High efficiency process for separating fillers from catalyst and gases in a fluid bed catalytic pyrolysis process of plastics

Abstract

To provide a simple, continuous process for chemically recycling mixtures of polymers that contain fillers to chemical intermediates for further upgrading.SOLUTION: A process that separates the fillers found in plastics from catalyst and the gases in a fluid bed catalytic pyrolysis process for the conversion of waste plastics, polymers, and other waste materials to useful chemical and fuel products such as paraffins, olefins, and aromatics such as BTX, is described.SELECTED DRAWING: Figure 1

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, and 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 United States generated 55.2 million tons of plastic, accounting for 13% of MSW. 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, with only 9% of that amount recycled. Plastic recycling involves recovering scrap and waste plastic and reprocessing the material into useful products. However, since China banned the import of waste plastic in 2018, the U.S. recycling rate is estimated to have fallen to just 4.4%. Plastic recycling is difficult due to the chemical properties of long-chain organic polymers and the low economic benefits. Waste plastic materials often need to be separated into various 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. Additionally, plastic materials often contain particulate materials introduced into polymer formulations to reduce costs and improve properties. Fillers, materials added to plastic formulations, take up space and replace expensive resins with cheaper compounds. Cost reductions depend on the relative costs of the polymer and filler. As of May 2020, polymer prices ranged approximately ($ / kg) from ABS 10-16.5, HDPE 3.8-8.6, PET 1-3, PP 2.3-3.7, PS 10.9-16.8, and 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, growing at a 5.2% rate. Many of these fillers facilitate molding and shaping while ensuring the stability of the plastic. For plastics requiring heat resistance, mineral fillers increase thermal deformation and reduce thermal expansion. Large filler particle sizes can cause crack propagation and weaken the material. Particles larger than about 10-20 microns begin to significantly affect the impact resistance and elongation at break of the composite.Coarse particles result in poor surface finish, low gloss, and high transparency, so 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 with 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 might 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 xylene ("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 continuous removal of materials from the process, such as fillers, inorganic materials, salts, minerals, and glass and metal debris, to prevent their accumulation. Accumulation can reduce catalyst activity and adversely affect 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 material particles (<40 microns, 95% <20 microns) and large catalyst particles (>40 microns, 95% >65 microns). Effective separation of packing material from this stream and minimizing catalyst loss from the process are critical to consistent performance and minimize catalyst costs.

[0007] Filtration of hot melts to remove fillers from plastics 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). Filtration of 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] Dissolution plastics recycling involves dissolving polymers in a solvent to separate the solids, as practiced in CreaSolv® technology (https: / / www.creacycle.de / en / ) applied to polystyrene and PureCycle technology applied to polypropylene. This process requires filtering the polymer solution to remove particulate matter. In addition to issues arising from periodic cleaning and replacement of filters, this process requires large amounts of expensive solvent and near-100% solvent recovery for it to be viable. Furthermore, this process is limited to one type of polymer or polymer mixtures in which 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. Patent No. 9,803,035, describe a purification process in which polyethylene is contacted with a fluid solvent under elevated 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. Patent No. 10,465,058, describe a process for purifying recycled polymers 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 separating the polymer from the resulting solution. Layman et al., in U.S. Patent No. 1,100,843,3B2, describe a process for purifying recycled polymers 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 blends of filled polymers into chemical intermediates. [Means for solving the problem]

[0012] The present invention provides a simple system and continuous, one-step process for separating solids from a continuous reactor exhaust gas stream resulting from the pyrolysis of a carbonaceous feedstock containing a high concentration (up to 10%) of filler. This configuration involves a multi-stage cyclone system, with the first stage preferably being 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 that allows as much filler (small particles) as possible to be discharged with the cyclone gas and as much catalyst (large particles) as possible to be 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 minimum objective of meeting these separation goals and 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] In their article "Air Classifiers" published in the March 1986 issue of Chemical Engineering, I. Klumpar et al. present various classifiers and their size selection curves. Generally, these classifiers do not achieve the current cut size and are inefficient. This effect of industrial classifiers is described as a sharpness index, which can lead to a bypass of up to 30%! Other sources, such as the 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. Several common scientific techniques can be used to determine the particle size distribution (PSD) of a mixture: 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, this method exploits the strand separation effect in high-load cyclones and the bimodal particle size distribution of the incoming solids stream. Generally, the separation behavior (or efficiency) of high-load cyclones is driven by two main mechanisms: (1) Because of the limited turbulence within the cyclone, only a certain amount of solids can be carried in the inlet gas stream, also known as the critical load. When the solids load in the gas exceeds this critical load value, the excess solids mass is removed immediately after the cyclone inlet, forming 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 within the cyclone vortex (internal separation). Internal separation is determined by the balance between centrifugal force and particle resistance.

[0015] Strand separation becomes a 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 cyclone geometry. This describes the particle size boundary between large solids undergoing strand separation and small solids undergoing internal separation. Cyclones are typically designed to have the smallest possible cut size, resulting in the greatest removal of solids from the gas stream and maximizing separation efficiency. In this proposed application, the cyclone is designed so that only 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 specifically designed to reduce solids losses due to internal separation by modifying the dimensions of the vortex finder. These small solids (fines) are then discharged from the cyclone with the gas stream, effectively operating the cyclone as a solids classifier. The first cyclone is designed to separate coarse particles and achieve a bimodal particle size distribution, entraining fine particles into the off-gas for removal by a single cyclone or a series of high-efficiency multi-cyclones. Highly efficient Multiclone is used to reduce the concentration of elutriated particles to meet the solids loading limits 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 through a catalyst and filler recovery system comprising 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 stream comprising plastics, at least one of which comprises a filler, to a fluidized bed reactor containing a catalyst, the filler having a cut size or particle size smaller than the 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 comprising a first mass ratio of catalyst to filler; recovering a vapor effluent from the product mixture, the vapor effluent comprising catalyst particles and filler; and 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 is a classifying cyclone, and the first bottoms fraction has a second mass ratio greater than the first mass ratio; sending 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 and 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 be passed through an additional cyclone before the recovery step. Particle size in the claimed method can be measured by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), or scanning transmission electron microscopy (STEM). Size can be quantified as the median diameter of a volume fraction less than 50 vol% according to ASTM D4464-00.

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

[0022] In any aspect, the present invention may be further characterized by one or any combination of the following features: The solids separation system is comprised of one or more low-efficiency cyclones or classifying cyclones, or one or more recovery cyclones or multi-cyclones, or both. The inlet flow rate of the low-efficiency cyclones or classifying cyclones is greater than the inlet flow rate of the recovery cyclones. At least a portion of the solids recovered at the bottom from the one or more low-efficiency cyclones or classifying 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 ranging from 300°C to 800°C, or from 350°C to 700°C, or from 400°C to 650°C, or from 450°C to 625°C, or from 500°C to 600°C. An ethylene or propylene, or both, enriched stream is separated from the volatile products, and an ethylene or propylene, or both, enriched stream 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 40 to 300 microns, or 50 to 250 microns, or 75 to 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 to 40 microns, or 2 to 30 microns, or 5 to 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 reactor volume 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 temperature and pressure conditions.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 may be a circulating bed, bubbling bed, turbulent bed, or riser reactor. The fluidizing gas for catalytic pyrolysis may include H2, CO, CO2, H2O, C1-C4 paraffins or olefins or both, N2, Ar, He, or a recycle stream, or a combination thereof. The catalyst is a solid catalyst, and the catalytic pyrolysis process involves pyrolyzing the solid catalyst in the fluidized-bed reactor to produce a fluid product stream and spent catalyst containing 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 classifying cyclone is returned to the catalytic pyrolysis reactor, sent to a catalyst regenerator, or disposed of. A catalyst and packing solids separation system consisting of a classifying cyclone and a recovery cyclone is used, returning the solids from the classifying cyclone to the fluidized-bed reactor and recovering olefins or aromatics from the vapor discharged from the final recovery cyclone. The classifying cyclone is designed to have a cutoff size between the packing particle size distribution and the catalyst particle size distribution, separating the larger particle size fraction and entraining the smaller particle size fraction in the off-gas for removal in a series of high-efficiency recovery cyclones. The feedstream may comprise plastics selected from among polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymer, polyethylene furanoate (PEF), polyamide, polyurethane, polyether, polycarbonate, poly(oxide), poly(sulfide), polyarylate, polyetherketone, polyetherimide, polysulfone, polyurethane, polyvinyl alcohol, and polymers produced by polymerization of monomers such as dienes, olefins, styrene, 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 powder, fluorine mica, fly ash, fumed nanosilica, glass beads, glass fiber, glass flakes, glass spheres, graphene, graphite The filler may be selected from the group consisting of: slate, 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 a combination thereof. The filler may be selected from the group consisting of calcium carbonate, carbon black, silica, kaolin clay, talc, or a combination thereof. The catalyst in the fluidized bed reactor includes 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 includes ZSM-5. The catalyst in the fluidized bed includes a binder material selected from alumina, zirconia, silica, magnesia, thoria, titania, boria, or a combination thereof. The catalyst in the fluidized bed includes a catalytic molecular sieve, which accounts for 30 to 90 wt % or 40 to 70 wt % 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 into a fluidized-bed catalytic pyrolysis reactor. The pyrolysis reactor can be a moving-bed reactor, a single-screw extruder, a twin-screw extruder, an auger reactor, a static mixer reactor, a rotary kiln reactor, or a 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°C to 100°C, or 20°C to 50°C, at or near the inlet port, and 300°C to 700°C, e.g., 325°C to 650°C, or 350°C to 600°C, at the outlet port. The pyrolysis reactor can include 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 H, CO, or olefins, or a combination 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 a combination thereof. The output vapor mixture from the fluidized-bed catalytic reactor comprises at least 10 wt.% olefins, and in some embodiments, from 10 to 90 wt.% 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% to 90%, or 30% to 70%, or 45% to 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 mass % 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 another 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 a combination 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 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 gases in the product mixture are 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 a combination thereof. The combustion product gas (exhaust gas) generated in either or both of the catalyst regenerator and packing regenerator is sent to a solids separation system, or multiple solids separation systems, which include 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 cyclones 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 Figure 5] to the cylinder diameter ("D" in Figure 5) is within the ranges 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, or 0.49-0.51; alternatively, the ratio of the vortex length to the cylinder length is within the ranges of 0.5, 0.6, 0.7, 0.8, 0.9, 0.3-0.95, 0.5-0.95, 0.8-0.95, or 0.85-0.95; alternatively, the ratio of the underflow diameter to the vortex diameter is within the ranges of 0.02, 0.1, 0.15, 0. Alternatively, 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, 0.75 to 5, 1.5 to 4, 2 to 3, or 2.2 to 2.6; or the ratio of the vortex length (S) to the total height (H) is within the ranges of 0.1, 0.2, 0.3, 0.36, 0.4, 0.5, 0.6, 0.8, 0.1 to 0.8, 0.2 to 0.6, 0.3 to 0.4, or 0.34 to 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-cyclone.In the multiple small diameter cyclones in any multi-clone, 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, or 0.85 to 0.95, or the ratio of underflow diameter to vortex diameter is 0.02, 0.1, 0.15, Alternatively, 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 to 5, 1.5 to 4, 2 to 3, or 2.2 to 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 to 0.8, 0.2 to 0.6, 0.3 to 0.4, or 0.34 to 0.38. The flow velocity at the inlet of each 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 0.0000001 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, 0.0000001 to 0.1, 0.00001 to 0.01, or 0.0001 to 0.001. The number of small cyclones in one multi-cyclone is 4, 9, 16, 25, 36, 49, or 64, or 4 to 64, or 9 to 49, or 16 to 36. The efficiency of the low-efficiency cyclone, classifying cyclone, or cyclone combination 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 / 3 of the 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, or CO2, or a combination thereof, is fed to the thermal treatment reactor, and vapors are discharged. The plastic feedstock is heated to temperatures 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 discharged. 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 from 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 from 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, holding it at that temperature while removing steam, and then either sending the condensed phase to the catalytic pyrolysis reactor or pyrolyzing it at a higher temperature 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 from which the volatile organic compounds have been removed is sent to a catalyst regenerator, returned to the catalytic reactor, disposed of, or a combination thereof. The filler is recovered from the solids separation system.The packing material 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 the product gas, through the packing 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 packing material with the volatile organic compounds removed is sent to a packing regenerator or disposed of, or a combination thereof. [Effects of the Invention]

[0023] Chemically recycling plastics by pyrolysis in a thermochemical reactor offers many advantages, including: A solids separation system: Any type of plastic mixture is suitable; the long residence time in the pyrolysis reactor heats the plastic fragments to decomposition temperatures, eliminating the need for finely grinding plastic particles; 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 filler can be returned to the process, reducing catalyst losses and associated catalyst costs. Another advantage of the inventive process is that the production of a 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; this "distributed processing" scheme minimizes separation and purification costs for small, regional plastics upgrading facilities. [Brief explanation of the drawings]

[0024] [Figure 1] FIG. 1 shows a schematic of 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, and includes a cyclone solids separation system to separate fillers and other particulates from the system. [Figure 2]FIG. 2 shows a schematic of 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 a combination thereof, in which a thermal treatment reactor is used to remove contaminants before feeding them to the pyrolysis reactor, and a solids separation system is used to separate fillers and other particulates from the system. [Figure 3] Figure 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. [Figure 5] Figure 5 shows the parameters that define the cyclone design. [Figure 6] Figure 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 feeding plastic at a rate of 6.5 kg / hour for 3.5 hours (medium size peak), and after 75.5 hours TOS after feeding plastic at a rate of 6.5 kg / hour for 9.5 hours (highest peak). [Figure 10] Figure 10 shows the particle size distribution (PSD) of unstripped reactor catalyst from standpipe 1 at 27.5 hour TOS (low peak) after feeding plastic for 3.5 hours at a rate of 6.5 kg / hour and at 75.5 hour TOS (high peak) after feeding plastic for 9.5 hours at a rate of 6.5 kg / hour. [Figure 11]Figure 11 shows the PSD of the exfoliated reactor catalyst at 27.5 hours TOS (short peak) after feeding plastic at a rate of 6.5 kg / hr for 3.5 hours and at 75.5 hours TOS (high peak) after feeding plastic 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 hours TOS after feeding plastic at a rate of 6.5 kg / h for 3.5 hours. 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 material passing through a solids separation system (top data) and the PSD of the catalyst in a fluidized bed (bottom data). Each data point represents the mass fraction of the sample containing particles smaller than a particular diameter. DETAILED DESCRIPTION OF THE INVENTION

[0025] term Aromatic Compound—As used herein, the terms “aromatic compound” or “aromatic compound” are 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 varies depending on the particle size and density. Fine particles can also 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 into the separator. This arrangement prevents direct gas short-circuiting from the fluid inlet to the outlet. The solids to be separated are suspended in a high-velocity, tangentially introduced gas stream, creating a rotational motion within the vessel. Centrifugal force throws the particles against the vessel walls. As the gas velocity decreases, larger, denser particles fall to the bottom and collect at the solids outlet. The gas exits the central outlet at the top, entraining the smaller, 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] Catalyst—A catalyst component 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 influences 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 catalyst component can be acidic, neutral, or basic, as understood by one of ordinary skill in the art.

[0028] For catalytic pyrolysis, particularly advantageous catalysts include those containing internal porosity selected according to pore size (e.g., pore sizes typically associated with mesoporous and zeolites), such as those containing 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 even less. In some embodiments, catalysts having average pore sizes of about 0.5 nm to about 10 nm can be used. In some embodiments, catalysts having 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 having 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 can be selected from natural zeolites, synthetic zeolites, and combinations thereof. In certain embodiments, the catalyst can be a ZSM-5 zeolite catalyst, as will be understood by those skilled in the art. Optionally, such catalysts can contain acidic 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, and SSZ-23. Zeolites and other small pore materials are often characterized by a constraint index, which approximates the ratio of the cracking rate constants for normal hexane and 3-methylpentane. A method for determining the constraint index is described in more detail in U.S. Pat. No. 4,029,716, which is incorporated by reference for details of the method.

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

[0031] [Table 1]

[0032] The CI can vary within a range of 1 to 12. Similarly, other variables, such as crystal size and the presence of occluding contaminants or binders that may be tightly bound to the crystals, can also affect the CI. Those skilled in the art will appreciate that while the CI used herein provides a very useful means for characterizing the molecular sieves of interest, it is an approximation given the method of its determination, and that in some cases, extreme values ​​of the variables may be compounded. However, the CI value of any molecular sieve useful herein will be approximately within the range of 1 to 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 promoter 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. Furthermore, 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 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. Plastic or Polymer - 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 greater than 10,000. Polymers include thermoplastic polymers (e.g., polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymer, 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, acrylonitriles, methacrylates, methacrylonitriles, diacids, and Examples of suitable feedstocks include polymers produced by the polymerization of vinyl halides, vinyl esters, diols, lactones, diacids and diamines, lactams, vinyl halides, vinyl esters, their block copolymers, and their alloys; thermosetting polymers (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 ethylene-propylene-diene monomer polymers); and blends thereof. Mixtures of polymers separated from municipal solid waste or other waste streams are suitable feedstocks 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 thermal decomposition, such as polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), and other halogenated polymers, are typically minimized or excluded from the feedstocks 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, into one or more other substances, such as volatile organic compounds, gases, coke, etc., by heat, preferably without the addition of O or in the absence of O. Preferably, the volume fraction of O 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 described in more detail 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 particle size and density. Classifying cyclones work by using centrifugal force to separate a portion of the particles, defined by their cut size, from the gas stream. As the gas and particles enter the cyclone, the rotational motion creates a vortex, causing heavier particles to move toward the cyclone walls and lighter particles to remain in the center. The separated particles exit the cyclone through a separate outlet, while the gas or steam, along with the remaining particles, continues to flow through the cyclone and is discharged through another outlet.

[0036] A "recovery cyclone" is a type of cyclone that separates solids from a vapor stream, removing enough solids to allow the vapor stream to 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 exiting the recovery cyclone of, for example, 1 m3 of vapor product. 3 Remove enough particles to be below a target concentration, such as 200, 300, 400, or 500 μg per aliquot.

[0037] The separation efficiency (sometimes called recovery) of a cyclone 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 rates 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] Low-efficiency cyclones, i.e., most of the solids entering the cyclone pass through the cyclone and are discharged with the overflow, are called classifying cyclones. Classifying cyclones can be used to separate materials with different average particle sizes. High-efficiency cyclones, i.e., only a small portion of the solids entering the cyclone pass through the cyclone and are discharged with the overflow, and their purpose is to remove solids from the vapor 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 (up to 20% by weight) the polymer composition, such as 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, gas, etc. The preferred materials include 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, a liquid, a mixture of a gas and a liquid, or a gas or liquid containing dispersed solids, liquid 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 within 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 suspend the solid material and cause it to behave as if it were a fluid. Examples of fluidized bed reactors are described in D. Kunii and O. Levenspiel, “Fluidization Engineering” (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 D. Kunii and O. Levenspiel, “Fluidization Engineering” (Butterworth-Heinemann, 1991).

[0043] Bubbling fluidized bed reactors 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 fluidized bed reactors and turbulent fluidized bed reactors are described in Kirk-Othmer Encyclopedia of Chemical Technology (Online), Vol. 11, Hoboken, NJ: Wiley-Interscience, 2001, pp. 791-825, which are incorporated herein by reference.

[0044] Olefin—The term “olefin” or “olefinic compound” (also known as “alkene”) has its usual meaning in the art and 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 acyclic (aliphatic) olefins, 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 containing 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 generated and discharged, the feed mixture is melted, 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 listing exemplary components.

[0047] Detailed Description of the Invention FIG. 1 shows a schematic diagram of a process for converting plastic waste to olefins and aromatics. A plastic mixture 10 is introduced into an optional feed system 100, which prepares the plastic mixture for introduction into the process by removing undesired feed materials 102, such as metals, minerals, clays, halogenated materials, contaminants such as Cl and Br that can contaminate the catalyst, and other elements, and / or sizing the materials to a desired size range. The undesired feed material removal and sizing steps 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 cleaned, for example, by treatment with a washing solution 112 to remove unwanted materials such as dirt, labels, and coatings, producing a cleaned plastic mixture 111 and a spent solution 113. The plastic mixture 111 is then sent to an optional pyrolysis reactor 120. Optionally, a gas-phase co-reactant, or recycle stream (not shown), comprising H, CO, or olefins, or a combination thereof, can be fed directly to optional pyrolysis reactor 120 or catalytic pyrolysis reactor 140. In optional pyrolysis reactor 120, the mixture can be heated to a temperature that will decompose the plastics into a product mixture comprising a combination of gaseous, solid, and liquid phases. Without separation, at least a portion of raw pyrolysis product mixture 121 is sent to catalytic reactor 140 while maintaining the temperature of the pyrolysis product mixture at least at the temperature at which it exited pyrolysis reactor 120. The plastic mixture, i.e., raw plastic mixture 101, washed plastic mixture 111, or pyrolysis product mixture 121, is sent to high-temperature catalytic reactor 140, shown as catalytic vapor stream 141, which is packed with an aromatization catalyst effective to convert paraffins, olefins, or both, to aromatics. 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 it. The hot, regenerated catalyst 143 is returned to the reactor 140 to provide heat thereto, and the combustion product gas 152 is sent to a regenerator exhaust gas cleanup cyclone (not shown), vented, 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 inventive process for converting plastic waste to olefins and aromatics. A plastic mixture 10 is introduced into an optional feed system 100, which prepares the plastic mixture for introduction into the process by removing undesired feed materials 102, such as metals, minerals, clays, halogenated materials, contaminants such as Cl and Br that may contaminate the catalyst, and other elements, and / or sizing the material to a desired size range. The undesired feed material removal and sizing steps 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 cleaned, for example, by treatment with a washing solution 112 to remove unwanted materials such as dirt, labels, and coatings, producing a cleaned plastic mixture 111 and a spent solution 113. The prepared plastic mixture 111, along with an optional co-reactant 122, such as a heat transfer medium or getter, is sent to a thermal treatment reactor 115, where the mixture is heated to an intermediate temperature to partially decompose the plastic, e.g., decomposing PVC or PVDC to release HCl, or decomposing another halogenated polymer to release HCl, HBr, or HI, or releasing vapors such as NH, HO, etc. An optional sweep gas 124, such as HO, N, Ar, CO, or a combination thereof, is supplied to the thermal treatment reactor 115 to aid in the removal of vapors generated therein, which are then discharged through an exit port 125. With or without a sweep gas, the vapor 125 can be treated to capture or neutralize HCl and toxic substances 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 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 the raw product mixture 121 if the optional pyrolysis reactor 120 is used, is sent 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 can be continuously removed from the reactor 140 and / or separated from the product 141, at least a portion of which is sent 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, while the combustion product gases 152 are sent to a regenerator cyclone (not shown) or vented. Optionally, natural gas or a recycle stream can 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, xylene, naphthalene, and other fractions in a separation scheme using conventional separation techniques.

[0049] Figure 3 shows a more detailed schematic of the solids separation system 160. The catalyst vapor stream 141, containing the catalyst and filler, is sent to one or more classifying (low-efficiency) cyclones 170, where the catalyst 162, containing a small amount of filler particles, is separated and sent to catalyst regeneration 150, catalytic pyrolysis reactor 140, discarded, or a combination of these. The vapor stream 171 exiting the classifier 170 contains most of the filler and little catalyst except for some fines. The vapor stream 171 is sent to a series (N units) of high-efficiency multiclones 180, where the filler 182 is separated and optionally sent to a filler regeneration unit 190, where the filler is combusted with air to provide heat for the process or discarded. The regenerated filler 191 is discarded. The product stream 181, with most of the filler removed, is sent to separation and product collection. This stream contains a solids concentration that does not exceed the allowable limit for entrained particles released to the atmosphere.

[0050] The solids separation system of the present invention provides a means for separating the filler from the catalyst, wherein the cut size or particle size of the filler is smaller than the cut size or particle size of the fluidized-bed catalyst. The vapor effluent from catalytic pyrolysis, containing catalyst particles and filler, passes through a first cyclone to separate 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, which has a catalyst particle separation efficiency greater than the first separation efficiency, to separate into a second bottoms fraction and a second overflow fraction. The bottoms fraction from the second cyclone has a catalyst-to-filler mass ratio lower 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 packing regenerator can 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 can 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 can be returned to the catalytic pyrolysis reactor. Small particles recovered from the refining stage can be discarded.

[0052] Combustible gases such as methane, ethane, propane, butane, CO, H2, etc., can optionally be recovered from vapor stream 125, from the gases produced by catalytic pyrolysis in the fluidized bed reactor, or from product stream 141. The combustible gases can provide heat for 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 reactor 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 optionally be removed from the feed composition by an optional separation step, such as 100 in FIG. 1 or 2, before being fed to the reactor. In some cases, the separation step may include mechanical separation, sink / flotation 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 sized-reduced feed composition exiting 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 can 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) can 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 can be advantageous to feed smaller particles to the reactor. A size reduction system can 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, polyether ketone, 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, styrene, 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), and combinations thereof.The present invention includes subcombinations of these materials, optionally or available from particular locations, and the present 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, in which the feedstock is propelled along the length of the reactor by mechanical, gravitational, or both mechanical and gravitational means. 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 some embodiments, the thermal treatment reactor or pyrolysis reactor is equipped with a gas outlet in a region of the reactor where the temperature of the material within the reactor is below 300°C or between 250°C and 300°C, allowing low-temperature products, such as steam, HCl, NH3, or other materials, to be removed from the reactor. A separation screen can be installed in the pyrolysis reactor immediately downstream of the gas outlet to at least partially prevent gases evolved at lower temperatures from flowing into the hotter section of the reactor along with the melt and solid material. Immediately downstream of the gas vent and optional screen, a gas inlet can be installed for introducing hot inert or recycle gases, such as CH, H, CO, CO, C-C paraffins or olefins, or a mixture thereof.

[0056] Optionally, a solid co-reactant 122 (such as 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 in different sections 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 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. The kiln cylinder can be fitted with lifters, such as spiral 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 upward or downward toward the exit end of the kiln, depending on the desired residence time and flow rate of the condensed phase within the kiln, thereby utilizing 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 and 0.2 revolutions per minute, depending on the nature of the input mixture and added co-reactants, to achieve thorough mixing and high heat transfer. Rotary kilns can be heated externally by combustion of waste process gases, such as CH4, C2-C4 paraffins, H2, and CO, recycled from product separation or natural gas, or by electricity.

[0059] In any aspect of the invention, the temperature profile within any pyrolysis reactor can range from a low temperature near the feed inlet port to a high temperature 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. A 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. The hot exhaust gas 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 thermal treatment reactor 115, the raw product preferably does not come into contact with cold surfaces that could condense the product, and 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 any embodiment, the temperature of the mixture is maintained at a temperature 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 thermal treatment reactor.

[0061] In any embodiment of the present invention, the catalytic reactor 140 may be a fluidized bed reactor; wherein the catalyst is a solid catalyst, and the catalytic pyrolysis step includes pyrolyzing 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, and heat from the hot regenerated catalyst provides 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 both approaches, 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, which roughly separates small from large particles.

[0063] Cyclones are typically designed and installed to separate solids as efficiently as possible from a gas stream, such as when removing dust from exhaust gases. The overall separation efficiency of a cyclone 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. Therefore, if the solid mass flow rate is m in where the mass fractions of small and large particles are x small and x large When a bimodal solids flow of x enters a cyclone, typical cyclone design criteria aim for the highest possible efficiency. That is, the solids flow rate exiting 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 results in (x small )·m in A cyclone can be effectively designed so that a solids flow rate of 0.05% is discharged from the top of the cyclone, resulting in a lower efficiency for 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 = 0.05% for a typical cyclone design). JPEG2025170307000003.jpg16160Efficiency targeted in this application JPEG2025170307000004.jpg16160). Therefore, 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 the height of the inlet to the width of the inlet can be any of 0.02, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5, 1.0, or 1.25, or within the ranges of 0.2 to 1.25, 0.02 to 0.5, 0.1 to 0.3, or 0.15 to 0.25. The ratio of the height of the inlet to the width of the inlet can be any of 0.75, 1, 1.5, 2, 2.4, 3, 4, or 5, or within the ranges of 0.75 to 5, 1.5 to 4, 2 to 3, or 2.2 to 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 is within 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, over 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] Multiclone devices are used in later stages of separation. Multiclone devices, or multicyclones, consist of multiple small-diameter tubes arranged in parallel, each functioning like a miniature cyclone. This configuration combines the high efficiency of a small diameter with the ability to process large volumes of gas. The gas flow rate in each small-diameter tube is higher than in larger-diameter tubes, resulting in higher separation efficiency. Multiclone devices 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 this invention. Multiclone devices are widely used to reduce emissions levels in many biomass boilers, cement kilns, and lime kilns. Multiclone devices work by ensuring that downstream equipment, such as fractionators, fans, scrubbers, and settlers, operates with minimal energy input. They operate as a series of multiple high-efficiency cyclones operating in a parallel configuration using 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 multiple small cyclones are designed to provide 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 are capable of handling particles as small as 5 microns in diameter.

[0066] Referring to Figure 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 vortex length (S) to 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 ranges 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 vortex length (S) to total height (H) is 0.1, 0.2, 0.3, 0.36, 0.4, 0.5, 0.6, or 0.8, or within the ranges 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-cyclone 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 large particle size entrained solids can be sent to a catalyst regenerator, at least a portion can be returned to the catalytic pyrolysis reactor, or can be 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 solids-removed product vapor stream contains 1 m of product vapor. 3 It must not contain more than 150, 300, or 500 mg of solid matter 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, and 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, are sent to a charging regeneration unit, 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 vapor in 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 to 2.0 MPa (1 to 20 bar), or 0.1 to 1.0 MPa (1 to 10 bar), or 0.3 to 0.8 MPa (3 to 8 bar), preferably 0.4 to 0.6 MPa (4 to 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 H, CO, CO, H0, C1-C4 paraffins or olefins, or both, N, Ar, He, or a recycle stream, or combinations thereof.

[0070] For catalytic pyrolysis, useful catalysts include those containing internal porosity selected according to pore size (e.g., pore sizes typically associated with mesoporous and zeolites), e.g., those with average pore sizes of less than 10 nm, less than 5 nm, less than 2 nm, less than 1 nm, less than 0.5 nm, or even 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 an SAR (silica to alumina, SiO:AlO 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 a crystalline molecular sieve characterized by an SAR greater than 12 to 240 and a CI between 5 and 10, e.g., a molecular sieve 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 sieves used in the present invention, or catalyst compositions containing same, may be heat-treated at elevated temperatures. This heat treatment is typically carried out by heating at a temperature of at least 370°C for at least 1 minute, typically for up to 20 hours (typically in an oxygen-containing atmosphere, preferably air). Although subatmospheric pressures can be used for the heat treatment, atmospheric pressure is preferred for 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 can be used in combination with a support or binder material, such as 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 typically 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 varies widely, with the molecular sieve content ranging from 30 to 90 percent by weight of the composition, typically ranging from 40 to 70 percent. The catalyst composition may also be in the form of extrudates, beads, or fluidizable microspheres.

[0074] The molecular sieve or catalyst composition containing it 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 supplied to the regenerator via stream 151. The oxidant can be supplied from any source, such as an oxygen tank, atmospheric air, or steam. In the regenerator, the catalyst is reactivated by reacting with the oxidant to generate heat. The solid mixture containing the deactivated catalyst may contain residual carbon and / or coke, as well as coke or char from the process, which can be removed by reaction with the oxidant in the regenerator. A portion of the gaseous products from the catalytic pyrolysis process are supplied to the 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 supplied to the catalyst regenerator. The regenerator in FIG. 1 includes an exhaust stream 152, which may contain regeneration reaction products, residual oxidant, etc.

[0076] In either method, the exhaust vapor from the catalyst regenerator passes 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 another 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 vapor, averaged over a 24-hour or year period.

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

[0078] Referring to Figure 5, for the exhaust gas solids separation system, the dimensions of the classifying cyclone (optional) and the recovery cyclone (multi-clone) can conform to the same length ratios as those described above for the product vapor 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 can 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 can include a solid material that reacts with the sulfur or nitrogen compound to capture the sulfur or nitrogen species in a solid phase. The solid material of the optional co-reactant 122 can 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 waste plastic upgrading system 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) and C6-C8 20 Each plastic upgrading site forms 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 that is introduced into 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 Multiple plastics upgrading sites (spokes) constitute one "spoke" in a "hub-and-spoke" network for producing paraffins and olefins (ethylene, propylene, naphthalene, etc., or combinations thereof), each producing a condensed phase product that is sent to a central processing facility (hub) that includes a central fluidized bed catalytic processing plant (Plas-TCat™) and separation and purification product streams. In some embodiments of the system, the number of plastics pyrolysis facilities that can be present in the network feeding a 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 to 20, or 3 to 10, or 5 to 10 plastics pyrolysis facilities. The total amount of crude product mixture produced in 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. [Example]

[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 performed to determine the cyclone required to separate and remove the filler from the product effluent from the catalytic reactor. The filler was assumed to have a particle size of approximately 95% by mass less than 20 microns, and the catalyst was assumed to have a particle size of 95% by mass greater than 65 microns. Figure 4 shows the particle size distributions of the filler, catalyst, and the combined filler and catalyst feed ("cyclone inlet"). The plastic mixture was assumed to undergo catalytic pyrolysis in a fluidized-bed catalytic reactor, producing a product vapor flow of 5.2 kg / s containing entrained solids, including 1.2 kg / s of catalyst particles and 0.29 kg / s of filler particles. It was assumed that 10% of the feed mixture would deposit coke on the catalyst and be adsorbed into the interstitial pores of the catalyst, producing material 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 3The gas density of the vapor stream was assumed to be 1.65 kg / m3 at 500°C. The solids separation system designed for solids separation and removal included 28 cyclones: one classifier, a low-efficiency cyclone, and three stages of refinery multi-cyclones with nine internal cyclones per stage. The cyclone dimensions and performance are summarized in Table 3 for the parameters shown in Figures 5 and 6. The mass of material obtained from each cyclone stage of the solids separation system in Table 3 is summarized in Table 4. The percentage of each material fed to each stage and separated into the bottom and top sections is summarized in Table 5. The destination of the material entering the catalytic reactor is shown in Table 6. Calculations showed that the majority of the catalyst was separated in the first classifying cyclone, with the remainder exiting in stage 2. The first cyclone was designed with a low efficiency target of 80.5%, which would completely remove the packing material, which accounted for 19.4% of the solids in the cyclone inlet gas. After optimizing the cyclone dimensions, the calculated efficiency was 80.9%. The second, third, and fourth separation stages were then designed with an overall efficiency target of 99.6%, which would reduce the packing material content in the gas to the desired specification of 4 kg / h, corresponding to the solids limit allowed to enter the downstream processing unit. While the majority of the desired separation (94.2%) was achieved in the second cyclone, the third and fourth stages completed 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 highest achievable using the computational approach used, primarily 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 of 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 performed on the cyclones required to separate and remove fillers from the exhaust gas discharge from a catalyst regenerator in a plastics chemical recycling system processing 500 tonnes per day of mixed plastics containing 5% filler by weight to produce useful products. The fillers were assumed to be approximately 95% particles less than 20 microns in mass, and the catalyst was assumed to be 95% particles greater than 65 microns in mass. The particle size distribution of the solids discharged from the regenerator was determined experimentally and includes fillers and catalyst, and is shown in Figure 7. The separated solids included a particle with a density of 1300 kg / m3. 3 catalyst particles and a density of 2700 kg / m 3 The solid flow rate is 105 kg / s and 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 the separation and removal of solids, contains a total of 76 cyclones: one classifier, a low-efficiency cyclone, and three stages of tandem multi-cyclones with 25 internal cyclones in each stage. Table 7 summarizes the cyclone dimensions and performance for the items in Figures 5 and 6. Table 8 summarizes the mass of material obtained from each cyclone stage of the solids separation system in Table 5. Table 9 summarizes the percentage of each material fed to each stage and separated into bottoms and overhead. Table 10 lists the destinations of materials entering the catalyst regenerator.

[0089] Calculations show that all catalyst is separated in the first classifying cyclone. The first cyclone is designed for a low efficiency of 99.7%, allowing for complete removal of the filler, which accounts for 19.4% of the solids content of the inlet gas to the cyclone. The first-stage cyclone completely separates the filler from the catalyst, with all catalyst recovered from the bottom of the cyclone and 97.25% of the filler passing through with the gas phase. The second, third, and fourth separation stages are designed for an overall efficiency of 99.6%, allowing for reduction of the filler content in the gas to the desired specification of 4 kg / h, corresponding to the solids limit allowed into downstream processing units. While the majority of the desired separation (94.8%) was achieved in the second-stage cyclone, the third and fourth stages completed the separation to meet 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 cyclone use multicyclones containing 25 cyclones each, 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 within the pilot plant is shown in Figure 8. This diagram 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. 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. Large particles from both cyclones were returned to the reactor, and the vapor stream from the first cyclone was passed to the second cyclone. The cyclones separated larger particles (mainly catalyst) 162 from smaller particles in a vapor product stream 163, which was returned to the catalytic fluidized-bed reactor. The cyclone dimensions for the design in 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, the plant was brought into operation, and a flow of inert gas (N2) was established. 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 the filler-containing plastic feed. Samples were taken 3.5 hours after the plastic feed. After 5.5 hours of plastic feed, the reactor was run for 42 hours without feed but held at elevated temperature.

[0100] The plastic-containing filler feed 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 been fed plastic 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] Figure 9 confirms that the PSD of the regenerated catalyst sample is unimodal with similar distributions at 24, 27.5, and 75.5 hours after start-up. The maximum volume density was measured at particle sizes between 105 and 110 μm. Early in the start-up period (24-hour TOS), the PSD is broad. As the TOS progresses, the distribution narrows as larger particles are attrited and 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 unstripped catalyst in standpipe 1 was unimodal, with the maximum volume density measured at particle sizes between 105 and 110 μm at all time points during the flow. As previously noted, the PSD is broad at the initial TOS, with the distribution narrowing slightly as the TOS increases. Similarly, Figure 11 shows the PSD profiles of the stripped catalyst at three different times during the flow, with the earlier times having a broader distribution than the later TOS.

[0105] Figure 12 shows the PSDs for 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 / h. The higher peak is due to the regenerated catalyst, while the lower peak represents two other PSDs overlapping each other. The slightly broader PSD is likely due to coke that accumulated a few percent by weight on the catalyst 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 contained approximately 80% by mass of particles smaller than 50 microns, while the catalyst bed contained less than 1% by mass of particles smaller than 50 microns. This indicates that the two cyclones can efficiently classify particles by size into particles smaller than 80 microns and particles larger than 80 microns.

[0107] Example 4 In a system processing 500 tons per day of mixed plastics containing 5% filler by weight into useful products, 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. The filler was assumed to be approximately 95% particles by mass less than 20 microns, and the catalyst was assumed to be approximately 95% particles by mass greater than 65 microns. The particle size distributions of the filler, catalyst, and the combined filler and catalyst feed ("cyclone inlet") are shown in Figure 4. The plastic mixture is assumed to undergo catalytic pyrolysis in a fluidized-bed catalytic reactor, producing a product vapor flow of 5.2 kg / s containing entrained solids, including 1.2 kg / s of catalyst particles and 0.29 kg / s of filler particles. It was assumed that 10% of the feed mixture would deposit 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 is assumed to be 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 performed for various conditions of reactor inlet fluidization velocity and the amount of packing entering the reactor, and the results are summarized in Table 15. In all cases, the proposed classification design was able to remove 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 demonstrates that the classifying cyclone can efficiently separate the filler from the product vapor and recycle it to the reactor without loss of catalyst.

[0110] [Table 14]

[0111] [Table 15]

Claims

1. A process for producing olefins and aromatic compounds, comprising: feeding a stream comprising plastics containing at least one filler material to a fluidized bed reactor containing a catalyst, wherein the filler material has a cut size or particle size smaller than the cut size or particle size of the fluidized bed catalyst; catalytically reacting the feedstock with a catalyst in the fluidized bed reactor to form a product mixture comprising a first mass ratio of catalyst and filler material; recovering a vapor effluent from said product mixture, wherein said vapor effluent comprises 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; sending 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 fraction vapor discharged from said last cyclone; A method comprising:

2. 10. The method of claim 1, wherein the first cyclone comprises one or more low efficiency cyclones or classifier 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 are 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. 10. 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% by 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 between 40 and 300 microns, or between 50 and 250 microns, or between 75 and 150 microns.

10. 10. 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. 10. 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 0.1 to 2.0 MPa (1 to 20 bar), or 0.1 to 1.0 MPa, or 0.3 to 0.8 MPa, preferably 0.4 to 0.6 MPa.

13. 10. 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. 10. The method of claim 1, wherein the fluidizing gas for catalytic pyrolysis comprises H, CO, CO, H0, C1-C4 paraffins or olefins or both, N, Ar, He, or a recycle stream, or a combination thereof.

15. 10. The method of claim 1, wherein the catalyst is a solid catalyst and the step of catalytic pyrolysis comprises pyrolyzing in the presence of the solid catalyst in a fluidized bed reactor to produce a fluidized product stream and spent catalyst together with coke, wherein 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. 10. The process of claim 1, wherein a catalyst and packing solids separation system is used that includes a classifying cyclone and a recovery cyclone, wherein solids are returned from the classifying cyclone to the fluidized bed reactor, and olefins or aromatics are recovered from the vapors exiting the final recovery cyclone.

18. The method according to claim 17, wherein the classifying cyclone is designed to have a cut size between the particle size distribution of the filler and the particle size distribution of the catalyst, so that the large particle size fraction can be separated and the small particle size fraction can be entrained in the off-gas and removed in a series of high-efficiency recovery multi-cyclones.

19. the feed stream comprises plastics selected from polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymer, polyethylene furanoate (PEF), polyamide, polyurethane, polyether, polycarbonate, poly(oxide), poly(sulfide), polyarylate, polyetherketone, polyetherimide, polysulfone, polyurethane, polyvinyl alcohol, and polymers produced by polymerization of monomers such as dienes, olefins, styrene, 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 powder, fluorine mica, fly ash, fumed nanosilica, glass beads, glass fiber, glass flake, glass sphere, graphene, graphite, ground tire rubber, hollow gas 10. 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, superconductor (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 method 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 a combination 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 a catalytic molecular sieve, the catalytic molecular sieve 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, from 20 to 100°C, or from 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, from 325°C to 650°C, or from 350°C to 600°C.

34. 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 method of any one of claims 30 to 35, wherein a gas phase co-reactant, or recycle stream, comprising H, CO, or olefins, or a combination thereof, 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 a combination thereof, is fed 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 wt. % olefins, and in some embodiments in the range of 10 to 90 wt. % olefins.

41. 10. 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 the polymer feed.

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

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

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

46. 10. 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 to 100 wt. % of the CH4 and C2-C4 paraffins is 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 gases in the product mixture are 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 the 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 filler regenerator, or both, is sent to a solid separation system, or multiple solid separation systems, wherein the solid separation system or multiple solid separation systems comprises 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 the vortex diameter to the cylinder diameter is within the ranges of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 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; alternatively, the ratio of the vortex length to the cylinder length is within the ranges of 0.5, 0.6, 0.7, 0.8, 0.9, 0.3 to 0.95, 0.5 to 0.95, 0.8 to 0.95, or 0.85 to 0.95; alternatively, the ratio of the underflow diameter to the vortex diameter is within the ranges of 0.02, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5 , 1.0, 1.25, or 0.02 to 1.25, 0.02 to 0.5, 0.1 to 0.3, or 0.15 to 0.25; or the ratio of the inlet height to the inlet width is in the ranges of 0.75, 1, 1.5, 2, 2.4, 3, 4, 5, or 0.75 to 5, 1.5 to 4, 2 to 3, 2.2 to 2.6; or the ratio of the vortex length (S) to the 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 to 0.8, 0.2 to 0.6, 0.3 to 0.4, or 0.34 to 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 any of the plurality of small-diameter cyclones within a multiclone, 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, 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 to 1.25, 0.02 to 0.5, 0.1 to 0.3, or 0.15 to 0.25; or the ratio of the height of the inlet to the width of the inlet is within the range of 0.75, 1, 1.5, 2, 2.4, 3, 4, 5, or 0.75 to 5, 1.5 to 4, 2 to 3, 2.2 to 2.6; or the ratio of the vortex length to the total height is within the range of 0.1, 0.2, 0.3, 0.36, 0.4, 0.5, 0.6, 0.8, or 0.1 to 0.8, 0.2 to 0.6, 0.3 to 0.4, 0.34 to 0.

38. The method according to claim 2.

60. The flow velocity at the inlet of any 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 3 to 20, or 5 to 15, or 6 to 12 meters per second. The method according to claim 2.

61. The number of small cyclones within one multiclone is 4, 9, 16, 25, 36, 49, or 64, or 4 to 64, 9 to 49, or 16 to 36. The method according to any one of claims 57 to 60.

62. The efficiency of the low-efficiency cyclone or classification cyclone or combination of cyclones is 95% or less, 90% or less, 85% or less, 80% or less, or 75% or less. The method according to claim 2.

63. 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%. The method according to claim 2.

64. The particle concentration in the vapor product discharged from the recovery cyclone is 200 or less, 300 or less, 400 or less, or 500 μg or less per cubic meter of the vapor product. The method according to claim 2.

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 fed to the heat treatment reactor and vapor 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 thermal treatment reactor product stream 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 vapour, followed by passing the condensed phase to the catalytic pyrolysis reactor or pyrolysing at a 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 product gas, over 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, 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, 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. 10. 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 0.1 to 50, 0.5 to 30, or 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 5 to 10,000, 30 to 5,000, or 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, or from 0.0001 to 10, from 0.001 to 5, or from 0.01 to 1.

81. 10. 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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