Highly efficient process for separating fillers from catalyst and gases in fluidized bed catalytic pyrolysis of plastics

Abstract

A fluidized bed catalytic pyrolysis process for converting waste plastics, polymers and other waste materials into useful chemical and fuel products, such as paraffins, olefins, aromatics such as BTX, and the like, in which fillers contained in the plastics are separated from the catalyst and gases, is described.

Description

[Technical field]

[0001] Related Applications This application claims priority to U.S. Provisional Patent Application No. 63 / 338,013, filed May 3, 2022.

[0002] The present invention relates to a process for converting waste plastics, polymers, and other waste materials into useful chemical and fuel products, such as paraffins, olefins, aromatics such as BTX, including a highly efficient process for separating fillers from catalyst particles used in upgrading such waste materials. [Background technology]

[0003] In 2019, the amount of plastic generated in the United States was 55.2 million tons, which represents 13% of MSW generation. More than 368 million tons of plastic were produced worldwide. According to one estimate, of the 8.3 billion tons of plastic ever produced, 6.3 billion tons became waste, of which only 9% was recycled. Plastic recycling involves recovering scrap or waste plastic and reprocessing the material into useful products. However, since China banned the import of waste plastic in 2018, it is estimated that the recycling rate in the United States has dropped to just 4.4%. Recycling plastics is difficult due to the chemical properties and low economic benefits of long-chain organic polymers. Waste plastic materials often need to be separated into different plastic resin types, such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET), and then processed for recycling separately. In addition, plastic materials often contain particulate materials introduced into the polymer formulation to reduce costs and improve properties. Materials added to plastic formulations, so-called fillers, take up space and replace expensive resins with cheaper compounds. The cost reduction depends on the relative cost of the polymer and filler. The approximate price range for polymers in May 2020 was ($ / kg) ABS 10-16.5, HDPE 3.8-8.6, PET 1-3, PP 2.3-3.7, PS 10.9-16.8, PVC 1.8-2.5, while fillers generally cost significantly less than $1 / kg. The global plastic filler market was estimated at $10 billion in 2019 and is expected to exceed $14.5 billion by 2026, with a growth rate of 5.2%. Many of these fillers ensure the stability of the plastic while making it easier to mold and shape. For plastics that require heat resistance, mineral fillers increase thermal deformation and decrease thermal expansion. Large filler particle sizes cause cracks to grow and weaken the material. Particles larger than about 10-20 microns begin to have a significant effect on the impact resistance and elongation at break of the composite.Coarse particles result in poor surface finish, low gloss, and high transparency, therefore fillers are generally preferred in very small particle sizes, less than about 30 microns.

[0004] When polymers contain fillers, they typically make up 20-30% of the composite's mass, although materials such as PVC have been manufactured that contain as much as 90% filler by mass, and some contain less than 0.1% filler by weight.

[0005] Plas-TCat™ is a catalytic fluidized bed process that uses a zeolite catalyst to convert polymer / plastic materials, particularly waste plastics that may normally be sent to landfills or incinerators, into a mixture of permanent gases, C2-C4 light olefins, C1-C4 light paraffins, and C5+ hydrocarbons including benzene, toluene, and xylenes ("BTX"), aromatic and non-aromatic naphtha range molecules, C11+ hydrocarbons, coke and char, and minor by-products. Plastic mixtures with relatively high hydrogen to carbon molar ratios, such as polyethylene (PE), polypropylene, polystyrene, and combinations thereof, can be converted to olefins and aromatics. Plas-TCat™ requires that materials such as fillers, inorganics, salts, minerals, and glass and metal debris be continually removed from the process to prevent accumulation. Accumulation can reduce the activity of the catalyst and adversely affect the reactor fluid dynamics.

[0006] In the Plas-TCat™ process, both the reactor and regenerator gaseous effluents contain elutriated packing material, as well as some catalyst, resulting in a bimodal solids distribution in the gaseous effluent stream: small packing particles (<40 microns, 95% <20 microns) and large catalyst particles (>40 microns, 95% >65 microns). Effective separation of the packing material from this stream and minimizing catalyst losses from the process is critical to stable performance and minimize catalyst costs.

[0007] Removal of fillers from plastics by filtering hot melts can be done using screens or candle filters such as those offered by MAAG (https: / / maag.com / wp-content / uploads / LAF%20Brosch%C3%BCre_EN_16S_s.pdf). Filtering plastic hot melts requires raising the mixture to high temperatures (400°C) and pressures (300 bar) to force the viscous molten plastic through the filter, as well as regular cleaning or replacement of the filter elements, which requires the process to be taken offline.

[0008] In dissolving plastics recycling, the polymer is dissolved in a solvent to separate the solids, as practiced in the CreaSolv® technology applied to polystyrene (https: / / www.creacycle.de / en / ) and the PureCycle technology applied to polypropylene. The process requires filtering the polymer solution to remove particulate matter. In addition to problems arising from regular cleaning and replacement of filters, large amounts of expensive solvents and near 100% recovery of the solvent are required for the process to be viable. Furthermore, the process is limited to one type of polymer or polymer mixtures where all polymers in the mixture are soluble in the same solvent, necessitating further separation of the polymer mixtures found in real recycling streams into their individual component polymers.

[0009] Layman et al., in U.S. Pat. No. 9,803,035, describe a purification process in which polyethylene is contacted with a fluid solvent under high temperature and pressure, and the polyethylene solution is contacted with a solid medium to produce a purer polyethylene solution. Layman et al., in U.S. Pat. No. 10,465,058, describe a process for purifying a regenerated polymer by dissolving the polymer in a solvent, precipitating the solution to remove suspended contaminants, purifying the solution by contacting it with a solid medium, and isolating the polymer from the resulting solution. Layman et al., in U.S. Pat. No. 11,008,433B2, describe a process for purifying a regenerated polymer by dissolving the polymer in a solvent, precipitating the solution to remove suspended contaminants, purifying the solution by contacting it with a solid medium, separating the polymer from the resulting solution, and repeating the process for different polymers in the mixture. Summary of the Invention [Problem to be solved by the invention]

[0010] All dissolution processes require the handling of large amounts of solvent and constitute a separate process from the polymer chemical recycling process.

[0011] There is a need for a simple, continuous process for chemically recycling and further upgrading mixtures of filled polymers into chemical intermediates. [Means for solving the problem]

[0012] The present invention provides a simple system and a continuous one-step process for separating solids from a continuous reactor exhaust gas stream resulting from the pyrolysis of a carbonaceous feedstock containing high concentrations (up to 10%) of filler. The configuration includes a multi-stage cyclone system, with the first stage being preferably a single cyclone and each subsequent stage being an axial multicyclone (multiclone) operating in parallel. The efficiency of the first cyclone is adjusted to a level where as much of the filler (small particles) as possible is discharged with the cyclone gases and as much of the catalyst (large particles) as possible is discharged from the bottom of the cyclone. The goal of the present invention is for at least 85% of the filler (small diameter component) in the inlet gas stream to be discharged with the cyclone gas (top) outlet and for at least 95% of the catalyst (large diameter component) to be separated from the inlet gas stream discharged from the bottom of the cyclone and returned to the reactor. The cyclone dimensions are adjusted with the objective of meeting these separation objectives as a minimum and exceeding the maximum achievable. Subsequent stages further reduce the amount of filler in the exhaust gas discharged from the reactor and operate at an efficiency that meets solids loading limitations to downstream processing units.

[0013] I. Klumpar et al., in their article "Air Classifiers" published in Chemical Engineering, March 1986, present various classifiers and their size selection curves. In general, it can be said that these classifiers do not reach the current cut size and are less efficient. This effect of industrial classifiers is described as a sharpness index that leads to a bypass of up to 30%! Other sources, such as Metso Air Classifier (https: / / www.mogroup.com / products-and-services / plants-and-capital-equipment / classifiers / air-classifiers / ), claim that the cut size is limited to 10 μm and the maximum particle size is limited to 500 μm. To determine the particle size distribution (PSD) of a mixture, several common scientific techniques can be used, such as light scattering, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM).

[0014] Without being bound by theory, the method exploits the strand separation effect in high-load cyclones and the bimodal particle size distribution of the incoming solids stream. In general, the separation behavior (or efficiency) of high-load cyclones consists of two main mechanisms: (1) Due to the limited turbulence in the cyclone, only a certain amount of solids loading is carried in the inlet gas stream, also called the critical load. When the solids loading in the gas exceeds this critical load value, the excess solids mass is removed immediately after the cyclone inlet and forms strands or a continuous layer on the wall (strand separation); (2) Only a small portion of the finer particle size distribution remains in the gas stream and is centrifuged in the cyclone vortex (internal separation). Internal separation is determined by the balance between the centrifugal force and the resistance of the particles.

[0015] Strand separation becomes the more dominant mechanism at solids loadings above about 0.05 kg / kg, as shown in Muschelknautz, Edgar, and Volker Greif. "Cyclones and other gas-solids separators." Circulating Fluidized Beds. Springer, Dordrecht, 1997. 181-213, and Hugi, Erich, and Lothar Reh. "Focus on solids strand formation improves separation performance of highly loaded circulating fluidized bed recycle cyclones." Chemical Engineering and Processing: Process Intensification 39.3 (2000): 263-273.

[0016] Both of these separation mechanisms are characterized by a cut size, which is a function of the physical properties of the gas and solids and the geometry of the cyclone, describing the particle size boundary between larger solids that undergo strand separation and smaller solids that undergo internal separation. Cyclones are typically designed to have the smallest possible cut size, resulting in maximum removal of solids from the gas stream and maximizing separation efficiency. In this proposed application, the cyclone is designed so that only the catalyst (larger) particles are strand separated and easily removed from the gas stream, while the remaining solids (filler) remain in the gas stream within the cyclone vortex. This is designed to reduce solids losses due to internal separation, particularly by modifying the dimensions of the vortex finder. These smaller solids (fines) are then discharged from the cyclone with the gas stream, effectively making the cyclone operate as a solids classifier. The first cyclone is designed to have a cut size between the bimodal particle size distribution, separating the coarse particles and entraining the fine particles in the off-gas where they can be removed by one or a series of highly efficient multi-cyclones. Highly efficient Multiclone is used to reduce the concentration of elutriated particles to meet the solids loading limitations of downstream processes.

[0017] The present invention provides a method for producing olefinic and aromatic hydrocarbons from waste plastics, the method comprising feeding a plastic-containing stream to a fluidized bed catalytic pyrolysis reactor, catalytically reacting the feed with a catalyst to form a product mixture, passing the vapor discharge to a catalyst and filler recovery system including classifying cyclones and recovery cyclones, returning solids from the classifying cyclones to the fluidized bed reactor, disposing of recovered filler from the recovery cyclones, and recovering olefins or aromatics from the vapor discharged from the final recovery cyclone.

[0018] A first aspect of the present invention provides a method for converting plastics to olefins, aromatics, or a mixture of olefins and aromatics, the method comprising: feeding a stream comprising plastics, at least one of which contains a filler, to a fluidized bed reactor containing a catalyst, the filler having an average particle size smaller than the average particle size of the fluidized bed catalyst; catalytically reacting the feed with the catalyst in the fluidized bed reactor to form a product mixture; recovering a vapor discharge from the product mixture; passing the vapor discharge through a solids separation system; separating the catalyst from the filler and recovering olefins, aromatics, or a combination thereof from the vapor discharged from a final recovery cyclone.

[0019] A second aspect of the present invention provides a method for producing olefins and aromatics, the method comprising: feeding a plastics-containing stream, the filler being at least one of a filler and a plastics-containing stream, to a fluidized bed reactor containing a catalyst, the filler having a cut size or particle size smaller than a cut size or particle size of the fluidized bed catalyst; catalytically reacting the feed with the catalyst in the fluidized bed reactor to form a product mixture having a first mass ratio of catalyst to filler; recovering a vapor effluent from the product mixture, the vapor effluent comprising catalyst particles and filler; passing the vapor effluent through a solids separation system, the solids separation system passing the vapor effluent through a first cyclone to separate a first bottoms fraction and a second bottoms fraction. the first cyclone being a classifying cyclone, the first bottoms fraction having a second mass ratio greater than the first mass ratio; passing the overflow fraction to a second cyclone and separating a second bottoms fraction and a second overflow fraction, the first cyclone having a first separation efficiency for catalyst particles, the second cyclone having a second separation efficiency for catalyst particles, the second separation efficiency being greater than the first separation efficiency, and the second bottoms fraction having a third mass ratio less than the first mass ratio; and recovering olefins, aromatics, or a combination thereof from the second overflow fraction vapor discharged from the last cyclone.

[0020] The second overflow fraction may pass through an additional cyclone prior to the recovery step. Particle size in the claimed method may be measured by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), or scanning transmission electron microscopy (STEM). Size may be quantified as the median diameter of the volume fraction less than 50 vol% according to ASTM D4464-00.

[0021] The invention, in other aspects, includes any of the devices, systems (apparatus and conditions and / or chemical flows), or methods described herein.

[0022] In any aspect, the invention may be further characterized by one or any combination of the following features: The solid separation system is comprised of one or more low efficiency cyclones or classifier cyclones, or one or more recovery cyclones or multiclones, or both. The flow rate at the inlet of the low efficiency cyclone or classifier cyclone is greater than the flow rate at the inlet of the recovery cyclone. At least a portion of the solids recovered at the bottom from the one or more low efficiency cyclones or classifier cyclones are returned to the fluidized bed reactor. At least a portion of the solids recovered from the one or more recovery cyclones are discarded, and the catalytic pyrolysis is carried out at an operating temperature in the range of 300°C to 800°C, or 350°C to 700°C, or 400°C to 650°C, or 450°C to 625°C, or 500°C to 600°C. A stream enriched in ethylene or propylene, or both, is separated from the volatile products, and a stream enriched in ethylene or propylene, or both, is separated from the volatile products and at least partially recycled to the pyrolysis reactor. At least 80% by mass of the catalyst particles have a size of at least 40 microns, or at least 50 microns, or at least 60 microns, or at least 75 microns, or at least 100 microns, or between 40 and 300 microns, or between 50 and 250 microns, or between 75 and 150 microns, as measured by light scattering, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), or scanning transmission electron microscopy (STEM). At least 80% by mass of the filler particles have a size of 40 microns or less, or 30 microns or less, or 20 microns or less, or 15 microns or less, or 10 microns or less, or 1-40 microns, or 2-30 microns, or 5-20 microns, as measured by light scattering, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), or scanning transmission electron microscopy (STEM). The residence time of the fluidizing gas in the catalytic pyrolysis reactor, defined as the volume of the reactor divided by the volumetric flow rate of the fluidizing fluid, is 1 second to 480 seconds, or 1 second to 240 seconds, or 2 seconds to 60 seconds, or 3 seconds to 30 seconds, or 4 seconds to 15 seconds, under the conditions of temperature and pressure.The pressure in the fluidized bed reactor is at least 0.1 MPa, or at least 0.3 MPa, or at least 0.4 MPa, or 0.1-2.0 MPa (1-20 bar), or 0.1-1.0 MPa, or 0.3-0.8 MPa, preferably 0.4-0.6 MPa. The fluidized bed reactor is a circulating bed, bubbling bed, turbulent bed or riser reactor. The fluidizing gas for catalytic pyrolysis can include H2, CO, CO2, H2O, C1-C4 paraffins or olefins or both, N2, Ar, He, or a recycle stream, or combinations thereof. The catalyst is a solid catalyst, and the process of catalytic pyrolysis includes pyrolyzing in the presence of the solid catalyst in a fluidized bed reactor to produce a fluid product stream and spent catalyst including coke. At least 90% of the carbon in the feedstock is converted to coke and volatile products. At least a portion of the catalyst separated from the low-efficiency classifier cyclone is returned to the catalytic pyrolysis reactor, sent to a catalyst regenerator, or discarded. A catalyst and packing solids separation system consisting of a classifier cyclone and a recovery cyclone is used to return the solids from the classifier cyclone to the fluidized bed reactor and recover olefins or aromatics from the vapor discharged from the final recovery cyclone. The classifier cyclone is designed to have a cut size between the particle size distribution of the packing and the particle size distribution of the catalyst, separating the large particle size fraction and entraining the small particle size fraction in the off-gas for removal in a series of high-efficiency recovery multi-cyclones. The feed streams include plastics selected from among polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymers, polyethylene furanoate (PEF), polyamides, polyurethanes, polyethers, polycarbonates, poly(oxides), poly(sulfides), polyarylates, polyetherketones, polyetherimides, polysulfones, polyurethanes, polyvinyl alcohols, and polymers produced by polymerization of monomers such as dienes, olefins, styrenes, acrylates, acrylonitrile, methacrylates, methacrylonitrile, diacids and diols, lactones, diacids and diamines, lactams, vinyl esters, block copolymers thereof, and alloys thereof; thermosetting polymers such as epoxy resins; phenolic resins; melamine resins; alkyd resins; vinyl ester resins; unsaturated polyester resins; crosslinked polyurethanes; polyisocyanurates; crosslinked elastomers (including, but not limited to, polyisoprene, polybutadiene, styrene butadiene, styrene isoprene, ethylene propylene diene monomer polymers); and mixtures thereof. The feedstock comprises a mixture of waste plastics selected from polyethylene terephthalate (PET), high density polyethylene (HDPE), polyvinyl chloride (PVC), polyvinylidene (PVCD), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), mixed resins, or combinations thereof.The feedstock comprises a mixture of waste plastics selected from polyethylene terephthalate (PET), high density polyethylene (HDPE), polyvinyl chloride (PVC), polyvinylidene (PVCD), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), mixed resins, or combinations thereof.Fillers include alumina, aluminum, aluminum fiber, aluminum flake, aluminum hydroxide, aluminum nitride, antimony doped tin oxide, antimony oxide, aramid, attapulgite, barium sulfate, barium titanate, bentonite, bismuth carbonate, boron oxide, boron nitride, bronze powder, calcium carbonate, calcium fluoride, calcium phosphate, calcium silicate, calcium sulfate, calcium sulfate whiskers, carbon black, carbon fiber, carbon nanotubes, cellulose nanocrystals, chitosan, clay, compatibilizers, copper, diamond, diatomaceous earth, expanded graphite, ferromagnetic powders, fluorine mica, fly ash, fumed nanosilica, glass beads, glass fiber, glass flakes, glass spheres, graphene, grapha The filler is selected from the group consisting of cellulose, ground tire rubber, hollow glass microspheres, hollow silicates, hydrotalcite, iron, kaolin, lignin, magnesium hydroxide, magnesium oxide, magnetite, mica, microfibrous cellulose, molybdenum sulfide, montmorillonite, Ni-Batio3, nickel, phenolic microspheres, potassium titanate whiskers, potassium-magnesium aluminosilicate, PTFE, pyrophyllite, red mud, red phosphorus, rubber particles, sand, sepiolite, silane, silica, silicon carbide, silver powder, soot, starch, talc, tetrapod zinc oxide whiskers, titania nanoparticles, titanium dioxide, vermiculite, wollastonite, wood fiber, wood flour, zinc borate, zinc oxide, zirconium silicate, or combinations thereof. The filler is selected from the group consisting of calcium carbonate, carbon black, silica, kaolin clay, talc, or combinations thereof. The catalyst in the fluidized bed reactor comprises a zeolite. The catalyst has a SAR (silica to alumina, SiO2:Al2O3 mass ratio) greater than 12 or between 12 and 240, and a CI (constraint index) between 1 and 12 or between 5 and 10. The zeolite catalyst is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, or a combination thereof. The catalyst comprises ZSM-5. The catalyst in the fluidized bed comprises a binder material selected from alumina, zirconia, silica, magnesia, thoria, titania, boria, or a combination thereof. The catalyst in the fluidized bed comprises a catalytic molecular sieve, the catalytic molecular sieve comprising 30-90% by weight or 40-70% by weight of the composition of the catalyst particles. The catalyst in the fluidized bed is in the form of fluidizable microspheres. The plastic is pretreated in a pyrolysis reactor to remove chlorine before being fed to a fluidized bed catalytic pyrolysis reactor. The pyrolysis reactor may be a moving bed, single screw extruder, twin screw extruder, auger reactor, static mixer reactor, rotary kiln reactor, or staged grate reactor. The pyrolysis reactor includes a feed inlet port and an outlet port, and the temperature within the pyrolysis reactor ranges from a low temperature near the feed inlet port to a high temperature at the outlet port. The temperature within the pyrolysis reactor is 20°C to 225°C, e.g., 20-100°C, or 20-50°C, at or near the inlet port, and the temperature range at the outlet port is 300°C to 700°C, e.g., 325-650°C, or 350-600°C. The pyrolysis reactor includes two or more reactors connected in series. The residence time of the condensed phase in the thermal treatment or pyrolysis reactor is at least 1 minute, or at least 5 minutes, or at least 10 minutes, or at least 20 minutes, or at least 30 minutes, or from 1 to 60 minutes, or from 5 to 30 minutes, or from 10 to 30 minutes. A gas phase co-reactant, or recycle stream, comprising H2, CO, or olefins, or combinations thereof, is fed directly to one or more pyrolysis reactors or one or more catalytic pyrolysis reactors. The output vapor mixture from the fluidized bed catalytic reactor comprises at least 10 wt. % BTX, and in some embodiments ranges from 10 to 90 wt. % BTX.The solid co-reactant fed to the thermal treatment reactor comprises agricultural lime, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, limestone, hydrotalcite, activated carbon, zeolite, or other solid basic material, or combinations thereof. The output vapor mixture from the fluidized bed catalytic reactor comprises at least 10% by weight olefins, and in some embodiments, from 10 to 90% by weight olefins. The output vapor mixture from the fluidized bed catalytic reactor comprises at least 30%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60%, or from 20% to 90%, or from 30% to 70%, or from 45% to 60% olefins based on the weight of the polymer feed. The mass yield of BTX (benzene, toluene, xylenes) in the product vapor mixture from the catalytic conversion is at least 30%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60%, or 20%-90%, or 30%-70%, or 45%-60% BTX based on the mass of the polymer feed. The benzene, toluene, and xylenes are separated or recovered from the product vapor mixture. At least a portion of the aromatic products in the product vapor mixture are hydrogenated to produce naphthenes. Ethylene, propylene, butenes, or combinations thereof, are separated from the catalytic pyrolysis product vapor mixture. The product vapor mixture is subjected to a separation process to produce a gas stream enriched in CH4, CO, and H2, and at least a portion of the gas stream enriched in CH4, CO, and H2 is sent to a regenerator where it is combusted. The product vapor mixture contains CH4 and C2-C4 paraffins, and 50-100% by weight of the CH4 and C2-C4 paraffins are combusted in the regenerator. The catalyst in the fluidized bed catalytic pyrolysis reactor is removed, regenerated by oxidation with air or other oxidizing gas mixture, and returned to the catalytic pyrolysis reactor. The catalyst removed from the catalytic reactor, or recovered in a solids separation system, or both, is stripped of volatiles by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or combinations thereof, or a recycle stream from the product gas, through the catalyst particles.Condensables in the striper discharge stream are condensed, the organic and aqueous phases are separated, the liquid organic phase is sent to product recovery, the aqueous phase is sent to wastewater recovery, and the catalyst with the volatile organic compounds removed is sent to a catalyst regenerator. The regenerated hot catalyst provides heat to a catalytic pyrolysis reactor. At least a portion of the gas in the product mixture is combusted in the regenerator. At least a portion of the natural gas is supplied to the catalyst regenerator. The heat from the catalyst regeneration provides energy for the thermal treatment or pyrolysis or catalytic pyrolysis step. The heat recovered from the catalyst regenerator is used to heat the feedstock, thermal processing reactor, pyrolysis reactor, catalytic pyrolysis fluidized bed reactor, or combinations thereof. The combustion product gas (exhaust gas) generated in either the catalyst regenerator or the packing regenerator, or both, is sent to a solid separation system, or multiple solid separation systems, which includes a series of cyclones, optional classifying cyclones, followed by one or more high efficiency multi-cyclones. The flow velocity at the inlet of the low efficiency cyclone is greater than 5 meters / second, greater than 10 meters / second, greater than 15 meters / second, 5 to 40 meters / second, 10 to 30 meters / second, or 15 to 25 meters / second. In any of the above-mentioned classifying cyclones, the ratio of the vortex diameter ["De" in FIG. 5] to the cylinder diameter ("D" in FIG. 5) is within the range of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.1-0.8, 0.3-0.7, 0.4-0.6, 0.45-0.55, 0.49-0.51, or the ratio of the vortex length to the cylinder length is within the range of 0.5, 0.6, 0.7, 0.8, 0.9, 0.3-0.95, 0.5-0.95, 0.8-0.95, 0.85-0.95, or the ratio of the underflow diameter to the vortex diameter is within the range of 0.02, 0.1, 0.15, 0. 2, 0.25, 0.3, 0.5, 1.0, 1.25, or 0.02-1.25, 0.02-0.5, 0.1-0.3, or 0.15-0.25; or the ratio of inlet height to inlet width is within the ranges of 0.75, 1, 1.5, 2, 2.4, 3, 4, 5, or 0.75-5, 1.5-4, 2-3, 2.2-2.6; or the ratio of vortex length (S) to total height (H) is within the ranges of 0.1, 0.2, 0.3, 0.36, 0.4, 0.5, 0.6, 0.8, or 0.1-0.8, 0.2-0.6, 0.3-0.4, 0.34-0.38. One or more of the cyclones does not have a vortex detection device. One or more of the recovery cyclones includes at least one multi-clone.In the multiple small diameter cyclones in any one of the multi-clone, the ratio of the vortex diameter to the cylinder diameter is within the range of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.1 to 0.8, 0.3 to 0.7, 0.4 to 0.6, 0.45 to 0.55, or 0.49 to 0.51, or the ratio of the vortex length to the cylinder length is within the range of 0.5, 0.6, 0.7, 0.8, 0.9, or 0.3 to 0.95, 0.5 to 0.95, 0.8 to 0.95, or 0.85 to 0.95, or the ratio of the underflow diameter to the vortex diameter is within the range of 0.02, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5, 1.0, 1.25, or 0.02-1.25, 0.02-0.5, 0.1-0.3, or 0.15-0.25; or the ratio of the inlet height to the inlet width is within the ranges of 0.75, 1, 1.5, 2, 2.4, 3, 4, 5, or 0.75-5, 1.5-4, 2-3, 2.2-2.6; or the ratio of the vortex length to the total height is within the ranges of 0.1, 0.2, 0.3, 0.36, 0.4, 0.5, 0.6, 0.8, or 0.1-0.8, 0.2-0.6, 0.3-0.4, 0.34-0.38. The flow velocity at the inlet of any recovery cyclone is 25, or 20, or 15, or 10, or 5, or 3, or 3-20, or 5-15, or 6-12 meters per second. The mass ratio of catalyst particles to filler particles entering the classifying cyclone is at least 1, 2, 5, 10, 20, 30, or 50, or 0.1-50, 0.5-30, or 5-20. The mass ratio of catalyst particles to filler particles exiting the bottom of the classifying cyclone is at least 5, or at least 30, or at least 50, or at least 200, or at least 1000, or 5-10,000, 30-5,000, or 50-1000. The mass ratio of catalyst particles to filler particles in the overflow from the classifying cyclone is 10, 5, 2, 1, 0.2, or 0.1 or less, or 0.0001 to 10, 0.001 to 5, or 0.01 to 1. The mass ratio of catalyst particles to filler particles in the overflow from the recovery cyclone is 0.1 or less, 0.001, 0.00001, or 0.000001 to 0.1, 0.00001 to 0.01, or 0.0001 to 0.001.The mass ratio of catalyst particles to filler particles at the bottom from the recovery cyclone is 0.1 or less, 0.001, 0.00001, or 0.0000001-0.1, 0.00001-0.01, or 0.0001-0.001. The number of small cyclones in one multi-clone is 4, 9, 16, 25, 36, 49, or 64, or 4-64, or 9-49, or 16-36. The efficiency of the low-efficiency cyclone or classification cyclone or combination of cyclones is 95%, 90%, 85%, 80%, or 75% or less. The combined efficiency of the one or more recovery cyclones is at least 80%, or 85%, or 90%, or 95%, or 98%, or 99%, or 99.5%. The particle concentration in the steam product discharged from the recovery cyclones is at least 1 / m of steam product. 3The plastic feed stream is treated in a thermal treatment reactor and the condensed phase is sent to a catalytic pyrolysis reactor. A sweep gas such as H2O, N2, Ar, CO2, or a combination thereof is fed to the thermal treatment reactor and vapors are exhausted. The plastic feedstock is heated to a temperature of 250-300 °C in a thermal treatment furnace and the product is sent to a pyrolysis furnace. An inert gas is fed to the thermal treatment furnace and vapors are exhausted. The hot product stream from the thermal treatment reactor is filtered to remove solids before being fed to the pyrolysis reactor. The product produced in the optional thermal treatment reactor is transferred to a catalytic pyrolysis reactor containing a catalyst without separating most of the product. The non-vapor products of the thermal treatment reactor, or a portion of the gas remaining after removal of the desired product, or both, are combusted to provide energy for the catalytic reaction in the fluidized bed. A solid co-reactant is fed to the thermal treatment reactor. The solid co-reactant is separated from the process stream and transferred to a combustion regenerator where the carbonaceous material is reacted with air and at least a portion of the hot solid co-reactant is returned to the thermal treatment reactor. The hot exhaust gases leaving the solid co-reactant regenerator are sent to a catalytic heater to heat the catalyst in the catalytic pyrolysis reactor. Thermal treatment is accomplished by heating the feedstock to a temperature of 250-300°C and holding it at that temperature while removing steam, followed by either sending the condensed phase to a catalytic pyrolysis reactor or pyrolyzing it at further elevated temperatures in the pyrolysis reactor. The catalyst removed from the catalytic reactor or recovered in the solids separation system, or both, is stripped of volatiles by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or a combination thereof, or a recycle stream from the product gas, through the catalyst particles, the stream is condensed, the organic and aqueous phases are separated, the liquid organic phase is sent to product recovery, the aqueous phase is sent to wastewater recovery, and the catalyst with the volatile organic compounds removed is sent to a catalyst regenerator, returned to the catalytic reactor, discarded, or a combination thereof. The filler is recovered from the solids separation system.The filler recovered in the solids separation system is stripped of volatiles by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or a combination of these, or a recycle stream from the product gas, through the filler particles, the stream is condensed, the organic and aqueous phases are separated, the liquid organic phase is sent to product recovery, the aqueous phase is sent to wastewater recovery, and the filler with the volatile organic compounds removed is sent to a filler regenerator or disposed of, or a combination thereof. Effect of the Invention

[0023] Chemical recycling of plastics by pyrolysis in a thermochemical reactor has many advantages, including: Solids separation system: Any type of plastic mixture is suitable, the long residence time in the pyrolysis reactor heats the plastic pieces to decomposition temperature, eliminating the need to grind the plastic particles into small pieces, pyrolysis can be carried out at high temperatures, an optional thermal treatment reactor can remove undesirable contaminants, small particle size fillers can be efficiently separated from the catalyst and disposed of, and the catalyst separated from the fillers can be returned to the process, reducing catalyst losses and the associated catalyst costs. Another advantage of the inventive process is that the production of the crude liquid product stream made from recycled plastics by the inventive process can be carried out in a separate location from the product separation and purification system, and this "distributed processing" scheme minimizes the costs of separation and purification for small regional plastics upgrading facilities. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 illustrates generally a process for converting mixed plastic materials into useful products by pyrolyzing the mixed plastics and catalytically reacting the feed mixture to produce olefins, aromatics, or a combination thereof, which includes a cyclonic solids separation system to separate fillers and other particulates from the system. [Diagram 2]FIG. 2 illustrates generally a process for converting mixed plastic materials into useful products by pyrolyzing the mixed plastics and catalytically reacting the products to produce olefins, aromatics, or combinations thereof, in which a thermal treatment reactor is used to remove contaminants before feeding the pyrolysis reactor, and a solids separation system is used to separate fillers and other particulates from the system. [Diagram 3] FIG. 3 shows a schematic diagram of the solids separation system. [Figure 4] FIG. 4 shows the particle size distribution of the filler, catalyst, and the combined filler and catalyst in the feed of Example 1. [Diagram 5] FIG. 5 shows the parameters that define the cyclone design. [Figure 6] FIG. 6 shows the multiclone design. [Figure 7] FIG. 7 shows the particle size distribution of the solids discharged from the regenerator, which includes the filler and catalyst, as determined experimentally. [Figure 8] FIG. 8 shows a schematic diagram of a pilot plant reactor operated using a solids separation system. [Figure 9] Figure 9 shows the particle size distribution (PSD) measured for the catalyst regenerated from standpipe 3. The PSD was measured for the catalyst regenerated from standpipe 3 after 24 hours TOS before introducing the filler-containing plastic feed (lowest peak), after 27.5 hours TOS after 3.5 hours of feeding plastic at a rate of 6.5 kg / hr (medium size peak), and after 9.5 hours of feeding plastic at a rate of 6.5 kg / hr (highest peak). [Figure 10] FIG. 10 shows the particle size distribution (PSD) of unstripped reactor catalyst from standpipe 1 at 27.5 hour TOS (low peak) after feeding plastics at a rate of 6.5 kg / hr for 3.5 hours and at 75.5 hour TOS (high peak) after feeding plastics at a rate of 6.5 kg / hr for 9.5 hours. [Figure 11]FIG. 11 shows the PSD of the exfoliated reactor catalyst at 27.5 hour TOS (short peak) after feeding plastics at a rate of 6.5 kg / hr for 3.5 hours and at 75.5 hour TOS (high peak) after feeding plastics at a rate of 6.5 kg / hr for 9.5 hours. [Figure 12] Figure 12 shows the PSDs of samples taken from standpipes 1 (unstripped), 2 (stripped), and 3 (regenerated) at 27.5 h TOS after feeding plastics at a rate of 6.5 kg / h for 3.5 h. The higher peak is due to the regenerated catalyst, and the shorter peak represents the other two overlapping PSDs. [Figure 13] Figure 13 shows a comparison of the PSD of the material passing through the solids separation system (top data) and the PSD of the catalyst in the fluidized bed (bottom data). Each data point represents the mass fraction of the sample that contains particles smaller than a particular diameter. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] term Aromatic Compound - As used herein, the term "aromatic compound" or "aromatic compound" is used to refer to a hydrocarbon compound or group of compounds that contain one or more aromatic groups, such as, for example, single aromatic ring systems (e.g., benzyl, phenyl, etc.) and fused polycyclic aromatic ring systems (e.g., naphthyl, 1,2,3,4-tetrahydronaphthyl, etc.). Examples of aromatic compounds include, but are not limited to, benzene, toluene, indane, indene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, trimethylbenzene (e.g., 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, etc.), ethylbenzene, styrene, cumene, methylbenzene, propylbenzene, xylene (e.g., p-xylene, m-xylene, o-xylene, etc.), naphthalene, methylnaphthalene (e.g., 1-methylnaphthalene, anthracene, 9.10-dimethylanthracene, pyrene, phenanthrene, dimethylnaphthalene (e.g., 1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene, 2,5-dimethylnaphthalene, etc.), ethylnaphthalene, hydrindene, methylhydrindene, dimethylhydrindene. In some embodiments, single ring aromatics and / or polycyclic aromatics may also be produced.

[0026] Cyclone separators - Cyclone separators use centrifugal force to separate solids from liquids. The separation process depends on the size and density of the particles. It is also possible for fine particles to be entrained along with the liquid. A cyclone consists of a short vertical cylindrical vessel with a conical bottom. A tangential inlet is attached to the top of the vessel. The solids outlet is at the bottom. The fluid outlet is located at the center of the top and may extend to the inside of the separator. This arrangement prevents direct short-circuiting of gas from the fluid inlet to the outlet. The solids to be separated are suspended in the gas stream, which is introduced tangentially at high velocity, creating a rotational motion inside the vessel. Centrifugal force throws the particles against the walls of the vessel. As the gas velocity decreases, the larger and denser particles fall to the bottom and collect at the solids outlet. The gas exits through the central outlet at the top, entraining the smaller and less dense particles. The stream exiting the central outlet at the top of the cyclone is the overflow fraction, while the stream exiting the solids outlet at the bottom is the underflow or bottom fraction.

[0027] Catalysts - Catalytic components useful in the context of the present invention can be selected from any catalyst known in the art or understood by one of ordinary skill in the art. A catalyst promotes or affects a reaction. Thus, as used herein, a catalyst lowers the activation energy (increases the rate) of a chemical process and / or improves the distribution of products or intermediates in a chemical reaction (e.g., shape-selective catalysis). Examples of reactions that can be catalyzed include dehydration, dehydrogenation, isomerization, hydrogen transfer, hydrogenation, polymerization, cyclization, desulfurization, denitrogenation, deoxygenation, aromatization, decarboxylation, decarboxylation, aldol condensation, and combinations thereof. The catalytic components can be acidic, neutral, or basic, as will be understood by one of ordinary skill in the art.

[0028] For catalytic pyrolysis, particularly advantageous catalysts include those that include internal porosity selected according to pore size (e.g., pore sizes typically associated with mesoporous and zeolites), such as those that include average pore sizes of less than about 10 nm, less than about 5 nm, less than about 2 nm, less than about 1 nm, less than about 0.5 nm, or less. In some embodiments, catalysts with average pore sizes of about 0.5 nm to about 10 nm can be used. In some embodiments, catalysts with average pore sizes of about 0.55 nm to about 0.65 nm, or about 0.59 nm to about 0.63 nm can be used. In some cases, catalysts with average pore sizes of about 0.7 nm to about 0.8 nm, or about 0.72 nm to about 0.78 nm can be used.

[0029] In some preferred embodiments of catalytic pyrolysis, the catalyst may be selected from natural zeolites, synthetic zeolites, and combinations thereof. In certain embodiments, the catalyst may be a ZSM-5 zeolite catalyst, as will be appreciated by those skilled in the art. Optionally, such catalysts may contain acid sites. Other types of zeolite catalysts include ferrierite, zeolite Y, zeolite beta, mordenite, MCM-22, ZSM-23, ZSM-57, SUZ-4, EU-1, ZSM-11, (S)AlPO-31, SSZ-23, and the like. Zeolites and other small pore materials are often characterized by a constraint index. The constraint index approximates the ratio of the cracking rate constants of normal hexane and 3-methylpentane. Methods for determining the constraint index are described in more detail in U.S. Pat. No. 4,029,716, which is incorporated by reference for details of the method.

[0030] The Constraint Index (CI) values ​​of some common materials are as follows:

[0031] [Table 1]

[0032] The CI may vary within the range of 1-12. Similarly, other variables such as the size of the crystals and the presence of occluded contaminants or binders that may be tightly bound to the crystals may also affect the CI. Those skilled in the art will appreciate that the CI as used herein provides a very useful means for characterizing the molecular sieves of interest, but is an approximation given how it is determined, and in some cases, extreme values ​​of the variables may be compounded. However, the CI value of any molecular sieve useful herein is approximately within the range of 1-12. In other embodiments, non-zeolitic catalysts such as WOx / ZrO2, aluminum phosphate, etc. can be used. In some embodiments, the catalyst can include a metal and / or metal oxide. Suitable metals and / or oxides include, for example, nickel, palladium, platinum, titanium, vanadium, chromium, manganese, iron, cobalt, zinc, copper, gallium, and / or any of their oxides. In some cases, a promoting element selected from among rare earth elements, i.e., elements 57-71, cerium, zirconium, or their oxides, or combinations thereof, can be included to modify the activity or structure of the catalyst. Additionally, in some cases, the properties of the catalyst (e.g., pore structure, type and / or number of acid sites, etc.) can be selected to selectively produce the desired products.

[0033] Catalysts for other processes such as olefin alkylation, aromatization (hydrocarbon reforming), hydrogenation, hydrotreating, deoxygenation, denitrification, desulfurization, etc. are well known and can be selected for olefin conversion or other processes described herein. Plastics or Polymers - As used herein, the terms "plastic" and "polymer" are used interchangeably. A polymer is a carbon-based (usually at least 50% by weight C) material composed primarily of repeating units and having a number average molecular weight of at least 100, usually greater than 1000 or even 10,000. Polymers include thermoplastic polymers (e.g., polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymers, polyethylene furanoate (PEF), polyamides, polyurethanes, polyethers, polycarbonates, poly(oxides), poly(sulfides), polyarylates, polyetherketones, polyetherimides, polysulfones, polyurethanes, polyvinyl alcohols, etc.), and monomers (dienes, olefins, styrenes, acrylates, acrylonitrile, methacrylates, methacrylonitrile, diacids, and and diols, lactones, diacids and diamines, lactams, vinyl halides, vinyl esters, block copolymers thereof, and alloys thereof), thermosetting polymers (epoxy resins; phenolic resins; melamine resins; alkyd resins; vinyl ester resins; unsaturated polyester resins; crosslinked polyurethanes; polyisocyanurates, etc.); crosslinked elastomers (including but not limited to polyisoprene, polybutadiene, styrene-butadiene, styrene-isoprene, ethylene-propylene-diene monomer polymers); and blends thereof. Mixtures of polymers separated from municipal solid waste or other waste streams are suitable feeds if they contain only small amounts of contaminants such as S, N, O, halogens, minerals, metals, or carbon black. Polymers that produce halogenated materials upon pyrolysis, such as polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), and other halogenated polymers, are typically minimized or excluded from the feeds useful in this invention.

[0034] Pyrolysis - The terms "pyrolysis" and "pyrolyzing" are given their conventional meaning in the art and are used to refer to the conversion of compounds, such as solid hydrocarbon materials, to one or more other substances, such as volatile organic compounds, gases, coke, etc., by heat, preferably without the addition of O2 or in the absence of O2. Preferably, the volume fraction of O2 present in the pyrolysis reaction chamber is 0.5% or less. Pyrolysis can be carried out with or without the use of a catalyst. "Catalytic pyrolysis" refers to pyrolysis carried out in the presence of a catalyst and may include procedures detailed below. Examples of catalytic pyrolysis processes are outlined, for example, in Huber, GW et al, "Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering," Chem. Rev. 106, (2006), pp. 4044-4098.

[0035] A "classifying cyclone" is a type of cyclone separator used to separate solid particles from a gas or steam stream based on the particle size and density. Classifying cyclones work by using centrifugal force to separate a portion of the particles, defined by a cut size, from the gas stream. As the gas and particles enter the cyclone, the rotational motion creates a vortex that moves the heavier particles toward the walls of the cyclone while the lighter particles remain in the center. The separated particles exit the cyclone through a separate outlet while the gas or steam continues to flow through the cyclone with the remaining particles and is discharged through another outlet.

[0036] A "recovery cyclone" is a type of cyclone that separates solids from a vapor stream and removes enough of the solids so that the vapor stream can be processed in conventional condensing, distilling, or upgrading equipment in a chemical process. A typical recovery cyclone has a particle concentration in the vapor product discharged from the recovery cyclone of, for example, 1 m3 of vapor product. 3 Sufficient particles are removed so that the concentration is below a target concentration, such as 200, 300, 400, or 500 μg per unit volume or less.

[0037] The separation efficiency of a cyclone (sometimes called recovery) is the percentage of a selected cumulative solids in the stream that is sent to either product. The efficiency, E (or overall efficiency), is the difference between the recovery of the fine and coarse products and is calculated as follows: E=E P -E T =(X P ·W P -X T ·W T ) / X F ·W F where P is the product, T is the second (or fines), F is the feed, X is the fraction of particles of a particular size, and W is the mass of particles of a particular size. For details, see Klumpar, VI, "Measuring and Optimizing Air Classifier Performance," Sep. Technol., 2, 1992, 124-135.

[0038] Cyclones with low efficiency, i.e. most of the solids entering the cyclone pass through it and are discharged with the overflow, are called classifying cyclones. Classifying cyclones can be used to separate materials with different average particle sizes. Cyclones with high efficiency, i.e. only a small portion of the solids entering the cyclone pass through it and are discharged with the overflow, and their purpose is to remove solids from the steam stream, are called recovery cyclones.

[0039] Cut Size - In a particle size separation process, the term "cut size" (or d50) is the particle size at which a particle has an equal probability of reporting to the overflow or underflow. The value of dX indicates the particle size that has an X% probability of being removed in the underflow of solids discharged from the bottom of the cyclone rather than the overflow of gas containing entrained solids. The distribution curve shows the mass fraction of each particle size that is discharged to the crude product (underflow or bottom).

[0040] Fillers - The term "filler" refers to solid materials that are added to or become part of the polymer composition (up to 20% by weight), such as alumina, aluminum, aluminum fibers, aluminum flakes, aluminum hydroxide, aluminum nitride, antimony doped tin oxide, antimony oxide, aramid, attapulgite, barium sulfate, barium titanate, bentonite, bismuth carbonate, boron oxide, boron nitride, bronze powder, calcium carbonate, calcium fluoride, calcium phosphate, calcium silicate, calcium sulfate, calcium sulfate whiskers, carbon black, carbon fibers, carbon nanotubes, cellulose nanocrystals, chitosan, clays, compatibilizers, copper, diamond, diatomaceous earth, expanded graphite, ferromagnetic powders, fluorine mica, fly ash, fumed nanosilica, gas. lath beads, glass fibers, glass flakes, glass spheres, graphene, graphite, ground tire rubber, hollow glass microspheres, hollow silicates, hydrotalcite, iron, kaolin, lignin, magnesium hydroxide, magnesium oxide, magnetite, mica, fine fibrous cellulose, molybdenum sulfide, montmorillonite, Ni-BaTiO3, nickel, phenolic microspheres, potassium titanate whiskers, potassium magnesium aluminosilicate, PTFE, pyrophyllite, red mud, red phosphorus, rubber particles, sand, sepiolite, silane, silica, silicon carbide, silver powder, soot, starch, talc, tetrapod zinc oxide whiskers, titania nanoparticles, titanium dioxide, vermiculite, wollastonite, wood fibers, wood flour, zinc borate, zinc oxide, zirconium silicate, or combinations thereof.

[0041] Fluid - The term "fluid" refers to a gas, liquid, a mixture of gas and liquid, or a gas or liquid containing dispersed solids, droplets, and / or bubbles. The terms "gas" and "vapor" have the same meaning and may be used interchangeably. In some embodiments, it may be advantageous to control the residence time of the fluidizing fluid in the reactor. The fluidization residence time of the fluidizing fluid is defined as the volume of the reactor divided by the volumetric flow rate of the fluidizing fluid under process conditions of temperature and pressure.

[0042] Fluidized Bed Reactor - The term "fluidized bed reactor" is given its conventional meaning in the art and is used to refer to a reactor that includes a vessel that can contain particulate solid material (e.g., silica particles, catalyst particles, etc.) in which a fluid (e.g., gas or liquid) passes through the particulate solid material at a sufficient velocity to cause the solid material to be suspended and behave as if it were a fluid. Examples of fluidized bed reactors are described in "Fluidization Engineering" by D. Kunii and O. Levenspiel (Butterworth-Heinemann, 1991), which is incorporated herein by reference. The term "circulating fluidized bed reactor" is also given its conventional meaning in the art and is used to refer to a fluidized bed reactor in which the particulate solid material is discharged from the reactor, circulated through a line in fluid communication with the reactor, and returned to the reactor. Examples of circulating fluidized bed reactors are described in "Fluidization Engineering" by D. Kunii and O. Levenspiel (Butterworth-Heinemann, 1991).

[0043] Bubbling and turbulent fluidized bed reactors are also known to those skilled in the art. In a bubbling fluidized bed reactor, the fluid stream used to fluidize the particulate solid material is operated at a flow rate low enough that bubbles and voids are observed within the volume of the fluidized bed during operation. In a turbulent fluidized bed reactor, the flow rate of the fluidizing stream is higher than that used in a bubbling fluidized bed reactor, so that bubbles and voids are not observed within the volume of the fluidized bed during operation. Examples of bubbling and turbulent fluidized bed reactors are described in Kirk-Othmer Encyclopedia of Chemical Technology (online), Vol. 11, Hoboken, NJ: Wiley-Interscience, 2001, pages 791-825, which are incorporated herein by reference.

[0044] Olefins - The term "olefin" or "olefinic compound" (also known as "alkene") is used to refer to an unsaturated hydrocarbon containing one or more pairs of carbon atoms joined by a double bond. Olefins include both cyclic and non-cyclic olefins (aliphatic), where the double bond is between carbon atoms that form part of a cyclic (closed ring) or open chain group, respectively. Furthermore, olefins can contain any number of double bonds (e.g., monoolefins, diolefins, triolefins, etc.). Examples of olefinic compounds include, but are not limited to, ethene, propene, allene (propadiene), 1-butene, 2-butene, isobutene (2-methylpropene), butadiene, isoprene, etc. Examples of cyclic olefins include cyclopentene, cyclohexane, cycloheptene, etc. Aromatic compounds such as toluene are not considered olefins, but olefins that contain aromatic moieties (e.g., benzyl acrylate and styrene) are considered olefins.

[0045] Here, "thermal treatment" is used as a process in which the feed mixture is heated to a moderate temperature at which some pollutants such as HCl, H2S, and NH3 are evolved and exhausted, the feed mixture melts, and solids such as minerals, metals, and carbon black are removed by filtration.

[0046] As in standard patent terminology, the term "comprising" means "including" and does not exclude additional components. Aspects of the invention described in conjunction with the term "comprising" also include narrower embodiments in which the term "comprising" is replaced with the narrower terms "consisting essentially of" or "consisting of." As used herein, the terms "comprising" or "comprising" should not be construed as limiting the invention, but rather as reciting example components.

[0047] Detailed Description of the Invention FIG. 1 shows a schematic diagram of a process for converting plastic waste to olefins and aromatics. The plastic mixture 10 is introduced into an optional feed system 100, which prepares the plastic mixture for introduction into the process by removing undesirable feed materials 102, such as metals, minerals, clays, halogenated materials, contaminants such as Cl, Br, and other elements that may contaminate the catalyst, and / or sizing the materials to a desired size range. The steps of removing undesirable feed materials and sizing can be performed in any order, i.e., one step can be performed first and the other step can be performed second. The remaining plastic mixture 101 is sent to an optional washing process 110, where the plastic mixture is washed, for example by treatment with a washing solution 112 to remove unwanted materials such as dirt, labels, coatings, and the like, to produce a washed plastic mixture 111 and a spent solution 113. The plastic mixture 111 is sent to an optional pyrolysis reactor 120. Optionally, a gas phase co-reactant or recycle stream (not shown) including H2, CO, or olefins, or a combination thereof, can be fed directly to the optional pyrolysis reactor 120 or catalytic pyrolysis reactor 140. In the optional pyrolysis reactor 120, the mixture can be heated to a temperature that will break down the plastics into a product mixture including a combination of gas, solid, and liquid phases. Without separation, at least a portion of the raw pyrolysis product mixture 121 is sent to the catalytic reactor 140 while maintaining the temperature of the pyrolysis product mixture at least at the temperature at which it exited the pyrolysis reactor 120. The plastic mixture, i.e., raw plastic mixture 101, washed plastic mixture 111, or pyrolysis product mixture 121, is sent to the high temperature catalytic reactor 140, which is packed with an aromatization catalyst effective to convert paraffins, olefins, or both, to aromatics, as shown as catalytic vapor stream 141. A portion of the catalyst 142 is continuously removed from the reactor 140 and / or separated from the product 141 and sent to a catalyst regenerator 150 .In the catalyst regenerator 150, the catalyst is treated with an oxygen source such as air 151 to oxidize, the hot regenerated catalyst 143 is returned to the reactor 140 to provide heat thereto, and the combustion product gas 152 is sent to the regenerator exhaust gas cleanup cyclone (not shown), exhausted, or used to provide heat to any pyrolysis or catalytic pyrolysis reactors. The catalyst vapor stream 141 is sent to a solids separation system 160 where the catalyst 162 is separated from the charge 163 and catalyst product stream 161. The catalyst 162 can be returned to the reactor 140, passed to the catalyst regenerator 150, or discarded. The charge 163 can be passed to a charge regenerator (not shown) or discarded. The catalyst product stream 161 can be separated into components such as ethylene, propylene, butenes, C1-C5 paraffins, benzene, toluene, xylene, naphthalene, and other fractions in a separation scheme using conventional separation techniques not shown here.

[0048] FIG. 2 shows a schematic diagram of another embodiment of the process of the present invention for converting plastic waste to olefins and aromatics. The plastic mixture 10 is introduced into an optional feed system 100, which prepares the plastic mixture for introduction into the process by removing undesirable feed materials 102, such as metals, minerals, clays, halogenated materials, contaminants such as Cl, Br, and other elements that may contaminate the catalyst, and / or sizing the materials to a desired size range. The steps of removing undesirable feed materials and sizing can be performed in any order; that is, one step can be performed first and the other step can be performed second. The remaining plastic mixture 101 is sent to an optional washing process 110, where the plastic mixture is washed, for example, by treatment with a washing solution 112 to remove unwanted materials such as dirt, labels, coatings, and the like, to produce a washed plastic mixture 111 and a spent solution 113. The prepared plastic mixture 111 is sent to a thermal treatment reactor 115 along with an optional co-reactant 122, such as a heat transfer medium or getter, where the mixture is heated to an intermediate temperature to partially decompose the plastic, for example, decomposing PVC or PVDC to release HCl, or decomposing another halogenated polymer to release HCl, HBr, or HI, or releasing vapors such as NH3, HO, etc. An optional sweep gas 124, such as HO, N2, Ar, CO2, or combinations thereof, is fed to the thermal treatment reactor 115 to help remove the vapors generated therein and exits through an exit port 125. With or without a sweep gas, the vapor 125 can be treated to capture or neutralize HCl and toxic materials before being released or transferred to water treatment. The vapor 125 typically contains at least 60% or at least 80% HO and may contain HCl, halocarbon compounds, and other species that are more volatile than the molten polymer. The condensed phase 126 is sent to the optional pyrolysis reactor 120 where it is heated and decomposed into a product mixture comprising a combination of solid, liquid, and gas phases. If the optional pyrolysis reactor is used, the temperature of the pyrolysis product mixture is maintained at least at the temperature at which it exits the pyrolysis reactor 120.The plastic feed mixture, or raw product mixture 121 if optional pyrolysis reactor 120 is used, is fed to a high temperature catalytic reactor 140 packed with an aromatization catalyst effective to convert paraffins, olefins, or both to aromatics, shown as catalyst vapor stream 141. A portion of the catalyst 142 may be continuously removed from the reactor 140 and / or separated from the product 141, at least a portion of which is fed to a catalyst regenerator 150. In the catalyst regenerator 150, the catalyst is oxidized by treatment with an oxygen source such as air 151, and the regenerated catalyst 143 is returned to the reactor 140, and the combustion product gases 152 are fed to a regenerator cyclone (not shown) or exhausted. Optionally, natural gas or a recycle stream may be fed to the catalyst regenerator 150 to raise the temperature of the regenerated catalyst to the temperature required for the catalytic pyrolysis process. The catalyst vapor stream 141 is sent to a solids separation system 160 where the catalyst 162 is separated from the charge 163 and the catalyst product stream 161. At least a portion of the catalyst 162 can be returned to the reactor 140, sent to a catalyst regenerator 150, or disposed of. The charge 163 can be sent to a charge regenerator (not shown) where the charge is oxidized with air or oxygen to generate heat that can be used in the process or disposed of. The catalyst product 141 can be separated into components such as ethylene, propylene, butenes, C1-C5 paraffins, benzene, toluene, xylenes, naphthalene, and other fractions in a separation scheme using conventional separation techniques.

[0049] FIG. 3 shows a more detailed schematic diagram of the solids separation system 160. The catalyst vapor stream 141, which is loaded with catalyst and packing, is sent to one or more classification (low efficiency) cyclones 170, where the catalyst 162, which contains a small amount of packing particles, is separated and sent to catalyst regeneration 150, to catalytic pyrolysis reactor 140, or discarded, or a combination of these. The vapor stream 171 leaving the classification device 170 contains most of the packing and very little catalyst except for some fine particles. The vapor stream 171 is sent to a series (N units) of high efficiency multiclones 180, where the packing 182 is separated and optionally sent to packing regenerators 190, where the packing is combusted with air to provide heat for the process or discarded. The regenerated packing 191 is discarded. The product stream 181, with most of the packing removed, is sent to separation and product collection. This stream contains a concentration of solids that does not exceed the allowable limit for entrained particles to be discharged to the atmosphere.

[0050] The solids separation system of the present invention provides a means for separating the filler from the catalyst, the cut size or particle size of the filler being smaller than the cut size or particle size of the fluidized bed catalyst. The vapor effluent from the catalytic pyrolysis, including the catalyst particles and the filler, passes through a first cyclone for separation into a first bottoms fraction and a first overflow fraction. The bottoms fraction from the first cyclone has a catalyst to filler mass ratio greater than the catalyst to filler mass ratio in the effluent from the catalytic pyrolysis reactor, i.e., is enriched in catalyst. The overflow fraction from the first cyclone is sent to a second cyclone, having a catalyst particle separation efficiency greater than the first separation efficiency, for separation into a second bottoms fraction and a second overflow fraction. The bottoms fraction from the second cyclone has a catalyst to filler mass ratio less than that of the effluent from the catalytic pyrolysis reactor, i.e., is enriched in filler. It is recognized that the first cyclone can include multiple cyclones and the second cyclone can also include multiple cyclones.

[0051] The exhaust gas from the catalyst regenerator or filler regenerator may be passed through one or more cyclones to remove particulate matter therefrom. Optionally, if the exhaust gas from the catalyst regenerator contains catalyst particles that are desired to be recovered, the exhaust gas from the catalyst regenerator may be subjected to a series of cyclones including a classifying cyclone and one or more refining cyclones. The catalyst particles recovered from the classifying cyclones may be returned to the catalytic pyrolysis reactor. Small particles recovered from the refining stage may be discarded.

[0052] Combustible gases such as methane, ethane, propane, butane, CO, H2, etc., can optionally be recovered from the vapor stream 125, from the gases produced in the catalytic pyrolysis in the fluidized bed reactor, or from the product stream 141. The combustible gases can provide heat to the process. The heat required for the catalytic pyrolysis process reactor 140 or the optional pyrolysis reactor 120, or both, can be provided at least in part by the hot regenerated catalyst 143. Heat in the reactors 115 or 120 can also be provided by pressure / friction and / or other heat sources such as resistive or inductive heating.

[0053] In some embodiments, for example when recycled polymeric materials are used, impurities may be optionally removed from the feed composition by an optional separation step, such as 100 in FIG. 1 or FIG. 2, before being fed to the reactor. In some cases, the separation step may include mechanical separation, sink / float separation, air scrubbing, or other known separation processes (preferably in an automated mode). The particle size of the solid polymeric feed composition may be reduced in a size reduction system as part of 100, before passing the feed to the thermal treatment reactor or pyrolysis reactor. In some embodiments, the average diameter of the size-reduced feed composition discharged from the size reduction system may be 50% or less, 25% or less, 10% or less, 5% or less, or 2% or less of the mass average diameter of the feed composition fed to the size reduction system. The feed mixture may include a plastic mixture in which at least 85%, or at least 90%, or at least 95%, by weight, of the particles pass through a 0.25 inch (0.6 cm), or 0.5 inch (1.2 cm), or 1.0 inch (2.5 cm), or 1.5 inch (3.7 cm), or 2 inch (5.0 cm), or 4 inch (10.0 cm) screen. The average diameter (size) may be determined by sieving through a mesh (screen). Larger particle feed ingredients are easier to transport and process than smaller particle feed ingredients. However, it may be advantageous to feed smaller particles to the reactor. A size reduction system may be used to feed smaller particles to the reactor while transporting the larger particle feed between the source and the process.

[0054] Feedstocks suitable for use in the present invention can include any type of polymeric material, including: polyethylene (PE), polypropylene (PP), polyacetylene, polybutylene, polyolefin, polyethylene terephthalate (PET), polybutylene terephthalate, polyester, copolyester, polycarbonate, polyurethane, polyamide, polystyrene (PS), polyacetal, epoxy, polycyanurate, polyacrylic, polyurea, vinyl ester, polyacrylonitrile, polyamide, polyurethane, polyether, polycarbonate, poly(oxide), poly(sulfide), polyarylate, polyetherketone, polyetherimide, polysulfone, polyurethane, polyvinyl alcohol, polyvinyl chloride (PVC), polyvinyl chloride (PVDC), polyvinyl acetate, nylon, copolymers (ethylene-propylene, acrylonitrile-butadiene-styrene (ABS), nitrile rubber, natural and synthetic rubber, tires, styrene-butadiene, styrene-acrylonitrile, styrene-isoprene, styrene-maleic anhydride, ethylene-vinyl acetate, nylon 12 / 6 / 66, etc.), filled polymers, polymer composites, plastic alloys, other polymeric materials, and polymers or plastics dissolved in solvents (obtained as waste or discarded materials from polymer or plastic manufacturing processes, post-consumer recycled polymeric materials), materials separated from waste streams such as municipal solid waste, and polymers produced by polymerization of monomers (e.g., dienes, olefins, styrenes, acrylates, acrylonitrile, methacrylates, methacrylonitrile, diacids and diols, lactones, diacids and diamines, lactams, vinyl esters, block copolymers thereof, and alloys thereof, etc.); thermosetting polymers such as epoxy resins; phenolic resins; melamine resins; alkyd resins; vinyl ester resins; unsaturated polyester resins; crosslinked polyurethanes; polyisocyanurates, crosslinked elastomers (including but not limited to polyisoprene, polybutadiene, styrene butadiene, styrene isoprene), and combinations thereof.The present invention includes subcombinations of these materials, optionally or available from a particular location, and the invention can be described as including one or any combination of these materials.

[0055] In either method, the thermal treatment reactor 115 or the pyrolysis reactor 120, or one or more of them, may be a moving bed reactor, where the feed material is propelled along the length of the reactor by mechanical means, gravity, or both mechanical and gravity. Representative examples of reactors suitable for the thermal treatment reactor 115 or the pyrolysis reactor 120 include single screw extruders, twin screw extruders, auger reactors, static mixer reactors, rotary kiln reactors, or staged grate reactors. In either embodiment, the pyrolysis reactor may have multiple heating zones with successively higher temperatures in the subsequent zones. In some embodiments, the thermal treatment reactor or pyrolysis reactor is fitted with a gas outlet in an area of ​​the reactor where the temperature of the material in the reactor is below 300°C or between 250°C and 300°C, so that products produced at low temperatures, such as steam, HCl, NH3, or other materials, can be removed from the reactor. A separation screen can be installed immediately downstream of the gas outlet in the pyrolysis reactor to at least partially prevent the gases evolved at lower temperatures from flowing into the hotter section of the reactor along with the melt and solid materials. Immediately downstream of the gas vent and optional screen, a gas inlet can be installed for introducing hot inert or recycle gases such as CH4, H2, CO, CO2, gases containing any of C2-C4 paraffins or olefins, or mixtures thereof.

[0056] Optionally, a solid co-reactant 122 (CaO, MgO, hydrotalcite, activated carbon, zeolite, etc.) or combinations thereof that capture or remove undesirable components can be fed to the heat treatment reactor 115 and separated therefrom by filtration through a screen.

[0057] When auger reactors are utilized for thermal processing or pyrolysis, they may include helical augers, optionally with different pitch dimensions at different portions of the auger, to adjust the velocity of the condensed phase from the inlet to the outlet of the reactor. The thickness of the flights and the diameter of the shaft may be variable dimensions along the length of the auger to control the flow rates of the vapor and condensed phases. Augers with paddle, cut, or folding flights are also contemplated within the scope of the present invention.

[0058] Rotary kiln reactors can be used for thermal treatment or pyrolysis, and the kiln cylinder can be fitted with lifters, such as helical lifters attached to the cylinder wall, or plate lifters extending from the cylinder wall, folding lifters, or segmented lifters. Rotary kiln reactors can also be tilted up or down towards the exit end of the kiln depending on the desired residence time and flow rate of the condensed phase in the kiln, thus using gravity to control the residence time of the condensed phase. The rotational speed of the rotary kiln can be optionally adjusted, for example between 20 revolutions per minute and 0.2 revolutions per minute, depending on the nature of the input mixture and the co-reactants added, to achieve thorough mixing and high heat transfer. The rotary kiln can be heated externally by combustion of waste process gases, such as CH4, C2-C4 paraffins, H2, CO, recycled from product separation or natural gas, or by electricity.

[0059] In any of the invention aspects, the temperature profile in any pyrolysis reactor can range from low temperatures near the feed inlet port to high temperatures at the outlet port(s). The temperature range is 20°C to 225°C (e.g., 20-100°C, or 20-50°C) at or near the inlet port and 300°C to 700°C (e.g., 325-650°C, or 350-600°C) at the hot outlet port. Solid co-reactant can be fed to the thermal treatment reactor, and the solid co-reactant is optionally transferred to a combustion regenerator where the carbonaceous material reacts with air and at least a portion of the hot solid co-reactant is returned to the thermal treatment reactor. Hot exhaust gases exiting the solid co-reactant regenerator can be sent to a catalytic heater to heat the catalyst in the catalytic pyrolysis reactor.

[0060] After exiting the heat treatment reactor 115, the feed product preferably does not come into contact with cold surfaces that may condense the product, and the surfaces are preferably maintained at a temperature of at least 300° C., at least 325° C., or at least 350° C., or within 25° C. or 50° C. of the temperature exiting the reactor 115. Preferably, in either embodiment, the temperature of the mixture is maintained at least 2° C., or at least 3° C., or at least 5° C., or at least 10° C. higher than the temperature of the mixture at the exit end of the heat treatment reactor.

[0061] In any embodiment of the invention, the catalytic reactor 140 may be a fluidized bed reactor; where the catalyst is a solid catalyst and the catalytic pyrolysis step includes pyrolysis in the fluidized bed reactor in the presence of the solid catalyst to produce a fluid product stream 141 and a coke-containing spent catalyst 142; at least a portion of the coke-containing spent catalyst is transferred to a regenerator 150 where the coke reacts with oxygen or air to form a hot regenerated catalyst, and at least a portion of the hot regenerated catalyst 143 is returned to the fluidized bed reactor, with heat from the hot regenerated catalyst providing energy for the catalytic pyrolysis step.

[0062] The vapors exiting the catalytic pyrolysis reactor are passed through a solids separation system consisting of a series of cyclones to separate the entrained solids into large and small particle size fractions. In either approach, the solids separation system consists of a series of one or more cyclones and one or more multi-cyclones. Typically, the first cyclone in the series is a relatively inefficient classifying cyclone that provides a rough separation of small and large particles.

[0063] Cyclones are typically designed and installed to separate solids as efficiently as possible from a gas stream, for example when removing dust from exhaust gases. The separation efficiency of a cyclone as a whole is defined as the ratio of the solid mass flow rate from the bottom of the cyclone to the solid mass flow rate at the cyclone inlet. An efficiency of 1 indicates that no solids are discharged with the gas at the top of the cyclone, while an efficiency of 0.99 indicates that 0.01 of the solids are discharged with the gas at the top of the cyclone. Thus, if the solid mass flow rate is m in The mass fractions of small and large particles are x small and x large When a bimodal solids flow of x enters the cyclone, typical cyclone design criteria aim for the highest possible efficiency. That is, the solids flow rate leaving the bottom of the cyclone is (x small +x large )·m in In the proposed application, the target solids flow rate discharged from the bottom of the cyclone is (x large )·m in , which means (x small )·m in A cyclone can be effectively designed so that a solids flow rate of 1000 rpm is discharged from the top of the cyclone, making it less efficient at classifying particles. Specifically, the target efficiency will always be lower by an amount equivalent to the mass fraction of small particles in the solids feed (target efficiency for a typical cyclone design = JPEG2025515125000003.jpg16160Efficiency targeted in this application JPEG2025515125000004.jpg16160). Hence, the term "low efficiency" is used to describe the first stage cyclone. Referring to FIG. 5, the vortex diameter (D e The ratio of the vortex length (S) to the cylinder diameter (h) can be 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or can be in the range of 0.1 to 0.8, or 0.3 to 0.7, or 0.4 to 0.6, or 0.45 to 0.55, or 0.49 to 0.51. b The ratio of the underflow diameter (B) to the vortex diameter (D) is 0.5, 0.6, 0.7, 0.8, or 0.9, or is within the range of 0.3 to 0.95, 0.5 to 0.95, 0.8 to 0.95, or 0.85 to 0.95. e The ratio of inlet height to inlet width can be 0.75, 1, 1.5, 2, 2.4, 3, 4, 5, or within the ranges of 0.75-5, 1.5-4, 2-3, 2.2-2.6. The ratio of vortex length (S) to total height (H) is 0.1, or 0.2, or 0.3, or 0.36, or 0.4, or 0.5, or 0.6, or 0.8, or in the range of 0.1 to 0.8, or 0.2 to 0.6, or 0.3 to 0.4, or 0.34 to 0.38. The gas flow velocity at the inlet of the low efficiency cyclone or the inlet of the classifying cyclone is greater than 5, or greater than 10, or greater than 15, or 5 to 40, or 10 to 30, or 15 to 25 meters per second.

[0064] Optionally, the catalyst removed from the catalytic reactor or the catalyst recovered in the solids separation system, or both, can be stripped of volatiles by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or a combination thereof, or a recycle stream from the product gas, through the catalyst particles. The resulting vapor stream containing the steam and organics is condensed, the organic and aqueous phases are separated, and the liquid organic phase is sent to product recovery and the aqueous phase is sent to wastewater recovery. The catalyst from which the volatile organic compounds have been removed can be sent to a catalyst regenerator, returned to the catalytic reactor, disposed of, or a combination thereof.

[0065] Multiclones are used in later stages of separation. Multiclones or multicyclones are multiple small diameter tubes arranged in parallel, each acting like a small cyclone. This configuration combines the high efficiency of the small diameter with the ability to handle large volumes of gas. In each small diameter tube, the gas flow rate is higher than in the larger diameter tubes, resulting in higher separation efficiency. Multiclones typically experience a higher pressure drop than a single cyclone of comparable capacity. Figure 6 shows a schematic diagram of a multiclone (https: / / www.babcock.com / home / products / multiclone-dust-collectors / ) that can be used in the process of the present invention. Multiclones are widely used to reduce emission levels in many biomass boilers, cement kilns, and lime kilns. Multiclones work by ensuring that downstream equipment such as fractionators, fans, scrubbers, and settlers operate with minimal energy input. They operate as a series of multiple highly efficient cyclones operating in a parallel arrangement with a common inlet and outlet plenum. The process steam stream enters an inlet plenum and is distributed to a number of small, highly efficient, small diameter cyclones which may contain vortex generators. The heights of the small cyclones are each designed to have the same pressure drop and flow rate. Particles are discharged into a common solids outlet plenum and the steam exits the unit. These cyclones separate the majority of particles from the gas stream flowing through the system and can be used for particles as small as 5 microns in diameter.

[0066] Referring to FIG. 5, for each of the multiple small-diameter cyclones in the multi-clone, the vortex diameter (D e The ratio of the vortex length (S) to the cylinder diameter (h) is 0.2, 0.3, 0.4, 0.5, 0.6, or 0.7, or is within the range of 0.1 to 0.8, 0.3 to 0.7, 0.4 to 0.6, 0.45 to 0.55, or 0.49 to 0.51. b The ratio of the underflow diameter (B) to the vortex diameter (D) is 0.5, 0.6, 0.7, 0.8, or 0.9, or is within the range of 0.3 to 0.95, 0.5 to 0.95, 0.8 to 0.95, or 0.85 to 0.95. e The ratio of the vortex length (S) to the total height (H) is 0.02, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5, 1.0, or 1.25, or within the range of 0.02 to 1.25, 0.02 to 0.5, 0.1 to 0.3, or 0.15 to 0.25. The ratio of the vortex length (S) to the total height (H) is 0.1, 0.2, 0.3, 0.36, 0.4, 0.5, 0.6, or 0.8, or within the range of 0.1 to 0.8, 0.2 to 0.6, 0.3 to 0.4, or 0.34 to 0.38. The number of small cyclones in one multi-clone is 4, 9, 16, 25, 36, 49, or 64, or 4 to 64, or 9 to 49, or 16 to 36. The gas flow velocity at the inlet of the recovery cyclone is 25 or less, or 20 or less, or 15 or less, or 3 to 20, or 5 to 15, or 6 to 12 meters per second.

[0067] In the catalyst and filler separation, at least a portion of the separated larger particle size entrained solids can be sent to a catalyst regenerator, at least a portion can be returned to the catalytic pyrolysis reactor, or disposed of, or a combination of these. The separated smaller particle solids can be sent to a separate regenerator or sent to solid waste treatment. The solids-removed product vapor stream contains 1 m of product vapor. 3 It must not contain more than 150, 300, or 500 mg of solids per serving.

[0068] Optionally, the small solid particles recovered in the solid separation system can be stripped of volatiles by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or a combination thereof, or a recycle stream from the product gas through the small solid particles. The resulting vapor containing the steam and organics is condensed, the liquid organic phase is sent to product recovery, and the aqueous phase is sent to wastewater recovery. The solid particles from which the volatile organic compounds have been removed can be sent to a charge regenerator, disposed of, or a combination thereof. In either method, the catalytic pyrolysis step can include pyrolysis in the presence of a fluidized bed catalyst. The catalytic pyrolysis reactor can include a fluidized bed, circulating bed, bubbling bed, turbulent bed, or riser reactor operating at temperatures ranging from 300°C to 800°C, or 350°C to 750°C, or 400°C to 700°C, or 450°C to 650°C, or 500°C to 600°C. The residence time of the vapors in the catalytic pyrolysis can be 1 second to 480 seconds, or 1 second to 240 seconds, or 2 seconds to 60 seconds, or 3 seconds to 30 seconds, or 4 seconds to 15 seconds. The pressure in the catalytic pyrolysis reactor is at least 0.1 MPa (1 bar), or at least 0.3 MPa (3 bar), or at least 0.4 MPa (4 bar), or 0.1-2.0 MPa (1-20 bar), or 0.1-1.0 MPa (1-10 bar), or 0.3-0.8 MPa (3-8 bar), preferably 0.4-0.6 MPa (4-6 bar), the pressure being absolute.

[0069] The design and conditions of the fluidized bed catalytic reactor can be conventional. A fluidizing gas may be required during start-up, and during steady-state operation, recycled gas from the process can be used as a component of the fluidizing gas. The fluidizing gas can include H2, CO, CO2, H2O, C1-C4 paraffins or olefins or both, N2, Ar, He, or a recycle stream, or combinations thereof.

[0070] For catalytic pyrolysis, useful catalysts include those that contain internal porosity selected according to pore size (e.g., pore sizes typically associated with mesoporous and zeolites), e.g., average pore sizes less than 10 nm, less than 5 nm, less than 2 nm, less than 1 nm, less than 0.5 nm, or smaller. In some embodiments, catalysts with average pore sizes of 0.5-10 nm can be used. In some embodiments, catalysts with average pore sizes of 0.5-0.65 nm, or 0.59-0.63 nm can be used. In some cases, catalysts with average pore sizes of 0.7-0.8 nm, or 0.72-0.78 nm can be used.

[0071] Particularly advantageous catalyst compositions for the catalytic pyrolysis fluidized bed reactor of the present invention include crystalline molecular sieves characterized by a SAR (silica to alumina, SiO2:Al2O3, mass ratio) greater than 12 or between 12 and 240, and a CI (constraint index) between 1 and 12. Non-limiting examples of these crystalline molecular sieves include those having the structure of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, or combinations thereof. In embodiments, the catalyst composition includes crystalline molecular sieves characterized by a SAR greater than 12 to 240 and a CI between 5 and 10, such as molecular sieves having the structure of ZSM-5, ZSM-11, ZSM-22, ZSM-23, or combinations thereof. Methods for determining CI are described in more detail in U.S. Pat. No. 4,029,716, the details of which are incorporated herein by reference.

[0072] The molecular sieve or catalyst composition containing same used in the present invention may be heat treated at elevated temperatures. This is usually done by heating at a temperature of at least 370°C for at least 1 minute, usually up to 20 hours (typically in an oxygen-containing atmosphere, preferably air). Subatmospheric pressures can be used for the heat treatment, although atmospheric pressure is preferred for reasons of convenience. Heat treatment can be carried out at temperatures up to about 925°C. Heat treated products are particularly useful in the process of the present invention.

[0073] For catalyst compositions useful in the present invention, suitable molecular sieves may be used in combination with a support or binder material, such as, for example, a porous inorganic oxide support or a clay binder. Non-limiting examples of such binder materials include alumina, zirconia, silica, magnesia, thoria, titania, boria, and combinations thereof, which are generally in the form of dried inorganic oxide gels and gelatinous precipitates. Suitable clay materials include, for example, bentonite, diatomaceous earth, and combinations thereof. The relative proportion of suitable crystalline molecular sieves in the overall catalyst composition may vary widely, with the molecular sieve content ranging from 30 to 90 percent by weight of the composition, and typically ranging from 40 to 70 percent. The catalyst composition may be in the form of extrudates, beads, or fluidizable microspheres.

[0074] The molecular sieve or catalyst composition containing same may have the original cations replaced, at least in part, by ion exchange with hydrogen, hydrogen precursor cations, or non-noble metal ions of Group VIII of the Periodic Table, i.e., nickel, iron, cobalt, zinc, gallium, or combinations thereof, according to techniques well known in the art.

[0075] In the process of regenerating catalyst from catalytic pyrolysis, heat is generated by oxidation of coke, char, and other materials in a catalyst regenerator, which is used in the process or converted into electricity for export. In one set of embodiments, as shown in FIG. 1, an oxidant is fed to the regenerator via stream 151. The oxidant can be fed from any source, for example, an oxygen tank, air, steam, etc. In the regenerator, the catalyst is reacted with the oxidant to reactivate it and generate heat. The solid mixture containing the deactivated catalyst may include residual carbon and / or coke, as well as coke or char from the process, which may be removed by reaction with the oxidant in the regenerator. A portion of the gaseous products from the catalytic pyrolysis process is fed to a catalyst regenerator and combusted with the solid materials. The gaseous products are first separated into an olefin-rich stream and an olefin-lean stream, and at least a portion of the olefin-lean stream is fed to the catalyst regenerator. The regenerator of FIG. 1 includes an exhaust stream 152, which may include regenerated reaction products, residual oxidant, etc.

[0076] In either method, the exhaust vapor from the catalyst regenerator is passed through a solids separation system consisting of a series of cyclones to separate the entrained solids into large and small particle size fractions. The separated large particle size entrained solids can be sent to the catalytic pyrolysis reactor, disposed of, or a combination of these. The separated small particle solids can be sent to a separate regenerator or sent to solid waste treatment. The exhaust gas from the catalyst regenerator from which the solids have been removed does not contain more than 12, 35, 50, or 150 μg of solids per cubic meter of product steam, averaged over a 24-hour or annual period.

[0077] Regeneration separation system The combustion product gases (exhaust gas) produced by either the catalyst regenerator or the packing regenerator, or both, may be passed to a solids separation system similar to that described for the product vapor stream, may be passed to a separate solids separation system, or may be sent to a common solids separation system as a combination of exhaust gases from both the catalyst regenerator and packing regenerator. The solids separation system employed to remove particulates from the exhaust gas stream may consist of a series of cyclones and optional classifying cyclones followed by one or more high efficiency multi-cyclones. The exhaust gas from the catalyst regenerator from which solids have been removed will not contain more than 12, 35, 50, or 150 μmg of solids per cubic meter of product vapor, averaged over a 24-hour or annual period.

[0078] Referring to FIG. 5, for the exhaust gas solids separation system, the dimensions of the classifying cyclone (optional) and the recovery cyclone (multi-clone) can comply with the same length ratios as described above for the product steam purification solids separation system, although the absolute size of the cyclones may vary. The gas flow velocity at the inlet of the optional low efficiency cyclone or the classifying cyclone is greater than 5 meters / second, greater than 10 meters / second, greater than 15 meters / second, 5 meters / second to 40 meters / second, 10 meters / second to 30 meters / second, or 15 meters / second to 25 meters / second. The gas flow velocity at the inlet of the high efficiency recovery cyclone is 25 meters / second or less, 20 meters / second or less, 15 meters / second or less, 7 meters / second to 20 meters / second, 5 meters / second to 15 meters / second, or 6 meters / second to 12 meters / second.

[0079] In the method of the present invention, at least a portion of the solid material 123 may be removed from the thermal treatment reactor 115 and recycled to the feed of the thermal treatment reactor 115 as part of the optional co-reactant 122. The optional co-reactant 122 may include a solid material that reacts with the sulfur or nitrogen compounds to capture the sulfur or nitrogen species in the solid phase. The solid material of the optional co-reactant 122 may include one or more materials selected from agricultural lime, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, limestone, hydrotalcite, activated carbon, zeolite, or combinations thereof.

[0080] Multiple plastic upgrading units can be connected to feed a single product separation and refining facility in a hub-and-spoke system. The system for upgrading waste plastics consists of an optional first pyrolysis reactor and a catalytic fluidized bed reactor, which together produce refined chemical intermediates (e.g., benzene, toluene, xylene, p-xylene, m-xylene, o-xylene, BTX (a mixture of benzene, toluene, and xylene), C6-C 20 The plastic upgrading sites form one spoke of a "hub and spoke" network for producing paraffins and olefins, ethylene, propylene, naphthalene, etc., or combinations thereof, where each of the multiple plastic upgrading sites (spokes) produces a condensed phase product that is sent to a central processing facility (hub) for separation and purification into product streams. The number of plastic upgrading facilities that can be present in a network feeding a single central separation and purification facility can be at least 2, or at least 3, or at least 5, or at least 7, or at least 10, or at least 15, or 2-20, or 3-10, or 5-10 plastic upgrading facilities. The total crude product mixture produced by the plastic upgrading facilities introduced to the central separation and purification facility can be at least 20, or at least 50, or at least 100, or at least 150, or at least 200 metric tons per day, or 20-500, or 30-200, or 50-150 metric tons per day of crude product mixture.

[0081] The present invention also includes a plastics upgrading system in which plastics are first pyrolyzed in pyrolysis reactors, each pyrolysis reactor producing refinery chemical intermediates (e.g., benzene, toluene, xylene, p-xylene, m-xylene, o-xylene, BTX (a mixture of benzene, toluene, and xylene), C6-C8 20 The plastics upgrading sites constitute one "spoke" in a "hub and spoke" network for producing paraffins and olefins, such as ethylene, propylene, naphthalene, etc., or combinations thereof, with each of the multiple plastics upgrading sites (spokes) producing a condensed phase product that is sent to a central processing facility (hub) that includes a central fluidized bed catalytic process plant (Plas-TCat™) and product streams from separation and purification. In some embodiments of the system, the number of plastics pyrolysis facilities that can be in the network feeding the single central catalytic upgrading, separation, and purification facility can be at least 2, or at least 3, or at least 5, or at least 7, or at least 10, or at least 15, or 2-20, or 3-10, or 5-10 plastics pyrolysis facilities. The total amount of crude product mixture produced at the plastic pyrolysis facility and introduced into the central catalytic upgrading, separation, and refining facility can be at least 20, or at least 50, or at least 100, or at least 150, or at least 200 metric tons per day, or from 20 to 500, or from 30 to 200, or from 50 to 150 metric tons per day of crude product mixture. EXAMPLES

[0082] Example 1 For a system processing 500 tonnes per day of mixed plastics containing 5% filler by weight to produce useful products, calculations were made for the cyclones required to separate and remove the filler from the product discharge from the catalytic reactor. The filler was assumed to be approximately 95% by mass with a particle size less than 20 microns, and the catalyst was assumed to be 95% by mass with a particle size greater than 65 microns. The particle size distributions of the filler, catalyst, and the combined filler and catalyst in the feed ("cyclone inlet") are shown in Figure 4. The plastic mixture is assumed to be catalytically pyrolyzed in a fluidized bed catalytic reactor producing a product vapour flow of 5.2 kg / s with entrained solids including 1.2 kg / s catalyst particles and 0.29 kg / s filler particles. It was assumed that 10% of the feed mixture would produce coke that would deposit on the catalyst and material that would be adsorbed in the interstitial pores of the catalyst and sent for catalyst regeneration. The density of the catalyst particles was 1300 kg / m 3 , the density of the filler particles is 2700 kg / m 3was assumed. The gas density of the vapor stream is 1.65 kg / m3 at 500 °C. The solid separation system designed for separation and removal of solids includes 28 cyclones in total: one classifier, a low-efficiency cyclone, and three stages of purification multi-cyclones with nine internal cyclones in each stage. The dimensions and performance of the cyclones are summarized in Table 3 for the parameters in Figures 5 and 6. The mass of material obtained from each cyclone stage of the solid separation system in Table 3 is summarized in Table 4. The percentage of each material fed to each stage and separated at the bottom and top is summarized in Table 5. The destination of the materials entering the catalytic reactor is shown in Table 6. According to the calculations, most of the catalyst is separated in the first classifying cyclone, and the rest leaves in stage 2. The first cyclone was designed with a low efficiency target of 80.5% to completely remove the packing material, which constituted 19.4% of the solids in the inlet gas to the cyclone, and after optimizing the cyclone dimensions, the efficiency was calculated to be 80.9%. The second, third and fourth separation stages were then designed with an overall efficiency target of 99.6% to reduce the packing material content in the gas to the desired specification of 4 kg / h, which corresponds to the solids limit that can enter the downstream processing unit. Most of the desired separation (94.2%) was achieved in the second stage cyclone, while the third and fourth stages completed the separation to meet the target. The cycle efficiencies for the third and fourth stages were 77.4% and 74.4%, respectively. These efficiencies for the second, third and fourth stages were the best achievable using the computational approach used, mainly due to the low required separation specifications and the low solids content in the gas entering these stages. Three stages of purification after classification produced a gas stream containing 4 kg / h packed particles suitable for introduction into the fractionator.

[0083] [Table 3]

[0084] [Table 4]

[0085] [Table 5]

[0086] [Table 6]

[0087] Example 2 Calculations were made for the cyclones required to separate and remove the filler from the tail gas discharge from the catalyst regenerator in a plastic chemical recycling system processing 500 tonnes per day of mixed plastics containing 5% filler by weight to produce useful products. The filler was assumed to be approximately 95% particles with a mass less than 20 microns and the catalyst was assumed to be 95% particles with a mass greater than 65 microns. The particle size distribution of the solids discharged from the regenerator was determined experimentally and includes the filler and catalyst and is shown in Figure 7. The solids to be separated include a mixture of 1,300 kg / m2 of filler with a density of 1,300 kg / m2. 3 and a density of 2700 kg / m 3 The gas flow rate is 10.14 g / s. The gas density of the vapor stream is 1.8 kg / m3 at 500°C.

[0088] The solids separation system designed for separation and removal of solids contains a total of 76 cyclones, including one classifier, a low efficiency cyclone, and three stages of series multicyclones with 25 internal cyclones in each stage. The cyclone dimensions and performance for the items in Figures 5 and 6 are summarized in Table 7. The mass of material obtained from each cyclone stage of the solids separation system in Table 5 is summarized in Table 8. The percentage of each material fed to each stage and separated into the bottoms and overhead is summarized in Table 9. The destination of the materials entering the catalyst regenerator is shown in Table 10.

[0089] Calculations show that all of the catalyst is separated in the first classifying cyclone. The first cyclone is designed with a low efficiency target of 99.7%, allowing complete removal of the packing material, which represents 19.4% of the solids content of the inlet gas to the cyclone. The first stage cyclone completely separates the packing material from the catalyst, with all catalyst being recovered from the bottom of the cyclone and 97.25% of the packing material passing with the gas phase. The second, third and fourth separation stages are designed with an overall efficiency target of 99.6%, allowing the packing material content in the gas to be reduced to the desired specification of 4 kg / h, which corresponds to the solids limit that can enter the downstream processing unit. Most of the desired separation (94.8%) was achieved in the second stage cyclone, while the third and fourth stages completed the separation to reach the target. The efficiencies of the third and fourth stage cycles were 76.5% and 69.7%, respectively. These efficiencies for the second, third and fourth stages were the best achievable using the calculation method used, mainly due to the low separation specifications required and the low solids content in the gas entering these stages. The three stages of cleaning after the classification cyclones use multicyclones each containing 25 cyclones, resulting in an exhaust gas stream containing 3 kg / h of packed particles that can be released into the air.

[0090] [Table 7]

[0091] [Table 8]

[0092] [Table 9]

[0093] [Table 10]

[0094] Example 3 A small-scale pilot plant for upgrading waste plastics and other materials was constructed with a bubbling fluidized bed of catalyst, a stripper to remove and recover material deposited on the catalyst, a regenerator to regenerate the catalyst, and a solids separation system to separate the catalyst from the filler. The process parameters are shown in Table 11.

[0095] [Table 11]

[0096] A schematic diagram of the solids flow in the pilot plant is shown in Figure 8. It consists of a fluidized bed reactor 140, a stripper 145, a catalyst regenerator 150, and a solids separation system 160. Plastic 10 was fed to the catalytic fluidized bed reactor, and catalyst 142 was continuously removed and stripped with N2 to produce stripped catalyst 147, which was regenerated in the regenerator 150, and regenerated catalyst 143 was returned to the reactor. The fluid product stream 141 was sent to a solids separation system 160, which consisted of two solids separation cyclones connected in series, with larger particles from both cyclones returned to the reactor and the vapor stream from the first cyclone passed to the second cyclone. The cyclones separated larger particles (mainly catalyst) 162 from smaller particles in a vapor product stream 163, and the larger particles were returned to the catalytic fluidized bed reactor. The cyclone dimensions for the design of Figure 5 are summarized in Table 12.

[0097] [Table 12]

[0098] [Table 13]

[0099] The catalytic reactor was loaded with catalyst, the reactor and regenerator were heated to bring the plant into operation, and a flow was established with inert gas (N2). The reactor was run without feed for 24 hours to reach steady state. After 24 hours on stream, the plastic feed was started and the reactor was run for 5.5 hours with plastic feed containing filler. Samples were taken 3.5 hours after plastic feed. After 5.5 hours of plastic feed, the reactor was run for 42 hours without feed, but kept at elevated temperature in holding condition.

[0100] The feed of plastic-containing filler was resumed at the 71.5 TOS mark and continued for 5.5 hours. Samples were removed at the 75.5 TOS mark, at which point the system had had plastics for a total of 9.5 hours.

[0101] Several PSD samples were taken at different points in the process: sample SP1 (standpipe 1) was taken from the standpipe between the reactor and the stripper, SP2 was taken from the standpipe between the stripper and the regenerator, and SP3 was taken from the standpipe between the regenerator and the reactor (see Figure 8).

[0102] Particle size distribution (PSD) was determined by dispersing the material in deionized water and measuring the particle size (volume density) using a Mastersizer 3000 (manufacturer Malvern Panalytical).

[0103] In Figure 9, the PSD of the regenerated catalyst sample is confirmed to be unimodal with similar distributions at 24, 27.5, and 75.5 hours after start of operation. The maximum volume density was measured at particle sizes between 105 and 110 μm. Early on in the start of operation (TOS 24 hours), the PSD is broad. As the TOS progresses, the distribution narrows and larger particles are worn away while smaller particles are captured and removed from the product stream by the two cyclones in the solids separation system.

[0104] Figure 10 shows that the PSD profile of the unexfoliated catalyst in standpipe 1 is unimodal, with the maximum volume density measured at particle sizes between 105 and 110 μm at all time points in the flow. As previously noted, the PSD at the early TOS is broad, with the distribution narrowing slightly as the TOS increases. Similarly, Figure 11 shows the PSD profiles of the exfoliated catalyst at three different times in the flow, with the earlier times having a broader distribution than the later TOS.

[0105] Figure 12 shows the PSDs of samples taken from standpipes 1 (unstripped), 2 (stripped), and 3 (regenerated) at 27.5 hours TOS after 3.5 hours of plastic feeding at a rate of 6.5 kg / hr. The higher peak is due to the regenerated catalyst and the lower peak shows two other PSDs overlapping each other. The slightly broader PSD is likely due to coke that accumulated on the catalyst by a few percent by weight and was burned in the regenerator.

[0106] To understand the classification of the separation system, a sample of the solids trapped in the quench unit downstream of the solid separation system was calcined and evaluated. The PSD of the ash was measured and is shown in Figure 13 along with the PSD of the catalyst in the fluidized bed. The ash separated by the solid separation system contains approximately 80% by mass of particles less than 50 microns, while the catalyst bed contains less than 1% by mass of particles less than 50 microns. This indicates that the two cyclones can classify the particles by particle size into particles less than 80 microns and particles greater than 80 microns with high efficiency.

[0107] Example 4 Calculations were performed using a computational particle fluid dynamics (CPFD) model for the cyclones required to separate and remove the filler from the product effluent from the catalytic reactor in a system processing 500 tonnes per day of mixed plastics containing 5% filler by weight into useful products. The filler was assumed to be approximately 95% particles with a mass less than 20 microns, and the catalyst was assumed to be approximately 95% particles with a mass greater than 65 microns. The particle size distributions of the filler, catalyst, and the combined filler and catalyst in the feed ("cyclone inlet") are shown in Figure 4. The plastic mixture is assumed to be catalytically pyrolyzed in a fluidized bed catalytic reactor producing a product vapor flow of 5.2 kg / s with entrained solids including 1.2 kg / s catalyst particles and 0.29 kg / s filler particles. It was assumed that 10% of the feed mixture was deposited on the catalyst as coke or material adsorbed in the interstitial pores of the catalyst. The density of the catalyst particles is assumed to be 1300 kg / m3 and that of the filler particles 2700 kg / m3. The gas density of the steam stream is 1.65 kg / m3 at 500 °C.

[0108] The CPFD model includes a primary classification (low efficiency) cyclone designed to separate the packing from the catalyst material. The cyclone dimensions are summarized in Table 14. Simulations were run for various conditions of reactor inlet fluidization velocity and amount of packing entering the reactor, and the results are summarized in Table 15. In all cases, the proposed classification design allowed removal of the packing from the product vapor, with the percentage of removed packing ranging from 72 to 91%, and essentially 100% of the catalyst being recovered and returned to the reactor.

[0109] This example shows that the classifying cyclone can efficiently separate the filler from the product vapors and recycle it to the reactor without loss of catalyst.

[0110] [Table 14]

[0111] [Table 15]

Claims

1. 1. A process for producing olefins and aromatic compounds, comprising the steps of: feeding a plastic containing stream containing at least one filler material to a fluidized bed reactor containing a catalyst, wherein the cut size or particle size of the filler material is smaller than the cut size or particle size of the fluidized bed catalyst; catalytically reacting a feedstock with a catalyst in said fluidized bed reactor to form a product mixture comprising a first weight ratio of catalyst and filler material; recovering a vapor effluent from said product mixture, said vapor effluent comprising catalyst particles and filler material; passing the vapor discharge through a solids separation system, the solids separation system including passing the vapor discharge through a first cyclone to separate a first bottoms fraction and a first overflow fraction, wherein the first cyclone is a classifying cyclone, and the first bottoms fraction has a second mass ratio greater than the first mass ratio; directing the overflow fraction to a second cyclone to separate a second bottoms fraction and a second overflow fraction, wherein the first cyclone has a first separation efficiency for catalyst particles, the second cyclone has a second separation efficiency for catalyst particles greater than the first separation efficiency, and the second bottoms fraction has a third mass ratio less than the first mass ratio; recovering olefins, aromatics, or a combination thereof from said second overflow vapor fraction discharged from a last cyclone; A method comprising:

2. 2. The method of claim 1, wherein the first cyclone comprises one or more low efficiency cyclones or classification cyclones and the second cyclone comprises one or more recovery cyclones or multi-cyclones, or both.

3. 3. The method of claim 2, wherein the inlet flow velocity to the low efficiency or classifying cyclone is greater than the inlet flow velocity to the recovery cyclone.

4. 10. The method of claim 1, wherein at least a portion of the solids recovered at the bottom from the one or more low efficiency cyclones or classifying cyclones is returned to the fluidized bed reactor.

5. The method of claim 1 , wherein at least a portion of the solids recovered from the one or more recovery cyclones are discarded.

6. 2. The method of claim 1, wherein the catalytic reaction is carried out at an operating temperature in the range of 300°C to 800°C, or 350°C to 700°C, or 400°C to 650°C, or 450°C to 625°C, or 500°C to 600°C.

7. 10. The process of claim 1, wherein a stream enriched in ethylene or propylene, or both, is separated from the volatile products.

8. 10. The process of claim 1, wherein a stream enriched in ethylene or propylene, or both, is separated from volatile products and at least partially recycled to the pyrolysis reactor.

9. 10. The method of claim 1, wherein at least 80% of the mass of the catalyst particles are at least 40 microns, or at least 50 microns, or at least 60 microns, or at least 75 microns, or at least 100 microns, or from 40 to 300 microns, or from 50 to 250 microns, or from 75 to 150 microns.

10. 2. The method of claim 1, wherein at least 80% by mass of the filler particles are sized 40 microns or less, or 30 microns or less, or 20 microns or less, or 15 microns or less, or 10 microns or less, or 1 to 40 microns or less, or 2 to 30 microns or less, or 5 to 20 microns or less.

11. 2. The process of claim 1, wherein the residence time of the fluidizing gas in the catalytic pyrolysis reactor, defined as the volume of the reactor divided by the volumetric flow rate of the fluidizing fluid under process conditions of temperature and pressure, is from 1 second to 480 seconds, or from 1 second to 240 seconds, or from 2 seconds to 60 seconds, or from 3 seconds to 30 seconds, or from 4 seconds to 15 seconds.

12. 2. The process of claim 1, wherein the pressure in the fluidized bed reactor is at least 0.1 MPa, or at least 0.3 MPa, or at least 0.4 MPa, or from 0.1 to 2.0 MPa (1 to 20 bar), or from 0.1 to 1.0 MPa, or from 0.3 to 0.8 MPa, preferably from 0.4 to 0.6 MPa.

13. 2. The process of claim 1, wherein the fluidized bed reactor is a circulating bed, a bubbling bed, a turbulent bed, or a riser reactor.

14. 2. The method of claim 1, wherein the fluidizing gas for catalytic pyrolysis comprises H2, CO, CO2, H2O, C1-C4 paraffins or olefins or both, N2, Ar, He, or a recycle stream, or a combination thereof.

15. 2. The method of claim 1, wherein the catalyst is a solid catalyst and the step of catalytic pyrolysis comprises pyrolyzing in a fluidized bed reactor in the presence of the solid catalyst to produce a fluidized product stream and spent catalyst together with coke, and at least 90% of the carbon in the feed is converted to coke and volatile products.

16. 3. The method of claim 2, wherein at least a portion of the catalyst separated from the low efficiency classifying cyclone is returned to the catalytic pyrolysis reactor, sent to a catalyst regenerator, or disposed of.

17. 2. The process of claim 1, wherein a catalyst and packing solids separation system is used that includes a classifying cyclone and a recovery cyclone, from which solids are returned to the fluidized bed reactor, and from which olefins or aromatics are recovered from the vapors exiting the final recovery cyclone.

18. 18. The method of claim 17, wherein the classifying cyclone is designed to be a cut size between the particle size distribution of the filler and the particle size distribution of the catalyst, separating out the larger particle size fraction and entraining the smaller particle size fraction in the off-gas for removal in a series of highly efficient recovery multi-cyclones.

19. The feed stream may comprise plastics selected from among polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymers, polyethylene furanoate (PEF), polyamides, polyurethanes, polyethers, polycarbonates, poly(oxides), poly(sulfides), polyarylates, polyetherketones, polyetherimides, polysulfones, polyurethanes, polyvinyl alcohols, and polymers produced by polymerization of monomers such as dienes, olefins, styrenes, acrylates, acrylonitrile, methacrylates, methacrylonitrile, diacids and diols, lactones, diacids and diamines, lactams, vinyl esters, block copolymers thereof, and alloys thereof; thermosetting polymers such as epoxy resins; phenolic resins; melamine resins; alkyd resins; vinyl ester resins; unsaturated polyester resins; crosslinked polyurethanes; polyisocyanurates; crosslinked elastomers, including but not limited to polyisoprene, polybutadiene, styrene butadiene, styrene isoprene, ethylene propylene diene monomer polymers; and mixtures thereof.

10. The method of claim 1, wherein the feedstock comprises a mixture of waste plastics selected from polyethylene terephthalate (PET), high density polyethylene (HDPE), polyvinyl chloride (PVC), polyvinylidene (PVCD), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), mixed resins, or combinations thereof.

20. 10. The method of claim 1, wherein the feed stream comprises a mixture of waste plastics selected from polyethylene terephthalate (PET), high density polyethylene (HDPE), polyvinyl chloride (PVC), polyvinylidene (PVCD), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), mixed resins, or combinations thereof.

21. The filler may be selected from the group consisting of alumina, aluminum, aluminum fiber, aluminum flake, aluminum hydroxide, aluminum nitride, antimony doped tin oxide, antimony oxide, aramid, attapulgite, barium sulfate, barium titanate, bentonite, bismuth carbonate, boron oxide, boron nitride, bronze powder, calcium carbonate, calcium fluoride, calcium phosphate, calcium silicate, calcium sulfate, calcium sulfate whiskers, carbon black, carbon fiber, carbon nanotubes, cellulose nanocrystals, chitosan, clay, compatibilizers, copper, diamond, diatomaceous earth, expanded graphite, ferromagnetic powders, fluorine mica, fly ash, fumed nanosilica, glass beads, glass fiber, glass flakes, glass spheres, graphene, graphite, ground tire rubber, hollow gas.

2. The method of claim 1, wherein the porous silicate is selected from lath microspheres, hollow silicates, hydrotalcite, iron, kaolin, lignin, magnesium hydroxide, magnesium oxide, magnetite, mica, microfibrous cellulose, molybdenum sulfide, montmorillonite, ni-batio3, nickel, phenolic microspheres, potassium titanate whiskers, potassium-magnesium aluminosilicate, ptfe, pyrophyllite, red mud, red phosphorus, rubber particles, sand, sepiolite, silane, silica, silicon carbide, silver powder, soot, starch, superconductors (yba2cu3o7-x), talc, tetrapod zinc oxide whiskers, titania nanoparticles, titanium dioxide, vermiculite, wollastonite, wood fiber, wood flour, zinc borate, zinc oxide, zirconium silicate, or combinations thereof.

22. The method of claim 1 , wherein the filler is selected from calcium carbonate, carbon black, silica, kaolin clay, or talc, or a combination thereof.

23. The method of claim 1 , wherein the catalyst in the fluidized bed reactor comprises a zeolite.

24. 24. The process of claim 23, wherein the catalyst has a SAR (silica to alumina, SiO2:Al2O3 mass ratio) greater than 12 or between 12 and 240 and a CI (constraint index) between 1 and 12 or between 5 and 10.

25. 24. The method of claim 23, wherein the zeolite catalyst is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, or combinations thereof.

26. The method of claim 23, wherein the catalyst comprises ZSM-5.

27. 10. The method of claim 1, wherein the catalyst in the fluidized bed comprises a binder material selected from alumina, zirconia, silica, magnesia, thoria, titania, boria, or combinations thereof.

28. 10. The method of claim 1, wherein the catalyst in the fluidized bed comprises catalytic molecular sieves, the catalytic molecular sieves comprising 30 to 90 weight percent or 40 to 70 weight percent of the composition of the catalyst particles.

29. 10. The method of claim 1, wherein the catalyst in the fluidized bed is in the form of fluidizable microspheres.

30. 10. The method of claim 1, wherein the plastic is pretreated in a pyrolysis reactor to remove chlorine before being fed to the fluidized bed catalytic pyrolysis reactor.

31. 31. The method of claim 30, wherein the pyrolysis reactor is a moving bed, single screw extruder, twin screw extruder, auger reactor, rotary kiln reactor, static mixer reactor, or staged grate reactor.

32. 32. The method of claim 30 or 31, wherein the pyrolysis reactor includes a feed inlet port and an outlet port, and the temperature within the pyrolysis reactor ranges from a lower temperature near the feed inlet port to a higher temperature at the outlet port.

33. 33. The method of claim 32, wherein the temperature in the pyrolysis reactor is from 20°C to 225°C, for example 20 to 100°C, or 20 to 50°C, at or near the inlet port and the temperature range at the outlet port is from 300°C to 700°C, for example 325°C to 650°C, or 350°C to 600°C.

34. The method of any one of claims 30 to 33, wherein the pyrolysis reactor comprises two or more reactors connected in series.

35. 35. The method of any one of claims 30 to 34, wherein the residence time of the condensed phase in the thermal treatment or pyrolysis reactor is at least 1 minute, or at least 5 minutes, or at least 10 minutes, or at least 20 minutes, or at least 30 minutes, or from 1 to 60 minutes, or from 5 to 30 minutes, or from 10 to 30 minutes.

36. 36. The process of any one of claims 30 to 35, wherein a gas phase co-reactant comprising H2, CO, or olefins, or a combination thereof, or a recycle stream, is fed directly to the one or more pyrolysis reactors or the one or more catalytic pyrolysis reactors.

37. 31. The method of claim 30, wherein a solid co-reactant comprising agricultural lime, or calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, limestone, hydrotalcite, activated carbon, or zeolite, or other solid basic material, or combinations thereof, is provided to the heat treatment reactor.

38. 10. The method of claim 1, wherein the product vapor mixture from the fluidized bed catalytic reactor comprises at least 10 wt.% aromatics.

39. 10. The method of claim 1, wherein the product vapor mixture from the fluidized bed catalytic reactor comprises at least 10% by weight BTX, and in some embodiments in the range of 10 to 90% by weight BTX.

40. 10. The method of claim 1, wherein the product vapor mixture from the fluidized bed catalytic reactor comprises at least 10% by weight olefins, and in some embodiments in the range of 10 to 90% by weight olefins.

41. 2. The process of claim 1, wherein the product vapor mixture from the fluidized bed catalytic reactor comprises at least 30%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60%, or from 20% to 90%, or from 30% to 70%, or from 45% to 60% olefins based on the weight of the polymer feed.

42. 10. The method of claim 1, wherein the mass yield of BTX (benzene, toluene, and xylenes) in the product vapor mixture from the catalytic reactor is at least 30%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60%, or from 20% to 90%, or from 30% to 70%, or from 45% to 60% BTX based on the mass of polymer feed.

43. 10. The method of claim 1 , wherein benzene, toluene, or xylenes are separated or recovered from the product vapor mixture.

44. 40. The method of claim 38, wherein at least a portion of the aromatic products in the product vapor mixture is hydrogenated to produce naphthenes.

45. 10. The method of claim 1, wherein ethylene, propylene, butenes, or combinations thereof are separated from the catalytic pyrolysis product vapor mixture.

46. 2. The method of claim 1, wherein the product vapor mixture is subjected to a separation process to produce a gas stream enriched in CH4, CO, and H2, and at least a portion of the gas stream enriched in CH4, CO, and H2 is sent to the regenerator and combusted therein.

47. 10. The method of claim 1, wherein the product vapor mixture comprises CH4 and C2-C4 paraffins, and 50-100 wt.% of the CH4 and C2-C4 paraffins are combusted in the regenerator.

48. 10. The method of claim 1, wherein at least a portion of the catalyst in the fluidized bed catalytic pyrolysis reactor is removed, regenerated by oxidation with air or other oxidizing gas mixture, and returned to the catalytic pyrolysis reactor.

49. 49. The method of claim 48, wherein hot regenerated catalyst provides heat to the catalytic pyrolysis reactor.

50. 49. The method of claim 48, wherein at least a portion of the gas in the product mixture is combusted in the regenerator.

51. 49. The method of claim 48, wherein at least a portion of the natural gas is fed to the catalyst regenerator.

52. 49. The method of claim 48, wherein heat from the regeneration of the catalyst provides energy for the thermal treatment or pyrolysis or catalytic pyrolysis step.

53. 51. The method of claim 49 or 50, wherein heat recovered from the catalyst regenerator is used to heat the feedstock, the thermal treatment reactor, or the pyrolysis reactor, or the catalytic pyrolysis fluidized bed reactor, or a combination thereof.

54. 49. The method of claim 48, wherein the combustion product gas (exhaust gas) produced in either the catalyst regenerator or the packing regenerator, or both, is sent to a solid separation system, or multiple solid separation systems, comprising a series of cyclones, optional classifying cyclones, followed by one or more high efficiency multiclones.

55. 2. The method of claim 1, wherein the flow velocity at the inlet of the low efficiency cyclone is greater than 5 meters / second, or greater than 10 meters / second, or greater than 15 meters / second, or between 5 meters / second and 40 meters / second, or between 10 meters / second and 30 meters / second, or between 15 meters / second and 25 meters / second.

56. In any of the above-mentioned classifying cyclones, the ratio of vortex diameter to cylinder diameter is within the range of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.1-0.8, 0.3-0.7, 0.4-0.6, 0.45-0.55, 0.49-0.51, or the ratio of vortex length to cylinder length is within the range of 0.5, 0.6, 0.7, 0.8, 0.9, 0.3-0.95, 0.5-0.95, 0.8-0.95, 0.85-0.95, or the ratio of underflow diameter to vortex diameter is within the range of 0.02, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5 , 1.0, 1.25, or 0.02-1.25, 0.02-0.5, 0.1-0.3, or 0.15-0.25; or the ratio of inlet height to inlet width is in the ranges of 0.75, 1, 1.5, 2, 2.4, 3, 4, 5, or 0.75-5, 1.5-4, 2-3, 2.2-2.6; or the ratio of vortex length (S) to total height (H) is in the ranges of 0.1, 0.2, 0.3, 0.36, 0.4, 0.5, 0.6, 0.8, or 0.1-0.8, 0.2-0.6, 0.3-0.4, 0.34-0.

38.

57. The method of claim 2 , wherein the one or more recovery cyclones include at least one multiclone.

58. The method of claim 1 , wherein one or more of the cyclones does not have a vortex detection device.

59. In the multiple small diameter cyclones in any multiclone, the ratio of vortex diameter to cylinder diameter is within the range of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.1 to 0.8, 0.3 to 0.7, 0.4 to 0.6, 0.45 to 0.55, or 0.49 to 0.51, or the ratio of vortex length to cylinder length is within the range of 0.5, 0.6, 0.7, 0.8, 0.9, or 0.3 to 0.95, 0.5 to 0.95, 0.8 to 0.95, 0.85 to 0.95, or the ratio of underflow diameter to vortex diameter is within the range of 0.02, 0.1, 0.15, 0.2, 0. 25, 0.3, 0.5, 1.0, 1.25, or 0.02-1.25, 0.02-0.5, 0.1-0.3, or 0.15-0.25; or the ratio of inlet height to inlet width is in the ranges of 0.75, 1, 1.5, 2, 2.4, 3, 4, 5, or 0.75-5, 1.5-4, 2-3, 2.2-2.6; or the ratio of vortex length to total height is in the ranges of 0.1, 0.2, 0.3, 0.36, 0.4, 0.5, 0.6, 0.8, or 0.1-0.8, 0.2-0.6, 0.3-0.4, 0.34-0.

38.

60. 3. The method of claim 2, wherein the flow velocity at the inlet of any one of the recovery cyclones is 25 or less, or 20 or less, or 15 or less, or 10 or less, or 5 or less, or 3 or less, or from 3 to 20, or from 5 to 15, or from 6 to 12 meters per second.

61. 61. The method of any one of claims 57 to 60, wherein the number of small cyclones in one multiclone is 4, 9, 16, 25, 36, 49, or 64, or between 4 and 64, between 9 and 49, or between 16 and 36.

62. 3. The method of claim 2, wherein the efficiency of the low efficiency cyclone or classifying cyclone or combination of cyclones is 95% or less, 90% or less, 85% or less, 80% or less, or 75% or less.

63. 3. The method of claim 2, wherein the overall efficiency of the one or more recovery cyclones is at least 80%, or 85%, or 90%, or 95%, or 98%, or 99%, or 99.5%.

64. 3. The method of claim 2, wherein the particulate concentration in the steam product discharged from the recovery cyclone is no greater than 200, no greater than 300, no greater than 400, or no greater than 500 μg / m3 of steam product.

65. 10. The method of claim 1, wherein the plastic feed stream is treated in a thermal treatment reactor and the condensed phase is sent to the catalytic pyrolysis reactor.

66. 66. The method of claim 65, wherein a sweep gas, such as H2O, N2, Ar, CO2, or a combination thereof, is supplied to the thermal treatment reactor and vapors are exhausted.

67. 67. The method of claim 65 or 66, wherein the plastic feed stream is heated to a temperature of 250-300°C in the thermal treatment reactor and the product is sent to a pyrolysis reactor.

68. 68. The method of any one of claims 65 to 67, wherein an inert gas is supplied to the heat treatment reactor and steam is exhausted.

69. 69. The method of any one of claims 65 to 68, wherein the hot product stream from the thermal treatment reactor is filtered to remove solids before being fed to the pyrolysis reactor.

70. 70. The method of any one of claims 65 to 69, wherein the products produced in the optional thermal treatment reactor are transferred to a catalytic pyrolysis reactor containing a catalyst without separating the majority of the products.

71. 71. The method of any one of claims 65 to 70, wherein non-vapor products of the thermal treatment reactor, or a portion of the gas remaining after removing desired products, or both, are combusted to provide energy for the catalytic reaction in the fluidized bed.

72. 38. The method of claim 37, wherein at least a portion of the solid co-reactant is separated from the product stream of the thermal treatment reactor and transferred to a combustion regenerator where carbonaceous material reacts with air and at least a portion of the hot solid co-reactant is returned to the thermal treatment reactor.

73. 73. The method of claim 72, wherein hot exhaust gas exiting the solid co-reactant regenerator is sent to a catalytic heater to heat a catalyst for the catalytic pyrolysis reactor.

74. 74. A method according to any one of claims 65 to 73, wherein the thermal treatment is carried out by heating the feedstock to a temperature of 250-300°C and holding at that temperature whilst removing steam, followed by passing the condensed phase to the catalytic pyrolysis reactor or further pyrolysis at higher temperature in the pyrolysis reactor.

75. 49. The method of claim 48, wherein the catalyst removed from the catalytic reactor or the catalyst recovered in the solids separation system, or both, is stripped of volatiles by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or a combination thereof, or a recycle stream from the product gas through the catalyst particles, the streams are condensed, the organic and aqueous phases are separated, the liquid organic phase is sent to product recovery, the aqueous phase is sent to wastewater recovery, and the catalyst from which volatile organic compounds have been removed is sent to the catalyst regenerator, returned to the catalytic reactor, discarded, or a combination thereof.

76. The method of claim 2 , wherein the filler is recovered from the solids separation system.

77. 77. The method of claim 76, wherein the filler recovered in the solids separation system is stripped of volatiles by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or a combination thereof, or a recycle stream from product gas through the filler particles, the stream is condensed, the organic and aqueous phases are separated, the liquid organic phase is sent to product recovery, the aqueous phase is sent to wastewater recovery, and the filler from which volatile organic compounds have been removed is sent to the filler regenerator or disposed of, or a combination thereof.

78. 2. The method of claim 1, wherein the mass ratio of catalyst particles to filler particles entering the classifying cyclone is at least 1, 2, 5, 10, 20, 30, or 50, alternatively from 0.1 to 50, from 0.5 to 30, or from 5 to 20.

79. 2. The method of claim 1, wherein the mass ratio of catalyst particles to filler particles discharged from the bottom of the classifying cyclone is at least 5, or at least 30, or at least 50, or at least 200, or at least 1000, or from 5 to 10,000, from 30 to 5,000, or from 50 to 1000.

80. 2. The method of claim 1, wherein the mass ratio of catalyst particles to filler particles in the overflow from the classifying cyclone is 10 or less, 5 or less, 2 or less, 1 or less, 0.2 or less, or 0.1 or less, alternatively from 0.0001 to 10, from 0.001 to 5, or from 0.01 to 1.

81. 2. The method of claim 1, wherein the mass ratio of catalyst particles to filler particles in the overflow from the recovery cyclone is 0.1 or less, 0.001 or less, 0.00001 or less, or from 0.0000001 to 0.1, from 0.00001 to 0.01, or from 0.0001 to 0.

001.

82. 2. The method of claim 1, wherein the mass ratio of catalyst particles to filler particles at the bottom from the recovery cyclone is 0.1 or less, 0.001 or less, 0.00001 or less, or from 0.0000001 to 0.1, from 0.00001 to 0.01, or from 0.0001 to 0.001.

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