quenching medium, such as when the waste-based hydrocarbon quenching is provided by the 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 hydrocarbon 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 is fractionated within 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, among other hydrocarbon fractions that may be recovered, the ethylene and propylene streams may be further purified, if necessary, to provide a polymer-grade waste-derived olefin fraction having a purity higher than, for example, 99.8%. Such a waste-derived olefin fraction may then be provided to a polymerization unit to produce a cyclic polymer. As another example, the butene-containing fraction 57 or the C4-containing fraction may be further separated / or processed to produce waste-derived propylene and ethylene, which may then be provided to a polymerization unit to produce a cyclic polymer. As yet another example, the naphtha fraction 61 may be further purified and / or processed to recover a cyclic aromatic fraction. The waste-derived aromatic may then be provided for the production of aromatic-containing cyclic polymers such as polystyrene, styrene-butadiene rubber (SBR), and many other types of aromatic-containing polymers known in the art. The various product fractions or portions thereof may be further processed to provide a suitable feedstock for the production of polyethers, polyesters, and other cyclic polymers.

[0064] As can be readily imagined, any number of many types of cyclic polymers can be made from waste-derived fractions obtained from the pyrolysis and treatment of plastic waste according to the embodiments herein. Generally, embodiments herein may include supplying one or more monomers recovered from or derived from a waste-derived hydrocarbon product fraction directly or indirectly to a polymerization system to produce a cyclic polymer. Embodiments herein contemplate the production of cyclic polymers, including among the cyclic polymers contemplated, those 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 shown in FIG. 1A. The regenerated and mixed first and second catalysts 6 may be supplied to the bottom of the riser reactor 73 from a common catalyst regenerator 9 via a flow line 71 through a control valve 72. At the bottom of the riser reactor 73, the regenerated mixed catalyst is mixed with additional second catalyst supplied via a flow line 74. The catalyst in the flow line 74 may have a higher concentration of a larger and / or heavier second catalyst, such as ZSM-5.

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

[0067] When a cracking reaction occurs in the riser reactor 73, the plastic waste pyrolysis oil feed and the steam feed are maintained at a flow rate sufficient to carry both the first and second catalysts along with the cracked hydrocarbon products. The reactor effluent stream containing the catalyst mixture then enters a solids separation device (SSD) 77 that may be used to facilitate a higher concentration of the 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 is recycled back to the riser reactor 73 via the flow line 74 and continuously reacted to provide an even higher concentration of the second catalyst within the riser reactor 73 as described above.

[0068] The cracked hydrocarbons and the first catalyst in the flow line 79 are then fed to a separation tank 83 to separate the first catalyst from the cracked hydrocarbon products. The cracked waste-derived hydrocarbon products containing light olefins, C4 hydrocarbons, naphtha-range hydrocarbons, and heavier hydrocarbons may be recovered via the 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 separation tank 83 and returned to the catalyst regenerator.

[0069] In addition to the rising steam 75, it may be prepared to inject an additional waste-derived feed stream such as C4 olefins or paraffins, naphtha, or other external streams as the rising medium / reactants. The location of such a feed stream may be a location that provides preferential conditions for the cracking of the hydrocarbons contained in each stream.

[0070] The second reactor system 5 is illustrated in FIG. 1A as including a riser reactor, a solid separation device, and a stripping tank, but other configurations for separating and concentrating the second catalyst within the reactor may be used. Further, 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 a moving bed reactor, where the fluidization is sufficient to carry only the lighter or less dense of the two catalysts out of the reactor, thereby concentrating the second catalyst within the reactor and removing the first catalyst along with the hydrocarbon effluent. The second catalyst concentrated 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 that shown in FIG. 2, where like numbers represent like parts. Multiple reactor systems 5 may be used to advantageously pretreat waste-derived pyrolysis oil containing contaminants, for example, within a first stage reactor or reactor system 5A, and then further crack the treated waste-derived pyrolysis oil within a second stage reactor or reactor system 5B. Further, the use of the solid separation concepts discussed above may be used to concentrate an additive-type catalyst, a cracking catalyst, and / or a capture catalyst within 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 supplied to the mixed flow turbulent bed / moving bed reactor 5A. The capture catalyst 89 may be supplied to the mixed flow turbulent bed / moving bed reactor 5A. The capture catalyst may be formed from particles that are larger and / or denser than any of the catalysts in the mixed catalyst supplied from the regenerator. The flow regime within the reactor 5A is maintained such that the capture catalyst forms a turbulent or bubbling bed while the regenerated mixed catalyst forms a moving bed and flows with the hydrocarbon and other fluidizing gases, and the mixed catalyst and hydrocarbon are recovered as the effluent 91 from the first stage reactor 5A. Optionally, the capture catalyst may be recovered from the reactor system 5A via the flow line 93, discarded, or further processed to recover metals.

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

[0074] As shown in FIG. 2, the processing scheme integrates the removal of pyrolysis oil feed contaminants and catalytic processing for the production of light olefins and aromatics from the waste-derived hydrocarbon stream. This can advantageously enable the treatment and processing of contaminated waste-derived feedstocks and provides a means for treating waste-derived feedstocks that is more efficient and cost-effective than previously proposed hydrotreating systems, since various catalysts, including capture catalysts, can be concentrated.

[0075] FIG. 2 has been described above as including a three-particle system (mixed cracking catalyst + capture catalyst from the regenerator), but embodiments of the present specification further contemplate a two-particle - two-stage reactor system in which an FCC catalyst rich in additives and a capture catalyst are circulated from the regenerator. The catalyst containing the obtained contaminants may be recovered from the first-stage reactor 5A, while the FCC catalyst rich in additives may be advanced to the second-stage reactor 5B together with the treated feed steam. The flexibility of the reactor system of the present specification operating in a number of flow regimes (turbulent flow, mixing, and transport) allows for various other combinations of particles / catalysts and high concentrations of selected particles within the reactor stages.

[0076] As another example of the method according to FIG. 2, the polymer waste feedstock may be pyrolyzed to produce plastic waste pyrolysis oil 15 having one or more contaminants such as iron, calcium, chlorine, or other contaminants at a certain concentration. The catalyst mixture including the first catalyst and the second catalyst may be regenerated in the catalyst regenerator 9, and the second catalyst is configured to capture one or more contaminants. The first portion of the catalyst mixture may be fed to the first reactor system 3, and the second portion of the catalyst mixture may be fed to the 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 including a fossil-derived olefin, the first catalyst, and the second catalyst. The first effluent may then be treated in the same manner as described with respect to FIG. 1 to separate the first effluent and recover (i) a mixture of the spent first catalyst and the spent second catalyst and (ii) a first reactor system product stream including the fossil-derived olefin 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 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. The contact of the mixed catalyst in the first-stage reactor 5A may produce a first-stage reactor effluent containing treated plastic waste pyrolysis oil with a reduced contaminant concentration, the first catalyst, and the second catalyst containing the captured contaminants. Next, the first-stage reactor effluent may be separated to produce a first stream 91 containing the first catalyst and the treated plastic waste pyrolysis oil with a reduced contaminant concentration, and a second stream containing the second catalyst. Next, the second stream may be supplied to the second reactor as additional second catalyst, thereby increasing the concentration of the second catalyst (capturing catalyst) in the first-stage reactor system. Next, the first stream may be supplied to the second-stage reactor to crack the treated plastic waste pyrolysis oil and recover a second-stage reactor effluent containing the used catalyst and waste-derived olefins and other waste-derived hydrocarbons. Next, the second-stage reactor effluent may be separated to recover (i) the used catalyst and (ii) a second reactor system product stream 49 containing waste-derived olefins and other waste-derived hydrocarbons.

[0079] Next, each of (i) the mixture of the used first catalyst and the used second catalyst 11 recovered from the reactor system 3 and (ii) the used catalyst 12 recovered from the reactor system 5 may be supplied to the catalyst regenerator for regeneration and continuously used in the conversion of hydrocarbons.

[0080] Similar to the system of FIG. 1, it may be desirable to maintain the fossil-based hydrocarbon fraction recovered from the first reactor system 3 separately from the waste-derived hydrocarbon product recovered from the second reactor system 5. In this way, all products from the separation system 51 may be warrantable and correctly explainable as waste-derived products, which may be used, for example, to produce a cyclic polymer.

[0081] Although not shown in FIG. 2, the methods and systems herein may include feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the first stage reactor 5A of the second reactor system 5. For example, a light naphtha fraction of C4, C5, or a full range of naphtha may be fed to the first stage reactor 5A, which may operate under preferential conditions for the cracking of lighter hydrocarbons.

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

[0083] The reaction conditions in each of the reactor systems described with respect to FIG. 2 and the reactor system described with respect to FIG. 3 below may be the same as those described with respect to FIG. 1. For example, the 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. The reactors for converting the fossil-based and waste-based hydrocarbon feeds may operate at a temperature in the range of about 450 °C to about 750 °C. Similarly, the reactor effluents recovered in the embodiments of FIGS. 2 and 3 may be quenched if desired.

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

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

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

[0087] As shown in FIG. 3, the waste-derived hydrocarbon feed stream 15 may be fed to the first-stage reactor system 5A to convert (crack) the hydrocarbons contained therein into lighter hydrocarbons through contact with a mixed catalyst system containing 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 plastic waste pyrolysis oil. For example, a catalyst or non-catalyst 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] In the first-stage reactor system 5A, a waste-derived hydrocarbon stream 15 such as plastic waste pyrolysis oil may be contacted with a high-concentration catalyst mixture formed from the regenerated catalyst mixture 6 provided from the regenerator 9. Contact with the high-concentration catalyst mixture in the reactor system 5 may crack a portion of the waste-derived hydrocarbons and remove contaminants to produce a first-stage reactor system effluent containing waste-derived olefins and other waste-derived hydrocarbons, a first catalyst, and a second catalyst.

[0089] The high-concentration catalyst mixture in the first-stage reactor system includes a portion 6 of the catalyst mixture supplied from the regenerator 9 to the first-stage reactor system 5A and additional second catalyst, and thus the catalyst mixture in the first-stage reactor system 5A has a higher concentration of the second catalyst than in the catalyst regenerator 9. After conversion and recovery of the effluent in the first-stage reactor system 5A, the first-stage reactor effluent may be separated to produce a first stream containing the first catalyst and olefins and other hydrocarbons derived from the treated waste, and a second stream containing the second catalyst. The second stream may then be returned to the first-stage reactor system 5A as additional second catalyst, thereby increasing the concentration of the second catalyst in the first-stage reactor system.

[0090] The first stream with depleted second catalyst is fed to a catalyst separator to recover (i) a spent first catalyst fraction 12 and (ii) a first-stage reactor system product stream 49 containing 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 is 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.

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

[0093] Next, the illustrated treated waste-derived hydrocarbon feedstock or naphtha / unconverted oil 61A and 65 may be contacted with the catalyst mixture 100 in the second stage reactor system 5B to crack a portion of the treated waste-based feedstock. The effluent containing additional waste-derived olefins (cracked hydrocarbon products), the first catalyst, and the second catalyst may be recovered from the second stage reactor system 5B. Next, the effluent from the second stage reactor system 5B is advanced to a separation system 109 to separate the effluent into (i) a mixture 111 of spent first catalyst and spent second catalyst, and (ii) a second stage reactor system product stream 113 containing additional waste-derived olefins and other waste-derived hydrocarbon products obtained from the treatment of the treated waste-based hydrocarbon feedstocks 61A, 65. Next, the mixture 111 of spent catalysts may be returned to the 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 a fractionation system 51 and separated together with the vapor product 49 recovered from the 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 polymer 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 in the range of 350° C. to 850° C., such as in the range of about 400° C. to about 750° C. In some embodiments, the pyrolysis catalyst may comprise individual components or mixtures of used FCC and / or ZSM-5 catalysts. These catalysts / additives may be modified to provide desired objectives such as reactivity and / or adsorption capacity towards selected reactants, metals or contaminants. Pyrolysis of plastics can produce various hydrocarbons including light gas hydrocarbon products and liquid hydrocarbon products. The pyrolysis products may then be fed to a fractionation system 51 to be separated into various hydrocarbon fractions, which may include plastic waste pyrolysis oil and portions used as other waste-based feeds that may be fed to one or more second stage reactor systems 5B including a catalytic intensification reactor according to embodiments herein. As described above, the regenerator that provides catalyst to the second reactor system 5B may provide catalyst to a fossil-based reactor system (not shown) that may be similar to that described with respect to the reactor system 3 of FIG. 1, for example.

[0096] Example 1 This example illustrates the catalytic cracking performance of the reaction systems described herein. The experiments were carried out 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. Table 1 shows the basic properties of the feedstock obtained from the conversion of plastic waste treated in the pyrolysis unit. Feedstock A is a naphtha-range feedstock, while Feedstock B is a blend of naphtha and heavy oil.

[0097] The potential of various raw materials from the recycling of plastic waste to maximize light olefins was studied. The first performance data set from the pilot plant experiments reported in Table 2 corresponds to the naphtha feedstock, Feedstock A, defined in Table 1, while the second set corresponds to Feedstock B. As can be seen in Table 2, as a result of the catalytic cracking of the pyrolysis oil feedstock, very high yields of ethylene, propylene, and butylene were produced. Since both types of raw materials showed similar results, the potential of these raw materials to produce true recycle petrochemical components using the processes disclosed herein has been demonstrated.

[0098] The experimental data also shows the distinct features of the embodiments herein, but the catalysts, methods, and hardware may be adjusted to be advantageous for the catalytic reaction to maximize light olefins (ethylene, propylene, and butylene) while reducing the impact on the ecosystem and environmental pollution from plastic waste. This example clearly demonstrates the catalysts, reactor conditions, and mechanisms for cracking these unconventional feedstocks into light olefins using the systems described herein.

[0099] [Table 1]

[0100] [Table 2]

[0101] Example 2 In these experiments, the blend of liquid oil (naphtha range and heavy oil) products from the pyrolysis process unit was subjected to catalytic cracking in a CFB pilot plant in the presence of USY and ZSM-5 catalyst blends under the conditions described in Table 3 below. From the data presented in Table 3, it is clear that, combined with a relatively high C / O ratio, the result of raising the reactor temperature to 1050°F - 1100°F led to a higher yield of light olefins (propylene, ethylene, and butylene). Also, under the conditions provided for Case C and Case D, the pyrolysis-derived oil showed a higher olefin-forming ability, reflecting the preferential conditions for maximizing light olefins.

[0102]

Table 3

[0103] As described above, the embodiments of the present specification provide systems and methods that can provide a true circulating solution for plastic recycling. By utilizing a single regenerator dual catalyst (SRDC) reaction system that has its own separated product section while being associated with an FCC unit, or a stand-alone target production unit integrated with a pyrolysis unit, the resulting products will be 100% recyclable. Further, due to the characteristics of the fluidized bed catalytic reactor, it can be sized economically to receive products from pyrolysis units of essentially any capacity, such as pyrolysis units with a small capacity of 600 tons per day or more.

[0104] The embodiments of the present specification also help to address the raw material acquisition and processing costs, which are economic feasibility factors. Due to the FCC platform, and more importantly the SRDC platform, the systems according to the embodiments of the present specification have an inherent flexibility with respect to feed variations and contaminant content, thus reducing the costs associated with sorting and cleaning.

[0105] Accordingly, selecting an FCC and / or SRDC platform as the pyrolysis oil conversion step in the downstream facility addresses the factors listed above with respect to the quantity and quality requirements of the pyrolysis oil. Embodiments herein using these platforms can also eliminate the need for hydrotreating and hydroprocessing and minimize the impact on existing operations. The ability of the systems herein to concentrate the selected catalyst within the reactor system while using a single regenerator enables the treatment of contaminated feedstocks and hydrocarbon waste of various compositions that are very different from typical fossil-based hydrocarbon streams, with significant advantages over dilution and steam cracking with fossil-based hydrocarbons, and also provides advantages over FCC systems that may include parallel plastic pyrolysis oil riser reactors.

[0106] A further advantage of the embodiments herein relates to the factor of revenue from the sale of the products. By utilizing an SRDC unit that has its own separate product section while being bolted to the FCC unit, or a stand-alone target production unit integrated with the pyrolysis unit, the products will be 100% recyclable. The olefins and other valuable products obtained from the embodiments herein can be 100% recyclable and highly concentrated, such products are premium and can thus support the economic viability of this recycling pathway.

[0107] As a whole, the embodiments of this specification provide the ability to convert plastic waste pyrolysis oil into valuable products, whether integrated with existing facilities or in dedicated purpose production facilities, by applying the FCC / SRDC platform. The benefits are derived from (1) the flexibility of feedstock quality, (2) the ability to handle a wider range of compositions and potential contaminants without the need to dilute or blend with fossil-derived naphtha, (3) the ability to produce 100% recyclable and premium-priced separated products, (4) good integration with and low impact on the operation of existing downstream facilities, (5) the ability to process both the relatively small amount of pyrolysis oil (650 t / day) produced from currently planned pyrolysis facilities and the larger-sized pyrolysis oil (over 3,000 t / day) in the future at an economy of scale in the SRDC or FCC unit 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, shall each have an open and non-limiting meaning that does not exclude additional elements or steps.

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

[0112] When the words "about" or "approximate" are used, this term may mean that there can be variations in the value of 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 being from about one particular value to about another particular value and including those values. When such a range is expressed, another embodiment should be understood to be from the one particular value to the other particular value, along with all particular values within the above range and combinations thereof.

[0114] Although the present disclosure includes a limited number of embodiments, it will be understood by those skilled in the art having the benefit of this disclosure that other embodiments not departing from the scope of the present disclosure are contemplated. Accordingly, the scope should be limited only by the appended claims.

Claims

【Claim 1】 A method for converting plastic waste into a raw material for producing plastics, comprising: pyrolyzing a polymer waste raw material to produce plastic waste pyrolysis oil; regenerating a catalyst mixture containing a first catalyst and a second catalyst in a catalyst regenerator; feeding a portion of the catalyst mixture to a first reactor system; feeding a portion of the catalyst mixture to a second reactor system; in the first reactor system, contacting a fossil-based raw material with the catalyst mixture to crack a portion of the fossil-based raw material, thereby producing a first effluent containing a fossil-derived olefin, the first catalyst, and the second catalyst; In the second reactor system, contacting the plastic waste pyrolysis oil with a high-concentration catalyst mixture in a reactor to crack a portion of the plastic waste pyrolysis oil, wherein the high-concentration catalyst mixture includes 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, and the contacting produces a second reactor effluent containing a waste-derived olefin, other hydrocarbons, the first catalyst, and the second catalyst; separating the second reactor effluent to produce a first stream containing the first catalyst, the waste-derived olefin, and other hydrocarbons, and a second stream containing the second catalyst; feeding the second stream as the additional second catalyst to the second reactor system, thereby increasing the concentration of the second catalyst in the second reactor system; separating the first effluent to recover (i) a mixture of the spent first catalyst and the spent second catalyst, and (ii) a first reactor system product stream containing the fossil-derived olefin; separating the first stream to recover (i) the spent first catalyst, and (ii) a second reactor system product stream containing the waste-derived olefin and other waste-derived hydrocarbons; feeding 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; Supplying the product stream of the first reactor system to a first fractionation system and separating the product stream of the first reactor system to recover two or more fossil-derived hydrocarbon fractions, and supplying the product stream of the second reactor system to a second fractionation system and separating the product stream of the second reactor system to recover two or more waste-derived hydrocarbon fractions comprising wherein the pyrolysis includes pyrolyzing a polymer waste feedstock to produce a plastic waste pyrolysis oil having one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine at a certain concentration, wherein the catalyst mixture including the first catalyst and the second catalyst includes a second catalyst configured to capture the one or more contaminants, the contacting in the second reactor system is contacting 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, wherein the high-concentration catalyst mixture includes a portion of the catalyst mixture supplied to the second reactor system and an additional second catalyst, and thus the catalyst mixture in the first-stage reactor has a higher concentration of the second catalyst than in the catalyst regenerator, and the contacting produces a first-stage reactor effluent containing a treated plastic waste pyrolysis oil having a reduced contaminant concentration, the first catalyst, and the second catalyst containing the captured contaminants, separating the first-stage reactor effluent to produce a first stream including the first catalyst and the treated plastic waste pyrolysis oil having a reduced contaminant concentration, and a second stream including the second catalyst, supplying the second stream to the first-stage reactor as the additional second catalyst, thereby increasing the concentration of the second catalyst in the first-stage reactor, and supplying the first stream to a second-stage reactor and cracking the treated plastic waste pyrolysis oil to recover a second-stage reactor effluent containing a spent catalyst and waste-derived olefins and other waste-derived hydrocarbons comprising The separation of the first stream for recovering (i) the spent first catalyst and (ii) the second reactor system product stream includes separating the second stage reactor effluent to recover (i) the spent first catalyst and (ii) the second reactor system product stream containing the waste-derived olefins and other waste-derived hydrocarbons, wherein the second catalyst is, an additive-type cracking catalyst or a mixture of additive-type cracking catalysts selected from the group consisting of medium pore zeolites and pentasil-type zeolites, and MgO, CaO, CeO ２ , MgTiO ３ , CaTiO ３ , Li ２ Ti ２ O ７ and ZnTiO ３ , a pollutant capture additive or a mixture of pollutant capture additives selected from the group consisting of Ca / Mg, boron, rare earth-based capture additives or low-chlorine FCC catalysts comprises, a method. **Claim 2** The method according to claim 1, 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. **Claim 3** The method according to claim 1, further comprising directly or indirectly feeding one or more of the two or more waste-derived hydrocarbon fractions, or monomers obtained from the treatment of one or more of the two or more waste-derived hydrocarbon fractions, into a polymerization process to produce a recyclable polymer. **Claim 4** The method according to claim 1, further comprising maintaining the fossil-derived hydrocarbon fraction recovered from the first reactor system separately from the waste-derived hydrocarbon fraction recovered from the second reactor system. **Claim 5** The method according to claim 1, further comprising feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon fraction into the first reactor of the second reactor system. **Claim 6** The method according to claim 1, further comprising feeding one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon fraction into the second reactor of the second reactor system. **Claim 7** The method according to claim 1, further comprising withdrawing a portion of the second catalyst from the first reactor of the second reactor system.

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