Method for efficiently separating filler from catalyst and gas in fluidized bed catalytic pyrolysis process

Abstract

A process for separating fillers from catalysts and gases in plastics in a fluidized bed catalytic pyrolysis process is described that converts waste plastics, polymers, and other waste materials to useful chemicals and fuel products, such as aromatics such as paraffins, olefins, and BTX.

Description

[0001] Related Applications

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63 / 338,013, filed on May 3, 2022. Field of the Invention

[0003] The present invention relates to converting waste plastics, polymers and other waste materials into useful chemicals and fuel products, such as paraffins, olefins and aromatics (e.g. BTX) in a process that includes an efficient method for separating fillers from catalyst particles used for upgrading such waste materials.

[0004] introduction

[0005] In 2019, the United States generated 55.2 million tons of plastic, accounting for 13% of municipal solid waste generation. Worldwide, more than 368 million tons of plastic are produced. It is estimated that of the 8.3 billion tons of plastic ever produced, 6.3 billion tons end up as waste, of which only 9% is recycled. Plastic recycling is the recovery and reprocessing of waste or scrap plastic into useful products. However, since China banned the import of scrap plastics in 2018, the recycling rate in the United States is estimated to have dropped to only 4.4%. Plastic recycling is challenging due to the chemical properties of long-chain organic polymers and low economic returns. Waste plastic materials often need to be sorted into different plastic resin types, such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET) for separate recycling processes. In addition, plastic materials often contain particulate materials introduced into the polymer formulation to reduce costs and improve performance. The materials added to the plastic formulation, so-called fillers, take up space and replace expensive resins with cheaper compounds. Cost reduction depends on the relative costs of polymers and fillers. In May 2020, polymer prices ranged from approximately $1 / kg: 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 are generally well below $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 rate of 5.2%. Many fillers make plastics easier to shape while ensuring their stability. For plastics that require heat resistance, mineral fillers can increase heat deformation and reduce thermal expansion. Larger filler particles can weaken the material by providing a place for cracks to develop. Particles larger than about 10-20 microns begin to seriously affect the impact resistance and elongation at break of the composite. Coarser particles also result in poorer surface finish, i.e., low gloss, and increased permeability. Therefore, fillers are generally preferably very small particles, smaller than about 30 microns.

[0006] When fillers are present in polymers, they typically make up 20-30% of the composite mass. However, some materials (such as PVC) contain up to 90% fillers by weight, while others have filler content of less than 0.1% by weight.

[0007] Plas-TCat TMIt is a catalytic fluidized bed process that uses a zeolite catalyst to convert polymer / plastic materials, especially waste plastics that might otherwise be sent to landfills or incinerators, into a mixture of permanent gases, C2-C4 light olefins, C1-C4 light paraffins and C5+ hydrocarbons (including benzene, toluene and xylenes ("BTX")), aromatic and non-aromatic naphtha series 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. In Plas-TCat TM Materials such as fillers, inorganics, salts, minerals or glass or metal fragments must be constantly removed from the process to avoid accumulation, which can both reduce catalyst activity and adversely affect reactor fluid dynamics.

[0008] In Plas-TCat TM During the process, fillers will be elutriated in the gaseous effluents from the reactor and regenerator, along with some entrained catalyst, resulting in a bimodal distribution of solids in the gaseous effluent stream, with smaller filler particles (<40 microns, 95% <20 microns) and larger catalyst particles (>40 microns, 95% >65 microns). Effective separation of fillers from this stream while minimizing catalyst losses in the process is critical to stabilizing performance and reducing catalyst costs.

[0009] Fillers can be removed from plastics by filtering the hot melt using screens or candle filters, such as those offered by MAAG. (https: / / maag.com / wp-content / upl oads / LAF%20Brosch%C3%BCre_ EN_16S_s.pdf) Filtration of plastic hot melts requires heating the mixture to high temperatures (up to 400°C) and high pressures (up to 300 bar) to force the viscous molten plastic through the filter, and requires regular cleaning or replacement of the filter elements, which requires shutting down the entire process.

[0010] Dissolved plastic recycling involves dissolving the polymer in a solvent to separate the solids, as applied to polystyrene. technology (https: / / www.creacycle.de / en / ) Or PureCycle technology for polypropylene. The process requires filtering the polymer solution to remove particulate matter. In addition to the problems created by regular cleaning or replacement of filters, the process requires large amounts of expensive solvents and almost 100% recovery of the solvent is only feasible. The process is also limited to one type of polymer or polymer mixtures where all polymers in the mixture are dissolved in the same solvent, which requires additional separation of the polymer mixture into the individual component polymers in the actual recycling stream.

[0011] Layman et al. in US 9803035 describe a method for purifying polyethylene by contacting the polyethylene with a fluid solvent at high temperature and pressure, and then contacting the polyethylene solution with a solid medium to produce a purer polyethylene solution. Layman et al. in US 10465058 describe a method for purifying recycled polymers by dissolving the polymer in a solvent, settling the solution to remove suspended contaminants, purifying the solution by contacting with a solid medium, and separating the polymer from the resulting solution. Layman et al. in US 11008433B2 describe a method for purifying recycled polymers by dissolving the polymer in a solvent, settling the solution to remove suspended contaminants, purifying the solution by contacting with a solid medium, and separating the polymer from the resulting solution, and repeating the process for different polymers in the mixture.

[0012] All dissolution processes require handling of large volumes of solvent and are separate from the polymer chemical recovery process.

[0013] There is a need for a simple, continuous process for chemically recycling polymer mixtures containing fillers into chemical intermediates for further upgrading. SUMMARY OF THE INVENTION

[0015] The present invention provides a simple system and a continuous one-step process for separating solids from a continuous reactor effluent gas stream produced by the pyrolysis of a carbonaceous feed containing a high concentration (up to 10%) of fillers. The structure comprises a multi-stage cyclone system, the first stage preferably being a single cyclone, and the second and subsequent stages each comprising axial type multi-cyclone separators (multi-cyclones) operating in parallel. The efficiency of the first cyclone separator is adjusted to a level such that as much filler (smaller particles) as possible is discharged with the gas outlet of the cyclone separator, and as much catalyst (larger particles) as possible is discharged from the bottom of the cyclone separator. For the present invention, the goal is to have at least 85% of the filler (smaller diameter components) in the inlet gas stream discharged with the cyclone separator gas outlet (top outlet), and to separate at least 95% of the catalyst (larger diameter components) from the inlet gas stream discharged through the bottom of the cyclone separator and return it to the reactor. The minimum goal of sizing the cyclone separator is to meet these separation goals and to exceed these goals to the maximum achievable value as much as possible. Subsequent stages will operate at high efficiency, further reducing the amount of filler in the off-gas leaving the reactor to meet solids loading limits entering downstream processing units.

[0016] I. Klumpar et al. present different classifiers and their size selection curves in the article “Air Classifiers” in Chemical Engineering, March 1986. In general, it can be said that they do not achieve the current cut size and are less efficient. This effect of industrial classifiers is described as the sharpness index and can lead to bypass phenomena of up to 30%! Other sources, such as Metso Air Classifier (https: / / www.mogroup.com / products-and-services / plants-and-capital-equipment / classifiers / air-classifiers / ), claim that their cut size can be as low as 10μm and the maximum particle size limit is 500μm. The particle size distribution (PSD) of a mixture can be determined using any of several conventional scientific methods, such as light scattering, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning transmission electron microscopy (STEM).

[0017] Without wishing to be bound by theory, the present method exploits the striping effect in a high-load cyclone separator and the bimodal particle size distribution of the incoming solids stream. In general, the separation behavior (or efficiency) of a high-load cyclone separator consists of two main mechanisms: (1) The restricted turbulence in the cyclone separator only allows the inlet gas stream to carry a certain amount of solids, which is also called the critical load. If the solids load in the gas exceeds this critical load value, the excess solid mass is removed immediately after the cyclone inlet and forms a striped layer or a continuous layer on the wall (striping). (2) Only a small portion of the finer particle size distribution remains in the gas stream and is centrifugally separated in the vortex of the cyclone separator (internal separation). Internal separation is controlled by the balance between centrifugal force and particle drag.

[0018] When the solid loading is greater than about 0.05 kg / kg, strand separation becomes a more dominant mechanism, as described by Muschelknautz, Edgar, and Volker Greif in "Cyclones and Other Gas-Solid Separators" (see Circulating Fluidized Beds. Springer, Dordrecht, 1997. 181-213) and Hugi, Erich, and Lothar Reh. in "Focus on solids strand formation improves separation performance of highly loaded circulating fluidized bed recycle cyclones" (see Chemical Engineering and Processing: Process Intensification 39.3 (2000): 263-273).

[0019] Both 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, describing the particle size boundary between larger solids that undergo banding and smaller solids that undergo internal separation. Cyclones are typically designed to have a cut size as small as possible to maximize solids removal from the gas stream and maximize separation efficiency. In this proposed application, the cyclone is designed so that only the catalyst (larger) particles will undergo banding and be easily removed from the gas stream, while the remaining solids (fillers) will remain in the gas stream in the vortices of the cyclone. This design is intended to reduce solids losses due to internal separation, particularly by modifying the size of the vortex finder. These smaller solids (fines) are then discharged from the cyclone with the gas stream. Effectively the cyclone is used as a solids classifier. The cut size of the first cyclone is designed to be between the bimodal particle size distribution so that the coarse particles are separated, while the fine particles are entrained in the exhaust gas to be removed in one or more high efficiency multi-cyclones. The high efficiency multi-cyclones are used to reduce the concentration of elutriated particles to meet the solids loading limits of the downstream process.

[0020] The present invention provides a method for producing olefins and aromatics from waste plastics, comprising feeding a stream containing plastics into a fluidized bed catalytic pyrolysis reactor, catalytically reacting the feed with a catalyst to form a product mixture, passing the vapor effluent through a catalyst and filler recovery system including a classifying cyclone separator and a recovery cyclone separator, returning solids from the classifying cyclone separator to the fluidized bed reactor, discarding the filler recovered from the recovery cyclone separator, and recovering olefins or aromatics from the vapor discharged from the last recovery cyclone separator.

[0021] The first aspect of the present invention provides a method for converting plastics into olefins or aromatics or a mixture of olefins and aromatics, comprising: feeding a stream containing plastics (at least one of which contains fillers) into a fluidized bed reactor containing a catalyst; wherein the average particle size of the fillers is smaller than the average particle size of the fluidized bed catalyst; allowing the feed to undergo a catalytic reaction with the catalyst in the fluidized bed reactor to form a product mixture; recovering a vapor effluent from the product mixture; passing the vapor effluent through a solid separation system; separating the catalyst from the fillers, and recovering olefins or aromatics or a combination thereof from the vapor discharged from the last recovery cyclone separator.

[0022] A second aspect of the present invention provides a method for producing olefins and aromatics, comprising: feeding a stream containing plastics (wherein at least one plastic contains fillers) into a fluidized bed reactor containing a catalyst, wherein the cut size or particle size of the fillers is 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 containing a first mass ratio of catalyst to fillers; recovering a vapor effluent from the product mixture, wherein the vapor effluent contains catalyst particles and fillers; passing the vapor effluent through a solid separation system, including sending the vapor effluent to a first cyclone separator and separating a first bottom material portion. The invention relates to a method for preparing a catalyst particle separation device and a first overflow portion; wherein the first cyclone separator is a classifying cyclone separator; wherein the first bottom material portion has a second mass ratio greater than the first mass ratio; the overflow portion is sent to a second cyclone separator and the second bottom material portion and the second overflow portion are separated; wherein the first cyclone separator has a first separation efficiency for catalyst particles, and the second cyclone separator has a second separation efficiency for catalyst particles, and the second separation efficiency is greater than the first separation efficiency; wherein the second bottom material portion has a third mass ratio less than the first mass ratio; and olefins or aromatics or a combination thereof are recovered from the second overflow portion vapor discharged from the last cyclone separator.

[0023] The second overflow portion may be passed through an additional cyclone separator prior to the recovery step. The particle size in the claimed method may be measured by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) or scanning transmission electron microscopy (STEM). The size may be quantified according to ASTM D4464-00 as the median diameter with a volume fraction less than 50 vol%.

[0024] In other aspects, the invention comprises any device, system (device plus conditions and / or chemical flows), or method described herein.

[0025] In any aspect thereof, the present invention is further characterized by one or any combination of the following features: wherein the solid separation system comprises one or more low-efficiency classifying cyclone separators, or one or more recovery cyclone separators or multi-cyclone separators, or both; wherein the flow rate at the inlet of the low-efficiency classifying cyclone separator is greater than the flow rate at the inlet of the recovery cyclone separator; wherein at least a portion of the solids recovered from the bottom material of the one or more low-efficiency classifying cyclone separators is returned to the fluidized bed reactor; wherein at least a portion of the solids recovered from the one or more recovery cyclone separators is discarded; wherein the catalytic pyrolysis is carried out at 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 650°C ℃ to 600 ℃ operating temperature range; wherein the ethylene or propylene or both rich stream is separated from the volatile products; wherein the ethylene or propylene or both rich stream is separated from the volatile products and at least partly recycled to the pyrolysis reactor; wherein 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); wherein at least 80% by mass of the filler The size of the particles is no more than 40 microns, or 30 microns, or 20 microns, or 15 microns, or 10 microns, 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); wherein the residence time of the fluidizing gas in the catalytic pyrolysis reactor is defined as the volume of the reactor divided by the volume flow rate of the fluidizing fluid under the process temperature and pressure conditions, and 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; 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; wherein the fluidized bed reactor is a circulating bed, a bubbling bed, a turbulent bed or a riser reactor; wherein the fluidizing gas used for catalytic pyrolysis may include H2, CO, CO2, H2O, C1-C4 paraffins or olefins or both, N2, Ar, He or a recycled stream, or some combination thereof; wherein the catalyst is a solid catalyst, the catalytic pyrolysis step comprises pyrolysis in the presence of the solid catalyst in a fluidized bed reactor to produce a fluid product stream and a spent catalyst containing coke, and wherein at least 90% of the carbon in the feed is converted to coke and volatile products;wherein at least a portion of the catalyst separated from the low-efficiency classifying cyclone separator is returned to the catalytic pyrolysis reactor, or is transferred to a catalyst regenerator, or is discarded; wherein a catalyst and filler solid separation system comprising a classifying cyclone separator and a recovery cyclone separator is used, the solid from the classifying cyclone separator is returned to the fluidized bed reactor, and olefins or aromatics are recovered from the vapor discharged from the last recovery cyclone separator; wherein the cut size of the classifying cyclone separator is designed to be between the particle size distribution of the filler and the particle size distribution of the catalyst, thereby allowing a larger particle size portion to be separated and a smaller particle size portion to be sandwiched The invention relates to a method for removing a plastic material from a waste gas stream in order to remove the plastic material in a series of high-efficiency recovery multi-cyclone separators; wherein the feed mixture comprises a plastic material selected from the group consisting of polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymers, polyethylene furanoate (PEF), polyamides, polyurethanes, polyethers, polycarbonates, polyoxides, polysulfides, polyarylates, polyetherketones, polyetherimides, polysulfones, polyurethanes, polyvinyl alcohols and polyvinyl alcohols obtained by monomers (e.g., dienes, olefins, styrenes, acrylates, acrylonitriles, methacrylates, methacrylonitrile, diacids and Polymers produced by polymerization of diols, lactones, diacids and diamines, lactams, vinyl esters), their block copolymers, and their alloys; thermosetting polymers, such as epoxy resins; phenolic resins; melamine resins; alkyd resins; vinyl ester resins; unsaturated polyester resins; cross-linked polyurethanes; polyisocyanurates; cross-linked elastomers, including but not limited to polyisoprene, polybutadiene, styrene-butadiene, styrene-isoprene, ethylene-propylene-diene monomer polymers; and mixtures thereof, wherein the raw material comprises a mixture of waste plastics selected from the group consisting of: polyethylene terephthalate (PE T), high density polyethylene (HDPE), polyvinyl chloride (PVC) or polyvinylidene fluoride (PVCD), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), or mixed resins, or some combination thereof; wherein the raw material comprises a mixture of waste plastics selected from the group consisting of polyethylene terephthalate (PET), high density polyethylene (HDPE), polyvinyl chloride (PVC) or polyvinylidene fluoride (PVCD), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), or mixed resins, or some combination thereof;The filler is selected from alumina, aluminum, aluminum fiber, aluminum sheet, aluminum hydroxide, aluminum nitride, antimony-doped tin oxide, antimony oxide, aromatic polyamide, 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 whisker, carbon black, carbon fiber, carbon nanotube, cellulose nanocrystal, chitosan, clay, compatibilizer, copper, diamond, diatomaceous earth, expanded graphite, ferromagnetic powder, fluorine mica, fly ash, fumed nano-silica, glass beads, glass fibers, glass sheets, glass balls, graphene, graphite, tire rubber powder, hollow glass microspheres, hollow silicates , hydrotalcite, iron, kaolin, lignin, magnesium hydroxide, magnesium oxide, magnetite, mica, microfiber cellulose, molybdenum sulfide, montmorillonite, nickel-barium, nickel, phenolic microspheres, potassium titanate whiskers, potassium magnesium aluminum silicate, PTFE, pyrophyllite, red mud, red phosphorus, rubber particles, sand, sepiolite, silane, silicon dioxide, silicon carbide, silver powder, soot, starch, talc, tetrapod-shaped zinc oxide whiskers, titanium dioxide nanoparticles, titanium dioxide, vermiculite, wollastonite, wood fiber, wood powder, zinc borate, zinc oxide, zirconium silicate, or a combination thereof; wherein the filler is selected from calcium carbonate, carbon black, silicon dioxide, kaolin, or talc, or a combination thereof. wherein the catalyst in the fluidized bed reactor comprises a zeolite; wherein the SAR (silicon dioxide / alumina ratio, SiO2:Al2O3 mass ratio) of the catalyst is greater than 12, or 12 to 240, and the CI (constraint index) is 1 to 12 or 5 to 10; 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; wherein the catalyst comprises ZSM-5; wherein the catalyst in the fluidized bed comprises a binder material selected from alumina, zirconia, silica, magnesia, thoria, titania, boria or a combination thereof; wherein the catalyst in the fluidized bed comprises a catalytic molecular sieve, wherein the catalytic molecular sieve accounts for 30 wt% to 90 wt% or 40 wt% to 70 wt% of the catalyst particle composition; wherein the catalyst in the fluidized bed is in the form of fluidizable microspheres; wherein the plastic is pretreated in the pyrolysis reactor to remove chlorine and then fed into the fluidized bed catalytic pyrolysis reactor; wherein the pyrolysis reactor is a moving bed, a single screw extruder, a twin screw extruder, a screw reactor, a static mixer reactor, a rotary kiln reactor or a stepped grate reactor; wherein the pyrolysis reactor comprises a feed inlet and an outlet, and the temperature in the pyrolysis reactor ranges from a lower temperature near the feed inlet to a higher temperature at the outlet; wherein at or near the inlet, the temperature in the pyrolysis reactor may range from 20°C to 225°C, such as 20 to 100°C or 20 to 50°C, and the temperature at the outlet may range from 300°C to 700°C, such as 325 to 650°C or 350 to 600°C; wherein the pyrolysis reactor comprises two or more reactors connected in series;wherein the residence time of the condensed phase in the thermal treatment or pyrolysis reactor is at least 1, or at least 5, or at least 10, or at least 20, or at least 30, or from 1 to 60, or from 5 to 30, or from 10 to 30 minutes; wherein a vapor phase co-reactant or recycle stream comprising H2, CO or olefins or some combination of these is fed directly to one or more pyrolysis reactors or one or more catalytic pyrolysis reactors; wherein the product vapor mixture from the fluidized bed catalytic reactor comprises at least 10 mass % BTX, and in some embodiments, comprises in the range of 10 to 90 mass % BTX; wherein the solid co-reactant fed to the thermal treatment reactor comprises agricultural lime or calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, limestone, hydrotalcite, activated carbon or zeolite or other solid alkaline material, or some combination thereof; wherein the product vapor mixture from the fluidized bed catalytic reactor comprises at least 10% by mass of olefins, in some embodiments, comprises olefins in the range of 10 to 90% by mass; 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 20% to 90%, or 30% to 70%, or 45% to 60% of olefins based on the mass in the polymer feed; wherein the BTX (benzene, toluene and xylene) in the product vapor mixture from the catalytic conversion The mass yield of BTX 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% based on the mass in the polymer feed; wherein benzene, toluene or xylenes are separated or recovered from the product vapor mixture; wherein at least a portion of the aromatic products in the product vapor mixture are hydrogenated to produce cycloalkanes; wherein ethylene, or propylene, or butenes, or a combination thereof are separated from the catalytic pyrolysis product vapor mixture; wherein the product vapor mixture is subjected to a separation process to produce a gas stream rich in CH4, CO and H2; and at least a portion of the gas stream is passed to a regenerator where they are combusted; wherein the product vapor mixture comprises CH4 and C2-C4 paraffins; and wherein 50 to 100 mass % of the CH4 and C2-C4 paraffins are combusted in the regenerator; wherein the catalyst in the fluidized bed catalytic pyrolysis reactor is removed and regenerated by oxidation with air or other oxidizing gas mixture and returned to the catalytic pyrolysis reactor; wherein the catalyst removed from the catalytic reactor or the catalyst recovered in the solid separation system, or both, is stripped of volatile materials by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or some combination of these, or a recycle stream from the product gas through the catalyst particles;wherein condensable materials in the stream exiting the stripper are condensed, the organic phase and the aqueous phase 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 a catalyst regenerator; wherein the hot regenerated catalyst provides heat to the catalytic pyrolysis reactor; wherein at least a portion of the gas in the product mixture is combusted in the regenerator; wherein at least a portion of the natural gas is sent to the catalyst regenerator; wherein the heat from the catalyst regeneration provides energy for the thermal treatment or pyrolysis or catalytic pyrolysis step; wherein the heat recovered from the catalyst regenerator is used to heat the feed, the thermal treatment reactor or the pyrolysis reactor or a catalytic pyrolysis fluidized bed reactor or a combination thereof; wherein the combustion product gas (flue gas) produced in the catalyst regenerator or the filler regenerator or both is conveyed to a solid separation system or a separate plurality of solid separation systems, the one or more solid separation systems comprising a series of cyclone separators, wherein there is an optional classified cyclone separator, followed by one or more high-efficiency multi-cyclone separators; wherein the flow velocity at the inlet of the low-efficiency classified cyclone separator is greater than 5, or greater than 10, or greater than 15, or 5 to 40, or 10 to 30, or 15 to 25 m / s; wherein in any one of the classified cyclone separators, the vortex diameter [; Figure 5 "De" in] and the inner diameter of the cylinder ( Figure 5, or the ratio of the underflow diameter to the vortex diameter may be 0.02, or 0.1, or 0.15, or 0.2, or 0.25, or 0.3, or 0.5, or 1.0, or 1.25, or 0.5, or 1.3, or 1.4, or 1.5, or 2.5, or 3.5, or 4.5, or 5.5, or 6.5, or 7.5, or 8.5, or 9.5, or 10.5, or 11.5, or 12.5, or 13.5, or 14.5, or 15.5, or 16.5, or 17.5, or 18.5, or 19.5, or 20.5. 0.02 to 1.25, or 0.02 to 0.5, or 0.1 to 0.3, or 0.15 to 0.25, or the ratio of inlet height to inlet width may be 0.75, 1, or 1.5, or 2, or 2.4, or 3, or 4, or 5, or may be in the range of 0.75 to 5, or 1.5 to 4, or 2 to 3, or 2.2 to 2.6, or the ratio of vortex length (S) to total height (H) may be 0.1, or 0.2, or 0.3, or 0.36, or 0.4, or 0.5, or 0.6, or 0.8, or in the range of 0.1 to 0.8, or 0.2 to 0.6, or 0.3 to 0.4, or 0.34 to 0.38; wherein one or more cyclone separators do not have vortex finders ; wherein the one or more recovery cyclone separators include at least one multi-cyclone separator; wherein for each of the plurality of small diameter cyclone separators within any multi-cyclone separator, the ratio of the vortex diameter to the barrel diameter may be 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 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, or the ratio of the vortex length to the barrel length may be 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or in the range of 0.3 to 0.95, or 0.5 to 0.95, or 0.8 to 0.95, or 0.85 to 0.95, or the ratio of the underflow diameter to the barrel length may be 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or in the range of 0.3 to 0.95, or 0.5 to 0.95, or 0.8 to 0.95, or 0.85 to 0.95, or the ratio of the underflow diameter to the barrel diameter may be 0.2, or 0.3, or 0.4, or ... The ratio of vortex diameters may be 0.02, or 0.1, or 0.15, or 0.2, or 0.25, or 0.3, or 0.5, or 1.0, or 1.25, or in the range of 0.02 to 1.25, or 0.02 to 0.5, or 0.1 to 0.3, or 0.15 to 0.25, or the ratio of inlet height to inlet width may be 0.75, or 1, or 1.5, or 2, or 2.4, or 3, or 4, or 5, or in the range of 0.75 to 5, or 1.5 to 4, or 2 to 3, or 2.2 to 2.6, or the ratio of vortex length to total height may be 0.1, or 0.2, or 0.3, or 0.36, or 0.4, or 0.5, or 0.6, or 0.8, or in the range of 0.1 to 0.8, or 0.2 to 0.6, or 0.3 to 0.4, or 0.34 to 0.38; wherein the flow rate at the inlet of any recovery cyclone does not exceed 25, or 20, or 15, or 10, or 5, or 3, or is 3 to 20, or 5 to 15, or 6 to 12 meters per second; wherein the mass ratio of catalyst particles to filler particles entering the classification cyclone is at least 1, 2, 5, 10, 20, 30 or 50, or is 0.1 to 50, 0.5 to 30, or 5 to 20 ... The mass ratio of catalyst particles to filler particles discharged from the bottom of the classifying cyclone separator 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, or 30 to 5,000, or 50 to 1000; wherein the mass ratio of catalyst particles to filler particles in the overflow of the classifying cyclone separator does not exceed 10, 5, 2, 1, 0.2 or 0.1, or is 0.0001 to 10, 0.001 to 5, or 0.01 to 1; wherein the overflow of the recovery cyclone separator is The mass ratio of catalyst particles to filler particles in the stream does not exceed 0.1, 0.001, 0.00001, or is between 0.0000001 and 0.1, 0.00001 and 0.01, or between 0.0001 and 0.001; wherein the mass ratio of catalyst particles to filler particles in the bottom material of the recovery cyclone separator does not exceed 0.1, 0.001, 0.00001, or is between 0.0000001 and 0.1, 0.00001 and 0.01, or between 0.0001 and 0.001; wherein The number of small cyclone separators in any one of the multi-cyclone separators may be 4, 9, 16, 25, 36, 49 or 64, or 4 to 64, or 9 to 49, or 16 to 36 cyclone separators; wherein the efficiency of the low efficiency classification cyclone separator or the combination of cyclone separators does not exceed 95%, or 90%, or 85%, or 80%, or 75%; wherein the efficiency of one or more recovery cyclone separators combined is at least 80%, or 85%, or 90%, or 95%, or 98%, or 99%, or 99.5%; wherein the particle concentration in the vapor product discharged from the recovery cyclone separator does not exceed 200, or 300, or 400, or 500 μg per cubic meter of vapor product; wherein the plastic feed stream is treated in a thermal treatment reactor and the condensed phase is conveyed to a catalytic pyrolysis reactor; wherein a purge gas (e.g., H2O, N2, Ar, CO2, or a combination thereof) is fed to the thermal treatment reactor and the vapor is discharged; wherein the plastic feed stream is heated to a temperature between 250 and 300°C in the thermal treatment reactor and the product is conveyed to the pyrolysis reactor; wherein an inert gas is fed to the thermal treatment reactor and the vapor is discharged; wherein the hot product stream from the thermal treatment reactor is subjected to wherein the product produced in the optional thermal treatment reactor (without separating a majority of the product) is transferred to a catalytic pyrolysis reactor containing a catalyst; wherein the non-vapor product of the thermal treatment reactor or a portion of the gas remaining after removal of the desired product, or both, is burned to provide energy for the catalytic reaction in the fluidized bed; wherein solid co-reactant material is fed to the thermal treatment reactor; wherein the solid co-reactant material is separated from the process stream and transferred to a combustion regenerator, wherein the carbonaceous material reacts with air and at least a portion of the hot solid co-reactant material is returned to the thermal treatment reactor; wherein the hot flue gas leaving the solid co-reactant material regenerator is heated by passing it through a catalyst a catalytic pyrolysis reactor to heat the catalyst for the catalytic pyrolysis reactor; wherein the thermal treatment is carried out by heating the feed to a temperature between 250 and 300° C., maintaining it at that temperature while removing the vapor, and then sending the condensed phase to the catalytic pyrolysis reactor or further pyrolyzing it at a higher temperature in the pyrolysis reactor; wherein volatile materials are removed from the catalyst removed from the catalytic reactor or from the catalyst recovered in the solid separation system, or both, by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or some combination of these, or a recycle stream from the product gas through the catalyst particles, condensable materials in the condensation stream, separating the organic phase and the aqueous phase, sending the liquid organic phase to product recovery, and sending the aqueous phase to wastewater recovery, and the catalyst from which volatile organic compounds have been removed is sent to a catalyst regenerator, or returned to the catalytic reactor, or discarded, or some combination of these operations, wherein the packing is recovered from the solid separation system; wherein volatile materials are removed from the packing recovered in the solid separation system by passing a stream of steam, nitrogen, CO, CO2, CH4, He or some combination of these gases or a recycle stream from the product gas through the packing particles, condensable materials in the condensation stream, separating the organic phase and the aqueous phase, sending the liquid organic phase to product recovery, sending the aqueous phase to wastewater recovery, and the packing from which volatile organic compounds have been removed is sent to a packing regenerator, or discarded, or some combination of the above operations. .

[0026] Chemical recycling of plastics by pyrolysis in a thermochemical reactor including a solid separation system has many advantages: any type of plastic mixture is suitable; the plastic particles do not need to be ground to a small size, as the long residence time in the pyrolysis reactor ensures that the plastic fragments are heated to the decomposition temperature; the pyrolysis can be operated at high temperatures; unwanted contaminants can be removed in an optional thermal treatment reactor; small particle size fillers can be effectively separated from the catalyst and discarded; the catalyst separated from the fillers can be returned to the process, thereby reducing catalyst losses and the resulting catalyst costs. Another advantage of the process of the present invention is that the production of a crude liquid product stream made from recycled plastics by the process of the present invention can be carried out at a different location from the product separation and purification system, and this "distributed processing" scheme minimizes the separation and purification costs of small-scale regional plastic upgrading facilities. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 A method for converting mixed plastic materials into valuable products by pyrolyzing the mixed plastics and catalytically reacting the crude product mixture to produce olefins, aromatics, or some combination thereof is schematically shown, the method including a solids separation system of a cyclone separator for separating fillers and other fines from the system.

[0029] Figure 2 A method for converting mixed plastic materials into valuable products by pyrolyzing the mixed plastics and catalytically reacting the products to produce olefins, aromatics, or some combination thereof is schematically shown, wherein a thermal treatment reactor is used to remove contaminants before feeding the pyrolysis reactor, and a solids separation system separates fillers and other fines from the system.

[0030] Figure 3 A schematic diagram of the solid separation system is shown.

[0031] Figure 4 The particle size distribution of the filler, catalyst, and the sum of filler and catalyst in the feed of Example 1 is shown.

[0032] Figure 5 The parameters defining the cyclone separator design are shown.

[0033] Figure 6 The design of a multi-cyclone separator is shown.

[0034] Figure 7 The experimentally determined particle size distribution of regenerator exiting solids (including filler and catalyst) is shown.

[0035] Figure 8 A schematic diagram of the pilot plant reactor operating with the solids separation system is shown.

[0036] Fig. 9 The particle size distribution (PSD) measured for the regenerated catalyst from standpipe 3 is shown. The PSD measured for the regenerated catalyst from standpipe 3 was: before introduction of the plastic feed containing filler, after 24 hours TOS (lowest peak); after 3.5 hours of feeding plastic at a rate of 6.5 kg / hour, at 27.5 hours TOS (medium size peak); after 9.5 hours of feeding plastic at a rate of 6.5 kg / hour, at 75.5 hours TOS (highest peak).

[0037] Fig.10 The particle size distribution (PSD) of the unstripped reactor catalyst from standpipe 1 after feeding plastic for 3.5 hours at 6.5 kg / hr at TOS 27.5 hours (lower peak) and after feeding plastic for 9.5 hours at 6.5 kg / hr at TOS 75.5 hours (higher peak) is shown.

[0038] Fig.11 The PSD of the stripped reactor catalyst after feeding plastic for 3.5 hours at 6.5 kg / hr at TOS 27.5 hours (shorter peak) and after feeding plastic for 9.5 hours at 6.5 kg / hr at TOS 75.5 hours (higher peak) are shown.

[0039] Fig.12 The PSDs of samples from standpipes 1 (unstripped), 2 (stripped) and 3 (regenerated) at TOS 27.5 hours are shown after feeding plastic at 6.5 kg / hour for 3.5 hours. The taller peak is from the regenerated catalyst, while the shorter peak shows two other PSDs that overlap each other.

[0040] Fig.13 The PSD of material passing through the solid separation system (upper data) is shown compared to the PSD of the catalyst in the fluidized bed (lower data). Each data point represents the mass fraction of the sample containing particles smaller than a particular diameter.

[0041] the term

[0042] Aromatics - As used herein, the term "aromatics" or "aromatic compound" is used to refer to hydrocarbons containing one or more aromatic groups, such as single aromatic ring systems (eg, benzyl, phenyl, etc.) and fused polycyclic aromatic ring systems (eg, 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, trimethylbenzenes (e.g., 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, etc.), ethylbenzene, styrene, isopropylbenzene, methylbenzene, propylbenzene, xylenes (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, hydroindene, methylhydroindene, and dimethylhydroindene. In some embodiments, single-ring and / or higher-ring aromatic hydrocarbons may also be produced.

[0043] Cyclone Separator - In a cyclone separator, centrifugal force is used to separate solids from a fluid. The separation process depends on the particle size and particle density. It is also possible to allow fine particles to flow with the fluid. The cyclone separator consists of a short vertical cylindrical vessel with a conical bottom. The upper part of the vessel is equipped with a tangential inlet. The solids outlet is located at the bottom. The fluid outlet is arranged at the top center and can extend inward into the separator. This arrangement prevents the gas from short-circuiting directly from the inlet to the fluid outlet. The solids to be separated are suspended in a gas stream introduced tangentially at high speed, causing a rotational motion in the vessel. Centrifugal force throws the particles against the vessel wall. As the gas velocity decreases, the larger, denser particles fall to the bottom and accumulate at the solids outlet. The gas can escape from the top central outlet together with the smaller, less dense particles entrained therein. The flow discharged from the top central outlet of the cyclone separator is the overflow portion, and the flow discharged from the bottom solids outlet is the underflow or bottom material portion.

[0044] Catalyst - Catalyst components useful in the context of the present invention can be selected from any catalyst known in the art or as understood by those skilled in the art. Catalysts promote and / or affect reactions. Thus, as used herein, catalysts reduce the activation energy of a chemical process (increase the rate) and / or improve the distribution of products or intermediates in a chemical reaction (e.g., shape selective catalysts). Examples of reactions that can be catalyzed include: dehydration, dehydrogenation, isomerization, hydrogen transfer, hydrogenation, polymerization, cyclization, desulfurization, denitrogenation, deoxygenation, aromatization, decarbonylation, decarboxylation, aldol condensation, and combinations thereof. As understood by those skilled in the art, catalyst components can be considered to be acidic, neutral, or basic.

[0045] For catalytic pyrolysis, particularly advantageous catalysts include catalysts with internal porosity selected according to pore size (e.g., mesopores and pore sizes generally associated with zeolites), for example, average pore size is less than about 10nm, less than about 5nm, less than about 2nm, less than about 1nm, less than about 0.5nm or less. In some embodiments, a catalyst having an average pore size of about 0.5nm to about 10nm can be used. In some embodiments, a catalyst having an average pore size between about 0.55nm to about 0.65nm or between about 0.59nm to about 0.63nm can be used. In some cases, a catalyst having an average pore size between about 0.7nm to about 0.8nm or between about 0.72nm to about 0.78nm can be used.

[0046] 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 understood by those skilled in the art. Optionally, such catalysts can include acid sites. Other types of zeolite catalysts include: ferrierite, Y-type zeolite, beta-type zeolite, mordenite, MCM-22, ZSM-23, ZSM-57, SUZ-4, EU-1, ZSM-11, (S) AlPO-31, SSZ-23, etc. Zeolites and other small pore materials are typically characterized by their constraint index. The constraint index is similar to the ratio of the cracking rate constants of n-hexane and 3-methylpentane. The method for determining the constraint index is described in more detail in U.S. Patent No. 4,029,716, the details of which are incorporated herein by reference.

[0047] The Constraint Index (CI) values ​​for some typical materials are:

[0048] Table 1. Constraint Index of some common zeolites.

[0049]

[0050]

[0051] CI may vary within the range of 1 to 12 shown. Similarly, other variables (such as crystal size or contaminants that may be obscured and the presence of binders that are tightly bound to the crystals) may also affect CI. It should be understood by those skilled in the art that the CI used herein, although providing a very useful means of characterizing the target molecular sieve, is only an approximation, given its determination method, and in some cases, there may be extreme values ​​of composite variables. However, for any given molecular sieve useful herein, the value of CI is in the range of about 1 to 12. In other embodiments, non-zeolite catalysts may be used; for example, WOx / ZrO2, aluminum phosphate, and the like. In some embodiments, the catalyst may include metals and / or metal oxides. Suitable metals and / or oxides include, for example, nickel, palladium, platinum, titanium, vanadium, chromium, manganese, iron, cobalt, zinc, copper, gallium, and / or any oxide thereof. In some cases, a promoter element selected from a rare earth element, i.e., element 57-71, cerium, zirconium, or a combination of their oxides may be added to change the activity or structure of the catalyst. In addition, in some cases, the properties of the catalyst (e.g., pore structure, type and / or number of acidic sites, etc.) may be selected to selectively produce the desired product.

[0052] Catalysts for other processes such as olefin alkylation, aromatization (hydrocarbon reforming), hydrogenation, hydrotreating, deoxygenation, denitrogenation and desulfurization are well known and may be selected for olefin conversion or other processes described herein. Plastic or Polymer - The terms "plastic" and "polymer" are used interchangeably herein. A polymer is a carbon-based (usually at least 50 mass % C) material consisting primarily of repeating units and having a number average molecular weight of at least 100, typically greater than 1000 or greater than 10,000. Polymers include thermoplastic polymers such as polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymers, polyethylene furanoate (PEF), polyamides, polyurethanes, polyethers, polycarbonates, polyoxides, polysulfides, polyarylates, polyetherketones, polyetherimides, polysulfones, polyurethanes, polyvinyl alcohols, and polymers produced by polymerization of monomers (e.g., dienes, olefins, styrenes, acrylates, acrylonitriles, methacrylates, methacrylonitrile, diacids and diols, lactones, diacids and diamines, lactams, vinyl halides, vinyl esters), their block copolymers, and their alloys, thermosetting polymers such as epoxy resins; phenolic resins; melamine resins; alkyd resins; vinyl ester resins; unsaturated polyester resins; cross-linked polyurethanes; polyisocyanurates; cross-linked elastomers, including but not limited to polyisoprene, polybutadiene, styrene-butadiene, styrene-isoprene, ethylene-propylene-diene monomer polymers; and mixtures thereof. Polymer mixtures separated from municipal solid waste or other waste streams are suitable feeds, provided that they contain only small amounts of contaminants such as S, N, O, halogens, minerals, metals or carbon black. Polymers that produce halogenated species upon pyrolysis, such as polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE) and other halogenated polymers, are generally minimized or excluded from feeds used in the present invention. Pyrolysis - The terms "pyrolysis" and "pyrolyzing" have their conventional meanings in the art and are used to refer to the conversion of compounds (e.g., solid hydrocarbon materials) into one or more other substances (e.g., volatile organic compounds, gases and coke) by heating, preferably in the absence of added or present O2. Preferably, the volume fraction of O2 present in the pyrolysis reaction chamber is 0.5% or less. Pyrolysis can be carried out with or without a catalyst. "Catalytic pyrolysis" refers to pyrolysis carried out in the presence of a catalyst and may involve steps described in more detail below. Examples of catalytic cracking processes are summarized in, for example, Huber, GW et al., "Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering," Chem. Rev. 106, (2006), pp. 4044-4098.

[0053] A "classifying cyclone" is a cyclone used to separate solid particles from a gas or vapor stream based on particle size and density. The classifying cyclone works by using centrifugal force to separate a portion of the particles defined by the cut size from the gas stream. When the gas and particles enter the cyclone, the rotational motion creates a vortex that causes the heavier particles to move toward the walls of the cyclone, while the lighter particles remain in the center. The separated particles are discharged from the cyclone through a separate outlet, while the gas or vapor continues to flow through the cyclone with the remaining particles and is discharged through a different outlet.

[0054] A "recovery cyclone" is a cyclone that separates solids from a vapor stream and removes a sufficient portion of the solids to enable the vapor stream to be processed in conventional condensation, distillation or upgrading equipment in a chemical process. A typical recovery cyclone removes sufficient particles so that the concentration of particles in the vapor product discharged from the recovery cyclone is below a target concentration, such as no more than 200, 300, 400 or 500 μg per cubic meter of vapor product.

[0055] Cyclone separation efficiency (sometimes called recovery) is the percentage of the selected cumulative fraction of solids in the stream that goes to any one product. Efficiency E (or overall efficiency) is the difference between the fine product recovery and the crude product recovery and is calculated as follows:

[0056] E=E P -E T =(X P @W P -X T ·W T ) / X F ·W F

[0057] Wherein P represents product, T represents tails (or fines), F represents feed, X represents the mass fraction of particles of a specific size, and W represents the mass of particles of a specific size, as described by Klum par, VI in "Measuring and Optimizing AirClassifier Performance," Sep. Technol., 2, 1992, 124-135.

[0058] A cyclone with low efficiency, where most of the solids entering the cyclone pass through the cyclone and are discharged with the overflow, is called a classifying cyclone. Classifying cyclones can be used to separate materials with different average particle sizes. A cyclone with high efficiency, where only a small fraction of the solids entering the cyclone pass through the cyclone and are discharged with the overflow, is called a recovery cyclone because its purpose is to remove solids from the vapor stream.

[0059] Cut Size - In size separation processes, the term "cut size" (or d50) refers to the size of particle that has an equal probability of entering the overflow or underflow. The value of dX represents the particle size that has an X% probability of being removed with the underflow solids discharged at the bottom of the cyclone separator, rather than being removed with the overflow gas containing entrained solids. The distribution curve represents the mass fraction of each particle size discharged in the crude product (underflow or bottoms material).

[0060] Filler – The term “filler” means any solid substance added to or as part of a polymer composition in an amount up to 20% by weight, such as alumina, aluminum, aluminum fibers, aluminum flakes, aluminum hydroxide, aluminum nitride, antimony-doped tin oxide, antimony oxide, aramid, attapulgite, barium sulfate, barium titanate, bentonite, bismuth carbonate, boron oxide, boron nitride, bronze powder, calcium carbonate, calcium fluoride, calcium phosphate, calcium silicate, calcium sulfate, calcium sulfate whiskers, carbon black, carbon fibers, carbon nanotubes, cellulose nanocrystals, chitosan, clay, compatibilizer, copper, diamond, diatomaceous earth, expanded graphite, ferromagnetic powder, fluorinated mica, fly ash, fumed nanosilica, glass 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, microfiber cellulose, molybdenum sulfide, montmorillonite, Ni-BaTiO3, nickel, phenolic microspheres, potassium titanate whiskers, potassium magnesium aluminum silicate, polytetrafluoroethylene, pyrophyllite, red mud, red phosphorus, rubber particles, sand, sepiolite, silane, silicon dioxide, silicon carbide, silver powder, soot, starch, talc, tetrapod-shaped zinc oxide whiskers, titanium dioxide nanoparticles, titanium dioxide, vermiculite, wollastonite, wood fiber, wood flour, zinc borate, zinc oxide, zirconium silicate, or any combination thereof.

[0061] 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, droplets and / or gas bubbles. The terms "gas" and "vapor" have the same meaning and are sometimes used interchangeably. In some embodiments, it may be advantageous to control the residence time of the fluidizing fluid in the reactor. The fluidization residence time of the fluidizing fluid is defined as the volume of the reactor divided by the volume flow rate of the fluidizing fluid at the process conditions of temperature and pressure.

[0062] Fluidized bed reactor - The term "fluidized bed reactor" has its conventional meaning in the art and is used to refer to a reactor that includes a container that can hold particulate solid material (e.g., silica particles, catalyst particles, etc.), wherein a fluid (e.g., a gas or liquid) is passed through the particulate solid material at a sufficiently high velocity to suspend the solid material and cause it to behave like a fluid. Examples of fluidized bed reactors are described in D. Kunii and O. Levenspiel, Butterworth-Heinemann, "Fluidization Engineering", 1991, which is incorporated herein by reference. The term "circulating fluidized bed reactor" also has its conventional meaning in the art and is used to refer to a fluidized bed reactor in which particulate solid material is discharged from the reactor, circulated through a pipeline connected to the reactor fluid, and recycled back into the reactor. Examples of circulating fluidized bed reactors are described in D. Kunii and O. Levenspiel, Butterworth-Heinemann, "Fluidization Engineering", 1991.

[0063] Bubbling fluidized bed reactor and turbulent fluidized bed reactor are also well known to those skilled in the art. In a bubbling fluidized bed reactor, the fluid stream for fluidizing the granular solid material is operated with a sufficiently low flow rate so that bubbles and spaces can be observed in the fluidized bed volume during operation. In a turbulent fluidized bed reactor, the flow rate of the fluidizing stream is higher than the flow rate in the bubbling fluidized bed reactor, so bubbles and spaces will not be observed in the fluidized bed volume during operation. The example of bubbling and turbulent fluidized bed reactors is described in Kirk-Othmer Encyclopedia of Chemical Technology (online version), Vol. 11, Hoboken, Hoboken, NJ: Wiley-Interscience, 2001, pp. 791-825, which is incorporated herein by reference.

[0064] Olefins - The term "olefin" or "olefin compound" (also known as "alkene") has its ordinary meaning in the art and is used to refer to any unsaturated hydrocarbon containing one or more pairs of carbon atoms connected by double bonds. Olefins include cyclic olefins and non-cyclic (aliphatic) olefins, wherein the double bonds are located between carbon atoms that form part of a cyclic (closed ring) or open chain group, respectively. In addition, olefins can include any suitable number of double bonds (e.g., monoolefins, diolefins, triolefins, etc.). Examples of olefin compounds include, but are not limited to, ethylene, propylene, propadiene, 1-butene, 2-butene, isobutylene (2-methylpropylene), butadiene, and isoprene, etc. Examples of cyclic olefins include cyclopentene, cyclohexene, cycloheptene, etc. Aromatic compounds such as toluene are not considered olefins; however, olefins containing aromatic moieties are considered olefins, such as benzyl acrylate or styrene.

[0065] As used herein, "thermal treatment" is the process of heating the feed mixture to a moderate temperature at which some contaminants (e.g., HCl, H2S, NH3) are evolved and discharged, and the feed mixture is melted so that solids (e.g., minerals, metals, and carbon black) can be removed by filtration.

[0066] Following standard patent terminology, the word "comprising" means "including" and does not exclude additional components. Any inventive aspect described with the term "comprising" also includes narrower embodiments in which the term "comprising" is replaced by the narrower term "consisting essentially of" or "consisting of." As used in this specification, the terms "includes" or "including" should not be construed as limiting the invention, but rather listing exemplary components. DETAILED DESCRIPTION

[0067] Figure 1A schematic process flow diagram for converting waste plastics into olefins and aromatics is shown. A plastic mixture 10 is introduced into an optional feed system 100, which prepares the plastic mixture for introduction into the process by, for example, removing unwanted feed 102 (e.g., metals, minerals, clays, halides, contaminants (e.g., Cl, Br, or other elements that may poison the catalyst, etc.) or sizing the material to a desired size range, or both. The steps of removing unwanted feed and sizing can be performed in any order, i.e., either step can be performed before the other. The remaining plastic mixture 101 can be conveyed to an optional cleaning process 110, where the plastic mixture can be cleaned, for example by treating with a cleaning solution 112 to remove unwanted materials, such as dirt, labels, coatings, etc., to produce a cleaned plastic mixture 111 and a used solution 113. The plastic mixture 111 is conveyed to an optional pyrolysis reactor 120. Optionally, a vapor phase co-reactant or recycle stream (not shown) comprising H2, CO or olefins or some combination of these substances can be fed directly to the optional pyrolysis reactor 120 or catalytic pyrolysis reactor 140. In the optional pyrolysis reactor 120, the mixture can be heated to a temperature to decompose the plastic into a product mixture comprising a combination of vapor, solid and liquid phases. At least a portion of the crude pyrolysis product mixture 121 is sent to the catalytic reactor 140 without separation, while the temperature of the pyrolysis product mixture is maintained at least at the temperature at which it leaves the pyrolysis reactor 120. The plastic mixture (raw plastic mixture 101, or washed plastic mixture 111, or pyrolysis product mixture 121) is sent to the hot catalytic reactor 140, which is charged with an aromatization catalyst that is effective to convert paraffins or olefins or both to aromatics, as shown by the catalytic vapor stream 141. A portion of the catalyst 142 is continuously removed from the reactor 140, or can be separated from the product 141, or both, and sent to the catalyst regenerator 150. In the catalyst regenerator 150, the catalyst is oxidized by treatment with an oxygen source (e.g., air 151), the hot regenerated catalyst 143 is returned to the reactor 140 to provide heat for the reactor, and the combustion product gas 152 is sent to the regenerator flue gas cleaning cyclone separator (not shown), or is discharged, or used to provide heat for the optional one or more pyrolysis reactors or one or more catalytic pyrolysis reactors. The catalytic vapor stream 141 is sent to the solid separation system 160, where the catalyst 162 is separated from the filler 163 and the catalytic product stream 161. The catalyst 162 can be returned to the reactor 140, or sent to the catalyst regenerator 150, or discarded. The filler 163 can be sent to the filler regenerator (not shown), or discarded.The catalytic product stream 161 can be separated into ethylene, propylene, butene, C1-C5 paraffins, benzene, toluene, xylene, naphthalene and other components according to a separation scheme using conventional separation techniques not shown herein.

[0068] Figure 2A schematic diagram of another embodiment of the process of the present invention for converting waste plastics into olefins and aromatics is shown. A plastic mixture 10 is introduced into an optional feed system 100, which prepares the plastic mixture for introduction into the process by, for example, removing unwanted feed 102 (e.g., metals, minerals, clays, halides, contaminants (e.g., Cl, Br, or other elements that may poison the catalyst, etc.) or sizing the material to a desired size range, or both. The steps of removing unwanted feed and sizing can be performed in any order, i.e., either step can be performed before the other. The remaining plastic mixture 101 is conveyed to an optional cleaning process 110, where the plastic mixture can be cleaned, for example by treating with a cleaning solution 112 to remove unwanted materials, such as dirt, labels, coatings, etc., to produce a cleaned plastic mixture 111 and a used solution 113. The prepared plastic mixture 111 is conveyed to a thermal treatment reactor 115 along with an optional co-reactant 122 (e.g., a heat transfer medium or a getter, etc.) where the mixture is heated to an intermediate temperature to partially decompose the plastic, such as decomposing PVC or PVDC to release HCl, or decomposing another halogenated polymer to release HCl, HBr or HI, or to release vapors such as NH3, H2O, etc. An optional purge gas 124 such as H2O, N2, Ar, CO2, or some combination thereof is fed into the thermal treatment reactor 115 to help remove vapors generated therein, which are exhausted through outlet 125. With or without the purge gas, the vapor 125 can be treated to capture or neutralize HCl and toxic substances before release or transfer to water treatment. The vapor 125 typically contains at least 60% or at least 80% H2O, and may contain HCl, halogenated carbon compounds, and other substances that are more volatile than the molten polymer. The condensed phase 126 may be conveyed to an optional pyrolysis reactor 120 where they are heated to decompose into a product mixture comprising a combination of solid, liquid and gas phases. When the optional pyrolysis reactor is used, the temperature of the pyrolysis product mixture is maintained at least at the temperature at which it leaves the pyrolysis reactor 120. When the optional pyrolysis reactor 120 is used, the plastic feed mixture or raw product mixture 121 is conveyed to a hot catalytic reactor 140 containing an aromatization catalyst effective to convert paraffins or olefins or both into aromatics, as shown by the catalytic vapor stream 141. A portion of the catalyst 142 may be continuously withdrawn from the reactor 140, or may be separated from the product 141, or both, and at least a portion thereof is conveyed to a catalyst regenerator 150. In the catalyst regenerator 150, the catalyst is oxidized by treatment with an oxygen source (e.g., air 151), and the regenerated catalyst 143 is returned to the reactor 140, while the combustion product gas 152 is conveyed to a regenerator cyclone separator (not shown), or is exhausted.Optionally, natural gas or a recycle stream can be sent to a catalyst regenerator 150 to raise the temperature of the regenerated catalyst to the temperature required for the catalytic pyrolysis process. The catalytic vapor stream 141 is sent to a solid separation system 160, where a catalyst 162 is separated from a filler 163 and a catalytic product stream 161. At least a portion of the catalyst 162 can be returned to the reactor 140, or can be sent to a catalyst regenerator 150, or can be discarded. The filler 163 can be sent to a filler regenerator (not shown), where the filler is oxidized by air or oxygen to generate heat that can be used for the process, or can be discarded. The catalytic product 141 can be separated into ethylene, propylene, butene, C1-C5 paraffins, benzene, toluene, xylene, naphthalene and other components according to a separation scheme using conventional separation techniques.

[0069] Figure 3 A schematic diagram of the solids separation system 160 is shown in more detail. A catalytic vapor stream 141 containing entrained catalyst and filler is sent to one or more classifying (low efficiency) cyclone separators 170, where catalyst 162 containing a small amount of filler particles is separated and sent to catalyst regeneration 150, or to the catalytic pyrolysis reactor 140, or is discarded, or some combination of these. The vapor stream 171 discharged from the classifier 170 has most of the filler entrained and contains almost no catalyst except for some fine particles. The vapor stream 171 is sent to a series (N units) of high efficiency multi-cyclone separators 180, where filler 182 is separated and optionally sent to a filler regenerator 190, where it is burned with air to provide heat for the process, or is discarded. The regenerated filler 191 is discarded. The product stream 181, from which most of the filler has been removed, is sent for separation and product collection; it contains solids at a concentration that does not exceed the allowable limit for entrained particles discharged to the atmosphere.

[0070] The solid separation system of the present invention provides a method for separating filler from 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 containing catalyst particles and filler from catalytic pyrolysis passes through a first cyclone separator to separate a first bottom material portion and a first overflow portion. The mass ratio of catalyst to filler in the bottom material portion of the first cyclone separator is greater than the mass ratio of catalyst to filler in the effluent of the catalytic pyrolysis reactor, that is, it is rich in catalyst. The overflow portion of the first cyclone separator is conveyed to a second cyclone separator to separate the second bottom material portion and the second overflow portion, and the separation efficiency of the second cyclone separator for catalyst particles is greater than the first separation efficiency. The mass ratio of catalyst to filler in the bottom material portion of the second cyclone separator is less than the mass ratio of catalyst to filler in the effluent of the catalytic pyrolysis reactor, that is, it is rich in filler. It can be recognized that the first cyclone separator may include more than one cyclone separator, and the second cyclone separator may include more than one cyclone separator.

[0071] The exhaust gas from the catalyst regenerator or the packing regenerator can be passed through one or more cyclone separators to remove particulate matter therein. Optionally, when the exhaust gas from the catalyst regenerator contains catalyst particles that need to be recovered, the exhaust gas from the catalyst regenerator can be passed through a series of cyclone separators, including a classification cyclone separator and one or more purification cyclone separators. The catalyst particles recovered from the classification cyclone separator can be returned to the catalytic pyrolysis reactor. Smaller particles recovered from the purification stage can be discarded.

[0072] Combustible gases (e.g., methane, ethane, propane, butane, CO, and H2) may optionally be recovered from vapor stream 125, or from gases produced by catalytic pyrolysis in a fluidized bed reactor, or from product stream 141. Combustible gases may provide heat for the process. The heat required for the catalytic pyrolysis process reactor 140 or the optional pyrolysis reactor 120 or both may be provided at least in part by hot regenerated catalyst 143. Heat in reactors 115 or 120 may also be provided by pressure / friction and / or other heat sources (e.g., resistive heating or induction heating).

[0073] In some embodiments, such as when recycled polymeric material is used, impurities may be optionally removed from the feed composition prior to feeding the feed composition to the reactor, such as by an optional separation step, such as Figure 1 or Figure 2 100 in. In some cases, the separation step may include mechanical separation, sink-float separation, air elutriation or other known separation processes, preferably in an automated mode. Before the solid polymer feed composition is conveyed to the thermal treatment reactor or the pyrolysis reactor, its particle size may be reduced in a particle size reduction system as part of 100. In some embodiments, the average diameter of the feed composition with reduced particle size discharged from the particle size reduction system may account for no more than 50%, no more than 25%, no more than 10%, no more than 5% or no more than 2% of the mass average diameter of the feed composition fed to the particle size reduction system. The feed mixture may contain a plastic mixture in which at least 85% by mass, or at least 90% by mass, or at least 95% by mass 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 inches (5.0 cm), or 4 inches (10.0 cm) sieve. The average diameter (size) may be determined by screening with a mesh (sieve). Large particle feeds may be easier to transport and less difficult to process than small particle feeds. On the other hand, in some cases it may be more advantageous to feed small particles into the reactor. The use of a particle size reduction system allows large particle feeds to be transported between the source and the process while enabling small particles to be fed into the reactor.

[0074] The feed suitable for the present invention can include all types of polymer materials, including polyethylene (PE), polypropylene (PP), polyacetylene, polybutene, polyolefins, polyethylene terephthalate (PET), polybutylene terephthalate, polyesters, copolyesters, polycarbonates, polyurethanes, polyamides, polystyrene (PS), polyacetals, epoxies, polycyanurates, polyacrylic acids, polyureas, vinyl esters, polyacrylonitrile, polyamides, polyurethanes, polyethers, polycarbonates, poly(oxides), poly(sulfides), polyarylates, polyetherketones, polyetherimides, polysulfones, polyurethanes, polyvinyl alcohol, polyvinyl chloride (PVC), polyvinyl dichloride (PVDC), polyvinyl acetate, nylon, copolymers such as ethylene-propylene and acrylonitrile-butadiene-styrene (ABS), nitrile rubber, natural and synthetic rubbers, tires, styrene-butadiene, styrene-acrylonitrile, styrene-isoprene, styrene-maleic anhydride, ethylene-vinyl acetate vinyl esters, nylon 12 / 6 / 66, filled polymers, polymer composites, plastic alloys, other polymer materials, and polymers or plastics dissolved in solvents, whether waste or discarded materials obtained from polymer or plastic manufacturing processes, post-consumer recycled polymer materials, materials separated from waste streams such as municipal solid waste, and polymers produced by polymerization of monomers (e.g., dienes, olefins, styrenes, acrylates, acrylonitriles, methacrylates, methacrylonitrile, diacids and diols, lactones, diacids and diamines, lactams, vinyl esters), their block copolymers, and their alloys; thermosetting polymers, such as epoxy resins; phenolic resins; melamine resins; alkyd resins; vinyl ester resins; unsaturated polyester resins; cross-linked polyurethanes; polyisocyanurates; cross-linked elastomers, including but not limited to polyisoprene, polybutadiene, styrene-butadiene, styrene-isoprene, or some combination of these elastomers. The present invention includes subcombinations of these materials (as needed or available from a particular location); the present invention may be described as including one or any combination of these materials.

[0075] In any method, the heat treatment reactor 115 or the pyrolysis reactor 120 or a plurality of reactors therein may be a moving bed reactor, wherein the feed is pushed along the length of the reactor by mechanical means, gravity means, or both mechanical and gravity means. Typical examples of reactors suitable for the heat treatment reactor 115 or the pyrolysis reactor 120 include a 1-screw extruder, a 2-screw extruder, a screw reactor, a static mixer reactor, a rotary kiln reactor, or a stepped grate reactor. In any embodiment, the pyrolysis reactor may have multiple heating zones, and the temperature of the latter zones increases successively. In some embodiments, the heat treatment reactor or the pyrolysis reactor is equipped with a gas outlet in a region where the temperature of the material in the reactor is less than 300°C or between 250°C and 300°C to allow removal of products produced at low temperatures, such as steam, HCl, NH3 or other materials, from the reactor. A separation net may be installed immediately downstream of the gas outlet in the pyrolysis reactor to at least partially prevent the gases released at low temperatures from entering the hotter part of the reactor together with the molten material and the solid material. A gas inlet may be installed immediately downstream of the exhaust port and optional screen for introducing hot inert gas or recycle gas, such as a gas containing any one of CH4, H2, CO, CO2 and C2-C4 paraffins or olefins or a mixture thereof.

[0076] Optionally, a solid co-reactant 122 (eg, CaO, MgO, hydrotalcite, activated carbon, or zeolite, or some combination of these) that captures or removes undesirable components may be fed into the thermal treatment reactor 115 and separated therefrom by mesh filtration.

[0077] When spiral reactors are used for thermal treatment or pyrolysis, these spiral reactors may include augers that optionally have different pitch sizes at different parts of the augers to adjust the speed of the condensed phase from the reactor inlet to the outlet. In order to control the flow rate of the vapor and condensed phase, the spiral sheet thickness and shaft diameter may also vary along the length of the augers. Augers with paddles, cutouts or folded spiral sheets are also considered to be within the scope of the present invention.

[0078] A rotary kiln reactor can be used for heat treatment or pyrolysis, and the kiln barrel can be equipped with a lifter, such as a spiral lifter attached to the barrel wall or a plate-shaped lifter, a folding lifter or a segmented lifter extending from the barrel wall. The rotary kiln reactor can also be tilted upward or downward toward the outlet end of the kiln, depending on the required residence time and flow rate of the condensed phase in the kiln, so that gravity can be used to control the residence time of the condensed phase. The rotation rate of the rotary kiln reactor can be adjusted as required, for example, between 20 revolutions per minute and 0.2 revolutions per minute, depending on the properties of the feed mixture and the added co-reactants, to provide sufficient mixing and high heat transfer. The rotary kiln reactor can be heated externally by burning process waste gases such as CH4, C2-C4 paraffins, H2, CO, etc. recovered from product separation, or natural gas, or by electricity.

[0079] In any aspect of the invention, the temperature profile within the optional pyrolysis reactor may range from a lower temperature near the feed inlet to a higher temperature at one or more outlets. At or near the inlet, the temperature range may be 20°C to 225°C, such as 20 to 100°C, or 20 to 50°C, and the temperature range at the high temperature outlet may be 300°C to 700°C, such as 325 to 650°C, or 350 to 600°C. The solid co-reactant may be fed into the thermal treatment reactor, and the solid co-reactant material may optionally be transferred to a combustion regenerator, in which the carbonaceous material reacts with air, and at least a portion of the hot solid co-reactant material is returned to the thermal treatment reactor. The hot flue gas exhausted from the solid co-reactant material regenerator is conveyed to a catalyst heater to heat the catalyst for the catalytic pyrolysis reactor.

[0080] After exiting the thermal treatment reactor 115, the crude product preferably does not contact any cold surfaces that could cause the product to condense, and the surfaces are preferably maintained at a temperature of at least 300°C, at least 325°C, or at least 350°C, or within 25°C or 50°C of the temperature exiting the reactor 115. Preferably, in either embodiment, the temperature of the mixture is maintained at a temperature that is 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 outlet end of the thermal treatment reactor.

[0081] In any aspect of the present invention, the catalytic reactor 140 can be a fluidized bed reactor; wherein the catalyst is a solid catalyst, and the catalytic pyrolysis step includes pyrolysis in the presence of the solid catalyst in the fluidized bed reactor to produce a fluid product stream 141 and a spent catalyst 142 containing coke; and wherein at least a portion of the spent catalyst containing coke is transferred to a regenerator 150, wherein the coke reacts with oxygen or air to form a hot regenerated catalyst, and at least a portion 143 of the hot regenerated catalyst is returned to the fluidized bed reactor, wherein heat from the hot regenerated catalyst provides energy for the catalytic pyrolysis step.

[0082] The vapors exhausted from the catalytic pyrolysis reactor are passed through a solid separation system comprising a series of cyclones to separate the entrained solids into a larger particle size fraction and a smaller particle size fraction. In either method, the solid separation system comprises a series of one or more cyclones and one or more multi-cyclones. The first cyclone in the series is typically a relatively low efficiency classifying cyclone that provides a rough separation of smaller and larger particles.

[0083] Cyclone separators are typically designed and installed to separate solids from a gas stream as efficiently as possible, for example to remove dust from flue gas. The overall separation efficiency of a cyclone separator is defined as the ratio of the solid mass flow rate at the bottom of the cyclone to the solid mass flow rate at the cyclone inlet, with an efficiency of 1 meaning no solids are discharged with the gas at the top of the cyclone, an efficiency of 0.99 meaning 0.01% of solids are discharged with the gas at the top of the cyclone, and so on. Thus, for a bimodal solids flow entering a cyclone separator, the solid mass flow rate is m 总 The mass fractions of particles with smaller diameters and particles with larger diameters are x 小 and x 大 Typical cyclone design criteria set the goal at the maximum possible efficiency, that is, the solids flow rate discharged from the bottom of the cyclone should be as close as possible to (x 小 +x 大 )·m 总 In the proposed application, the target solids flow rate discharged from the bottom of the cyclone separator is (x 大 )·m in , which allows (x 小 )·m 总 The solids flow rate is discharged from the top of the cyclone, effectively designing the cyclone to reduce the efficiency of classifying the particles. Specifically, the target efficiency will always be lower than the amount equivalent to the mass fraction of smaller diameter particles in the solid feed (typical cyclone design The target efficiency in this application is ). Therefore, the term "inefficient" is used to describe the first stage cyclone separator. Figure 5 For product vapor solid separation system or regenerator flue gas solid separation system or both, in the classifying cyclone separator, the vortex diameter (D e ) to the cylinder diameter (D) may be 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 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) can be 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or in the range of 0.3 to 0.95, or 0.5 to 0.95, or 0.8 to 0.95, or 0.85 to 0.95. The ratio of the underflow diameter (B) to the vortex diameter (D e ) ratio can be 0.02, or 0.1, or 0.15, or 0.2, or 0.25, or 0.3, or 0.5, or 1.0, or 1.25, or in the range of 0.2 to 1.25, or 0.02 to 0.5, or 0.1 to 0.3, or 0.15 to 0.25. The ratio of inlet height to inlet width can be 0.75, 1, or 1.5, or 2, or 2.4, or 3, or 4, or 5, or can be in the range of 0.75 to 5, or 1.5 to 4, or 2 to 3, or 2.2 to 2.6. The ratio of vortex length (S) to total height (H) may be 0.1, or 0.2, or 0.3, or 0.36, or 0.4, or 0.5, or 0.6, or 0.8, or in the range of 0.1 to 0.8, or 0.2 to 0.6, or 0.3 to 0.4, or 0.34 to 0.38. The gas velocity at the inlet of the low efficiency cyclone separator is greater than 5, or greater than 10, or greater than 15, or 5 to 40, or 10 to 30, or 15 to 25 m / s.

[0084] Optionally, volatile materials may be removed from the catalyst particles by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or some combination of these gases, or a recycle stream from the product gas through the catalyst removed from the catalytic reactor or the catalyst recovered in the solid separation system, or both. The resulting vapor stream containing steam and organic material may be condensed, the organic phase and the aqueous phase separated, the liquid organic phase may be sent to product recovery, and the aqueous phase may be sent to waste water recovery. The catalyst after removal of volatile organic compounds may be sent to a catalyst regenerator, or returned to the catalytic reactor, or discarded, or some combination of the above.

[0085] The later stages of separation involve multi-cyclones. Multi-cyclones (multiclones / multicyclones) consist of multiple small diameter tubes connected in parallel, each of which acts like a small cyclone. This configuration combines the high efficiency of a small diameter with the ability to handle large volumes of gas. In each small diameter tube, the gas velocity is higher than in the larger diameter tube, so the separation efficiency is higher. Multi-cyclones typically produce a greater pressure drop than a single cyclone of equivalent capacity. Figure 6 A multi-cyclone separator that can be used in the process of the present invention is shown. (https: / / www.babcock.com / home / products / multiclone-dust-collectors / )Schematic diagram of a. Multi-cyclone reactors are widely used to reduce emission levels from many biomass boilers, cement kilns and lime kilns. They work by keeping downstream equipment such as splitters, fans, scrubbers and precipitators operating reliably with minimal energy input. They operate as a series of multiple high-efficiency cyclones that work in parallel using common inlet and outlet chambers. The process vapor stream enters the inlet chamber and is distributed to a number of small, high-efficiency, small-diameter cyclones that accommodate cyclone generators. The different heights of the multiple smaller cyclones are designed to provide the same pressure drop and the same flow rate. The particulate matter is released into a common solids outlet chamber, while the vapor is discharged from the unit. These cyclones separate the majority of particles from the gas stream as it flows through the system and can be used for particles as small as 5 microns in diameter.

[0086] refer to Figure 5 For each of the multiple small diameter cyclones in the multi-cyclone separator, the vortex diameter (D e ) to the cylinder diameter (D) may be 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 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 ) can be 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or in the range of 0.3 to 0.95, or 0.5 to 0.95, or 0.8 to 0.95, or 0.85 to 0.95. The ratio of the underflow diameter (B) to the vortex diameter (D e ) can be 0.02, or 0.1, or 0.15, or 0.2, or 0.25, or 0.3, or 0.5, or 1.0, or 1.25, or in the range of 0.02 to 1.25, or 0.02 to 0.5, or 0.1 to 0.3, or 0.15 to 0.25. The ratio of vortex length (S) to total height (H) can be 0.1, or 0.2, or 0.3, or 0.36, or 0.4, or 0.5, or 0.6, or 0.8, or in the range of 0.1 to 0.8, or 0.2 to 0.6, or 0.3 to 0.4, or 0.34 to 0.38. The number of small cyclone separators in any one multi-cyclone separator can be 4, 9, 16, 25, 36, 49 or 64, or 4 to 64, or 9 to 49, or 16 to 36 cyclone separators. The gas velocity at the inlet of the recovery cyclone separator can be no more than 25, or no more than 20, or no more than 15, or 3 to 20, or 5 to 15, or 6 to 12 m / s.

[0087] In the separation of catalyst and filler, at least a portion of the separated larger particle size entrained solids can be sent to a catalyst regenerator, or at least a portion can be returned to the catalytic pyrolysis reactor, or discarded, or some combination of these methods. The separated smaller particle solids can be sent to a separate regenerator or solid waste treatment device. The product vapor stream from which solids have been removed contains no more than 150, or 300 or 500 mg of solids per cubic meter of product vapor.

[0088] Optionally, volatile substances in these smaller solid particles can be removed by passing a stream of steam, nitrogen, CO, CO2, CH4, He or some combination of these gases or a recycle stream from the product gas through smaller solid particles recovered in a solid separation system. The resulting vapor stream containing steam and organic materials can be condensed, the liquid organic phase can be sent to product recovery, and the aqueous phase can be sent to wastewater recovery. The solid particles from which volatile organic compounds have been removed can be sent to a packing regenerator, or discarded, or a combination of the two. In any 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, a circulating bed, a bubbling bed, a turbulent bed or a riser reactor, and its operating temperature range is 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 steam 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 of the catalytic pyrolysis reactor can be at least 0.1MPa (1 bar), or at least 0.3Mpa (3 bar), or at least 0.4Mpa (4 bar), or 0.1 to 2.0Mpa (1 to 20 bar), or 0.1 to 1.0Mpa (1 to 10 bar), or 0.3 to 0.8Mpa (3 to 8 bar), preferably 0.4 to 0.6Mpa (4 to 6 bar), and the pressure is absolute pressure.

[0089] The design and conditions of the fluidized bed catalytic reactor may be those known in the art. Fluidizing gas may be required at startup; during steady-state operation, circulating gas from the process may be used as a component of the fluidizing gas. The fluidizing gas may include H2, CO, CO2, H2O, C1-C4 paraffins or olefins or both, N2, Ar, He or a recycle stream, or some combination thereof.

[0090] For catalytic pyrolysis, useful catalysts include catalysts with internal porosity selected according to pore size (e.g., mesopores and pore sizes generally associated with zeolites), for example, average pore size is less than 10nm, less than 5nm, less than 2nm, less than 1nm, less than 0.5nm or less. In some embodiments, a catalyst having an average pore size of 0.5 to 10nm can be used. In some embodiments, a catalyst having an average pore size between 0.5 to 0.65nm or between 0.59 to 0.63nm can be used. In some cases, a catalyst having an average pore size between 0.7 to 0.8nm or between 0.72 to 0.78nm can be used.

[0091] Particularly advantageous catalyst compositions in the catalytic pyrolysis fluidized bed reactor of the present invention include crystalline molecular sieves, characterized in that SAR (silicon dioxide / alumina ratio, SiO2: Al2O3 mass ratio) is greater than 12, or 12 to 240, and CI (constraint index) is 1 to 12. Non-limiting examples of these crystalline molecular sieves are molecular sieves with the following structures: ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50 or a combination thereof. As an embodiment, the catalyst composition comprises a crystalline molecular sieve, characterized in that SAR is greater than 12 to 240 and CI is 5 to 10, for example, a molecular sieve or a combination thereof with a ZSM-5, ZSM-11, ZSM-22, ZSM-23 structure. The method for determining CI is described in more detail in U.S. Patent No. 4,029,716, the details of which are incorporated herein by reference.

[0092] The molecular sieve used herein or the catalyst composition containing the molecular sieve can be heat treated at high temperature. Such heat treatment is usually carried out by heating at a temperature of at least 370°C for at least 1 minute and usually not more than 20 hours (usually in an oxygen-containing atmosphere, preferably in air). Although subatmospheric pressure can be used for heat treatment, atmospheric pressure is preferably used for convenience. The heat treatment can be carried out at a temperature of up to about 925°C. The heat-treated product is particularly useful in this process.

[0093] For the catalyst composition for the present invention, suitable molecular sieves can be used in combination with carriers or binder materials (e.g., porous inorganic oxide carriers or clay binders). Non-limiting examples of such binder materials include aluminum oxide, zirconium oxide, silicon dioxide, magnesium oxide, thorium oxide, titanium dioxide, boron oxide, and combinations thereof, typically in the form of dry inorganic oxide gels and colloidal precipitates. Suitable clay materials include, for example, bentonite, diatomaceous earth, and combinations thereof. The relative proportion of suitable crystalline molecular sieves in the entire catalyst composition may vary greatly, with the molecular sieve content ranging from 30 to 90% of the composition weight, typically in the range of 40 to 70% of the composition weight. The catalyst composition can be in the form of extrudates, beads, or fluidizable microspheres.

[0094] The molecular sieve or the catalyst composition comprising it can be at least partially ion exchanged with hydrogen, or hydrogen precursor cations, or non-noble metal ions of Group VIII of the Periodic Table (i.e., nickel, iron or cobalt, or zinc, or gallium, or combinations thereof) to replace the original cations according to techniques well known in the art.

[0095] In the regeneration of the catalyst from catalytic pyrolysis, the coke, char and other materials are oxidized in the catalyst regenerator to generate heat for use in the process or for conversion to electrical output. In one embodiment, the oxidant is supplied by Figure 1 Stream 151 shown is fed into a regenerator. The oxidant may come from any source, including, for example, an oxygen tank, atmosphere, steam, etc. In the regenerator, the catalyst reacts with the oxidant and generates heat, thereby reactivating the catalyst. The solid mixture comprising the deactivated catalyst may contain residual carbon and / or coke and coke or char from the process, which can be removed by reacting with the oxidant in the regenerator. A portion of the gaseous products produced during the catalytic pyrolysis process can be fed into a catalyst regenerator and burned with solid matter. The gaseous products can first be separated into an olefin-rich stream and an olefin-depleted stream, and at least a portion of the olefin-depleted stream can be fed into a catalyst regenerator. Figure 1 The regenerator in includes an exhaust gas stream 152, which may include regeneration reaction products, residual oxidant, etc.

[0096] In either process, the vapors exhausted from the catalyst regenerator are passed through a solids separation system comprising a series of cyclones to separate the entrained solids into a larger particle size fraction and a smaller particle size fraction. The separated larger particle size entrained solids may be conveyed to a catalytic pyrolysis reactor, or discarded, or a combination of both. The separated smaller particle solids may be conveyed to a separate regenerator or solid waste treatment facility. The solids content of the flue gas (solids removed) from the catalyst regenerator shall not exceed 12, or 35, or 50 or 150 μg per cubic meter of product vapor, which is an average value over a 24-hour period or a year.

[0097] Regenerator separation system.

[0098] The combustion product gases (flue gases) produced in the catalyst regenerator or the packing regenerator or both may be passed to a solids separation system similar to that described for the product vapor stream, either to separate multiple solids separation systems or the flue gases from the catalyst regenerator and the packing regenerator may be combined and passed to a common solids separation system. The solids separation system for removing particulate matter from the flue gas stream may include a series of cyclone separators, optionally with a classifying cyclone separator, followed by one or more high efficiency multi-cyclone separators. The flue gas from the catalyst regenerator (with solids removed) shall not contain more than 12, or 35, or 50 or 150 μg of solids per cubic meter of product vapor, averaged over a 24 hour period or over a year.

[0099] refer to Figure 5 For the flue gas solid separation system, the sizes of the classifying cyclone separator (optional) and the recovery cyclone separator (multi-cyclone separator) can follow the same length ratio as the above-mentioned product vapor purification solid separation system, although the absolute sizes of the cyclone separators may be different. The gas flow rate at the inlet of the optional low-efficiency classifying cyclone separator 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. The gas flow rate at the inlet of the high-efficiency recovery cyclone separator is no more than 25, or no more than 20, or no more than 15, or 7 to 20, or 5 to 15, or 6 to 12 meters per second.

[0100] In the process of the present invention, at least a portion of solid material 123 can be removed from thermal treatment reactor 115 and can be recycled into the feed of thermal treatment reactor 115 as part of optional co-reactant 122. Optional co-reactant 122 can include solid materials that react with sulfur or nitrogen compounds to capture sulfur or nitrogen species in a solid phase. The solid materials in optional co-reactant 122 can include one or more materials selected from: agricultural lime, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, limestone, or hydrotalcite, activated carbon, or zeolite, or some combination thereof.

[0101] Multiple plastic upgrading units can be connected to feed a single product separation and purification facility in a hub-and-spoke system. The system for waste plastic upgrading includes an optional first pyrolysis reactor and a catalytic fluidized bed reactor, which together form a spoke of a "hub-and-spoke" network for the production of refined chemical intermediates such as benzene, toluene, xylene, p-xylene, m-xylene, o-xylene, BTX (a mixture of benzene, toluene and xylene), C6-C 20Alkanes and olefins, ethylene, propylene, naphthalene or other substances, or some combination of these, wherein each of the multiple plastic upgrading stations (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 in the network that feeds 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 to 20, or 3 to 10, or 5 to 10 plastic upgrading facilities. The total crude product mixture prepared in the plastic upgrading facilities and 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 to 500, or 30 to 200, or 50 to 150 metric tons of crude product mixture per day.

[0102] The present invention also includes a system for upgrading plastics, wherein the plastics are first pyrolyzed in pyrolysis reactors, each of which may include a "spoke" in a "hub and spoke" network for producing refined chemical intermediates such as benzene, toluene, xylene, p-xylene, m-xylene, o-xylene, BTX (a mixture of benzene, toluene and xylene), C6-C 20 paraffins and olefins, ethylene, propylene, naphthalene or other substances, or some combination of these, wherein each of the multiple plastics upgrading stations (spokes) produces a condensed phase product that is sent to a central fluidized bed catalytic process unit (Plas TCat TM ) to separate and purify into product streams. In some embodiments of the system, the number of plastic pyrolysis facilities 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 plastic pyrolysis facilities. The total crude product mixture prepared in the plastic pyrolysis facilities and introduced into the central catalytic upgrading, 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 to 500, or 30 to 200, or 50 to 150 metric tons of crude product mixture per day.

[0103] Example

[0104] Example 1

[0105] The number of cyclones required to separate and remove fillers from the product effluent of a catalytic reactor in a system processing 500 tons per day of mixed plastics containing 5 wt. % fillers to produce useful products was calculated. It was assumed that about 95% of the mass of the fillers came from particles with a size less than 20 microns, while about 95% of the mass of the catalyst came from particles with a size greater than 65 microns. Figure 4The particle size distribution of the filler, catalyst and the sum of filler and catalyst in the feed ("cyclone inflow") is shown. It is assumed that the plastic mixture is catalytically pyrolyzed in a fluidized bed catalytic reactor, producing a product vapor flow of 5.2 kg / s, in which the entrained solids include 1.2 kg / s of catalyst particles and 0.29 kg / s of filler particles. It is assumed that 10% of the feed mixture will produce coke deposited on the catalyst and materials adsorbed in the catalyst pores, and the catalyst is sent for catalyst regeneration. The density of the catalyst particles is assumed to be 1300 kg / m 3 , assuming the density of the filler particles is 2700kg / m 3 The gas density of the steam flow at 500°C is 1.65kg / m3.

[0106] The solids separation system designed for separation and removal of solids consists of 28 cyclones: a classifier (low efficiency cyclone) and three stages of purification multi-cyclones, each stage containing 9 internal cyclones. Table 3 summarizes the design of the solids separation system for separation and removal of solids. Figure 5 and Figure 6 The size and performance of the cyclone separators with the parameters in Table 3 are summarized in Table 4. The mass of materials produced by each cyclone separator of the solid separation system in Table 3 is summarized in Table 5. The fractions of the materials fed to each stage are separated into bottom materials and top materials. Table 6 shows the destination of the materials entering the catalytic reactor.

[0107] The calculations show that most of the catalyst is separated in the first classification cyclone, with the remainder being separated in the second stage. The first cyclone was designed to reduce efficiency to 80.5%, which would allow complete removal of filler representing 19.4% of the solid content in the gas entering the cyclone, and after optimizing the cyclone sizes, an efficiency of 80.9% was calculated. Subsequently, the second, third and fourth stage separations were designed to have an overall efficiency of 99.6%, which allowed the filler content in the gas to be reduced to the required specification of 4 kg / h, corresponding to the solid limit that can be introduced into the downstream processing units. Most of the required separation effect (94.2%) is achieved in the second cyclone, while the third and fourth stages complete the separation and reach the target, with efficiencies of 77.4% and 74.4% for the third and fourth cycles, respectively, mainly due to the low required separation specification and the low solid content in the gas entering these stages, these efficiencies for the second, third and fourth stages are the highest possible efficiencies achievable using the adopted calculation method. The 3-stage purification after classification produces a gas stream containing 4 kg / h of filler particles, suitable for introduction into the splitter.

[0108] Table 3. Examples 1 used for Figure 5 and Figure 6 Parameters of the cyclone separator in the project.

[0109]

[0110] Table 4. Flow rates of solids in the solid separation system of Example 1.

[0111]

[0112]

[0113] Table 5. Fractions of feed found in each of the separate streams in Example 1.

[0114]

[0115] Table 6. Destinations of materials fed to the catalytic pyrolysis reactor.

[0116]

[0117] Example 2

[0118] The number of cyclones required to separate and remove fillers from the flue gas effluent of a catalyst regenerator in a plastic chemical recycling system processing 500 metric tons per day of mixed plastics containing 5 wt. % fillers to produce useful products was calculated. It was assumed that about 95% of the mass of the fillers came from particles with a size less than 20 microns, while about 95% of the mass of the catalyst came from particles with a size greater than 65 microns. Figure 7 The experimentally determined particle size distribution of solids (including fillers and catalyst) discharged from the regenerator is shown. The solids to be separated include a density of 1300 kg / m 3 The catalyst particles and density are 2700kg / m 3 The solid flow rate is 105 kg / s, the gas flow rate is 10.14 g / s. The gas density of the steam flow at 500°C is 1.8 kg / m3.

[0119] The solids separation system designed for separation and removal of solids consists of 76 cyclones: a classifier (low efficiency cyclone) and three stages of multi-cyclone separators in series, each containing 25 internal cyclones. Table 7 summarizes the design of the solids separation system for separation and removal of solids. Figure 5 and Figure 6 The size of the cyclone separators and their performance in the project. Table 8 summarizes the mass of materials produced by each cyclone separator stage of the solid separation system in Table 5. Table 9 summarizes the fraction of each material fed to each stage separated into bottom material and top material. Table 10 shows the destination of the materials entering the catalyst regenerator.

[0120] The calculations show that all the catalyst is separated in the first classifying cyclone. The first cyclone was designed to reduce the efficiency to 99.7%, which completely removes the filler which accounts for 19.4% of the solids content in the gas entering the cyclone. The first cyclone shows complete separation of filler and catalyst, all catalyst is recovered from the bottom of the cyclone, and 97.25% of the filler passes with the gas phase. The second, third and fourth stage separations were designed to have an overall efficiency of 99.6%, which reduces the filler content in the gas to the required specification of 4 kg / hour, corresponding to the solids limit that can enter the downstream processing units. Most of the required separation effect (94.8%) is achieved in the second cyclone, while the third and fourth stages complete the separation and reach the target. The efficiencies of the third and fourth cycles are 76.5% and 69.7%, respectively. This is mainly due to the low separation specifications required and the low solids content in the gas entering these stages. These efficiencies of the second, third and fourth stages are the highest possible efficiencies achievable using the calculation method adopted. The three-stage purification after the staged cyclone separator has a multi-cyclone separator containing 25 cyclones in each stage, and the final flue gas flow contains 3 kg / h of filler particles, which can be discharged into the air.

[0121] Table 7. Examples 2 used for Figure 5 and Figure 6 Parameters of the cyclone separator in the project.

[0122]

[0123]

[0124] Table 8. Mass flow rate of solids in the solids separation system of the catalyst regenerator in Example 2.

[0125]

[0126] Table 9. Fractions of feed found in each of the separate streams in Example 2.

[0127]

[0128] Table 10. Destinations of feeds in Example 2.

[0129]

[0130] Example 3

[0131] A small pilot plant for upgrading waste plastics or other materials was built, which was equipped with a catalyst bubbling fluidized bed, a stripper for removing and recovering deposits on the catalyst, a regenerator for regenerating the catalyst, and a solid separation system for separating the catalyst from the packing. The process parameters are shown in Table 11.

[0132] Table 11. Process parameters for Example 3.

[0133] parameter value Bed height(m) 1.7 Catalyst circulation rate (kg / hour) 180 Fluidizing gas velocity (m / s) 0.18 Average plastic feed rate (kg / hour) 8.3 <![CDATA[WHSV (g 进料 / g 催化剂 h)]]> 0.193 Reactor temperature (℃) 550 Reactor pressure (bar) 4 Cyclone separator #1 temperature (℃) 438

[0134] Figure 8 A schematic diagram of the solid flow within the pilot plant is shown, which includes a fluidized bed reactor 140, a stripper 145, a catalyst regenerator 150, and a solid separation system 160. Plastic 10 is fed into the catalytic fluidized bed reactor, and catalyst 142 is continuously withdrawn and stripped with N2 to obtain a stripped catalyst 147. The stripped catalyst 147 is regenerated in the regenerator 150, and the regenerated catalyst 143 is returned to the reactor. The fluid product stream 141 is conveyed to the solid separation system 160, which includes two solid separation cyclone separators in series, the larger particles from the two cyclone separators are returned to the reactor, and the vapor stream from the first cyclone separator is conveyed to the second cyclone separator. The cyclone separator separates larger particles (mostly catalyst) 162 from smaller particles in the vapor product stream 163; the larger particles are returned to the catalytic fluidized bed reactor. Table 12 summarizes Figure 5 The dimensions of the cyclone separator designed in.

[0135] Table 12. Dimensions of cyclone separators used in Example 3.

[0136]

[0137]

[0138] Table 13. Cyclone separator characteristic parameters of the cyclone separator of Example 3.

[0139] parameter value De / D 0.343 <![CDATA[S / h b ]]> 0.4375 <![CDATA[B / D e ]]> 1 a / b 0.85 S / H 0.11

[0140] The catalytic reactor was loaded with catalyst and the unit was brought to operating state by heating the reactor and regenerator and establishing flow with inert gas (N2). The reactor was run for 24 hours without feed to reach steady state. Plastic feeding was started after 24 hours of operation and the reactor was run for 5.5 hours with plastic feed containing fillers. Samples were collected after 3.5 hours of plastic feed. After 5.5 hours of plastic feed, the reactor was run for 42 hours without any feed but kept hot under insulation conditions.

[0141] The plastic-containing charge was restarted at the 71.5 TOS mark and continued for 5.5 hours. A sample was taken at the 75.5 TOS mark, at which point the system had been fed with plastic for a total of 9.5 hours.

[0142] During this process, several PSD samples were collected from different locations. 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. Figure 8 shown.

[0143] The particle size distribution (PSD) was determined by dispersing the material in deionized water and measuring the particle size (bulk density) using a Mastersizer 3000 (manufacturer Malvern Panalytical).

[0144] exist Fig. 9 The PSD of the regenerated catalyst sample was determined to be unimodal with similar distributions at 24, 27.5, and 75.5 hours of operation. The maximum bulk density was measured at a particle size of 105–110 μm. In the early stages of the run (TOS 24 hours), the PSD was broad. As TOS progressed, the distribution narrowed because larger particles were ground while smaller particles were entrained by the 2 cyclones in the solid separation system and removed from the product vapor.

[0145] Fig.10 The PSD profile for the unstripped catalyst in standpipe 1 is shown to be unimodal, with the maximum bulk density being measured at a particle size of 105–110 μm throughout the run. As before, the PSD is broad at early TOS, while the distribution becomes slightly narrower as TOS increases. Similarly, Fig.11 The PSD of the stripped catalyst at three different time points in the run is shown, with the early distribution being broader than the later distribution.

[0146] Fig.12 The PSDs for samples from Stand 1 (unstripped), Stand 2 (stripped), and Stand 3 (regenerated) at TOS 27.5 hours are shown after feeding plastic at 6.5 kg / hour for 3.5 hours. The higher peak is from the regenerated catalyst, while the lower peak shows two other PSDs that overlap. It is believed that the slightly broader PSD may be due to a few percent of coke accumulated on the catalyst that was burned off in the regenerator.

[0147] To understand the fractionation of the separation system, a sample of the solids captured during the quenching process downstream of the solids separation system was calcined and evaluated. The PSD of the ash was measured and is shown together with the PSD of the catalyst in the fluidized bed. Fig.13The ash separated in the solid separation system has about 80 mass % of particles smaller than 50 microns, while the catalyst bed has less than 1 mass % of particles smaller than 50 microns. It can be seen that both cyclone separators can efficiently separate particles into particles smaller than 80 microns and particles larger than 80 microns according to particle size.

[0148] Example 4

[0149] Computational particle fluid dynamics (CPFD) modeling was used to calculate the number of cyclones required to separate and remove fillers from the product effluent of a catalytic reactor in a system that processes 500 tons per day of mixed plastics containing 5 wt.% fillers into useful products. It was assumed that about 95% of the mass of the fillers came from particles with a size less than 20 microns, while about 95% of the mass of the catalyst came from particles with a size greater than 65 microns. Figure 4 The particle size distribution of the filler, catalyst and the sum of filler and catalyst in the feed ("cyclone inflow") is shown. It is assumed that the plastic mixture is catalytically pyrolyzed in a fluidized bed catalytic reactor, producing a product vapor stream of 5.2 kg / s, in which the entrained solids include 1.2 kg / s of catalyst particles and 0.29 kg / s of filler particles. It is assumed that 10% of the feed mixture is deposited on the catalyst in the form of coke or materials adsorbed in the pores of the catalyst. The density of the catalyst particles is assumed to be 1300 kg / m3 and the density of the filler particles is assumed to be 2700 kg / m3. The gas density of the vapor stream at 500°C is 1.65 kg / m3.

[0150] The CPFD model included a primary classifying (low efficiency) cyclone designed to separate the filler from the catalyst material. The dimensions of the cyclone are summarized in Table 14. Simulations were performed under different conditions for the reactor inlet fluidization velocity and the amount of filler entering the reactor, and the results are summarized in Table 15. In all cases, the proposed classifier design was able to remove filler from the product vapor in the range of 72-91%, while essentially 100% of the catalyst was recovered and returned to the reactor.

[0151] This example demonstrates that a classifying cyclone can effectively separate filler from product vapor without loss of catalyst for recycle to the reactor.

[0152] Table 14. CFD evaluation parameters for the classifying cyclone separator.

[0153] parameter symbol unit size Number of cyclone separators per stage 1 Cylinder diameter D mm 1350 Eddy current diameter <![CDATA[D e ]]> mm 675 Entrance Width b mm 337 Cylinder length <![CDATA[h b ]]> mm 1350 Eddy current length S mm 1215 Overall height H mm 3375 Underflow diameter B mm 135 Entrance height a mm 810

[0154] Table 15. Results of CFD evaluation of cyclone separator performance.

[0155]

[0156]

Claims

1. A method for producing olefins and aromatics, comprising: feeding a stream comprising plastics, wherein at least one of the plastics contains a filler, into a fluidized bed reactor comprising a 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; allowing the feed and the catalyst to undergo a catalytic reaction 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, wherein the vapor effluent comprises catalyst particles and filler; passing the vapor effluent through a solids separation system, including passing the vapor effluent into a first cyclone separator and separating a first bottoms portion and a first overflow portion; wherein the first cyclone separator is a classifying cyclone separator; wherein the first bottom material portion has a second mass ratio greater than the first mass ratio; sending the overflow portion into a second cyclone separator and separating a second bottom material portion and a second overflow portion; wherein the first cyclone separator has a first separation efficiency for the catalyst particles, and the second cyclone separator has a second separation efficiency for the catalyst particles that is greater than the first separation efficiency; wherein the second bottom material portion has a third mass ratio that is less than the first mass ratio; and Olefins or aromatics or a combination thereof are recovered from the second overflow vapor portion discharged from the last cyclone separator.

2. The method of claim 1, wherein the first cyclone separator comprises one or more low-efficiency classifying cyclone separators, or the second cyclone separator comprises one or more recovery cyclone separators or multi-cyclone separators or both.

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

4. The process of claim 1 wherein at least a portion of the solids recovered from the bottoms of the one or more low efficiency 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. 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. The process of claim 1 wherein a stream rich in ethylene or propylene or both is separated from the volatile products.

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

9. The process of claim 1 wherein at least 80% by mass of the catalyst particles have a size of at least 40 microns, or at least 50 microns, or at least 60 microns, or at least 75 microns, or at least 100 microns, or between 40 and 300 microns, or between 50 and 250 microns, or between 75 and 150 microns.

10. The method of claim 1, wherein at least 80% by mass of the filler particles have a size no greater than 40 microns, or 30 microns, or 20 microns, or 15 microns, or 10 microns, or 1 to 40 microns, or 2 to 30 microns, or 5 to 20 microns.

11. The process of claim 1 , wherein the residence time of the fluidizing gas in the catalytic pyrolysis reactor 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, wherein the residence time is defined as the volume of the reactor divided by the volumetric flow rate of the fluidizing fluid under the temperature and pressure conditions of the process.

12. 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. The method of claim 1, wherein the fluidized bed reactor is a circulating bed, a bubbling bed, a turbulent bed or a riser reactor.

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

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

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

17. The process of claim 1, wherein a catalyst and filler solid separation system comprising a classifying cyclone and a recovery cyclone is used, solids from the classifying cyclone are returned to the fluidized bed reactor, and olefins or aromatics are recovered from the vapor discharged from the last recovery cyclone.

18. The method of claim 17, wherein the cut size of the classifying cyclone separator is designed to be between the particle size distribution of the filler and the particle size distribution of the catalyst, thereby allowing the larger particle size fraction to be separated while the smaller particle size fraction is entrained in the exhaust gas for removal in a series of high efficiency recovery multi-cyclone separators.

19. The process of claim 1, wherein the feed stream comprises a plastic selected from the group consisting of polyethylene, polypropylene, polyester, polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymers, polyethylene furanoate (PEF), polyamides, polyurethanes, polyethers, polycarbonates, polyoxides, polysulfides, polyarylates, polyetherketones, polyetherimides, polysulfones, polyurethanes, polyvinyl alcohols, and polymers produced by polymerization of monomers such as dienes, olefins, styrenes, acrylates, acrylonitriles, methacrylates, methacrylonitrile, diacids and diols, lactones, diacids and diamines, lactams, vinyl esters, their block copolymers, and their alloys; thermal Solid polymers, such as epoxy resins; phenolic resins; melamine resins; alkyd resins; vinyl ester resins; unsaturated polyester resins; cross-linked polyurethanes; polyisocyanurates; cross-linked elastomers, including but not limited to polyisoprene, polybutadiene, styrene-butadiene, styrene-isoprene, ethylene-propylene-diene monomer polymers; and mixtures thereof, wherein the raw material comprises a mixture of waste plastics selected from the group consisting of polyethylene terephthalate (PET), high-density polyethylene (HDPE), polyvinyl chloride (PVC) or polyvinylidene fluoride (PVCD), low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), or mixed resins, or some combination thereof.

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

21. The method of claim 1, wherein the filler is selected from the group consisting of alumina, aluminum, aluminum fiber, aluminum flakes, aluminum hydroxide, aluminum nitride, antimony-doped tin oxide, antimony oxide, aramid, attapulgite, barium sulfate, barium titanate, bentonite, bismuth carbonate, boron oxide, boron nitride, bronze powder, calcium carbonate, calcium fluoride, calcium phosphate, calcium silicate, calcium sulfate, calcium sulfate whisker, carbon black, carbon fiber, carbon nanotubes, cellulose nanocrystals, chitosan, clay, compatibilizer, copper, diamond, diatomaceous earth, expanded graphite, ferromagnetic powder, fluorine mica, fly ash, fumed nanosilica, glass beads, glass fibers, glass flakes, glass balls, graphene, graphite, tire rubber powder, hollow glass microspheres, hollow silicates, hydrotalcite, iron, kaolin, lignin, magnesium hydroxide, magnesium oxide, magnetite, mica, microfiber cellulose, molybdenum sulfide, montmorillonite, ni-batio3, nickel, phenolic microspheres, potassium titanate whiskers, potassium magnesium aluminum silicate, polytetrafluoroethylene, pyrophyllite, red mud, red phosphorus, rubber particles, sand, sepiolite, silane, silicon dioxide, silicon carbide, silver powder, soot, starch, superconducting material (yba2cu3o7-x), talc, tetrapod-shaped zinc oxide whiskers, titanium dioxide nanoparticles, titanium dioxide, vermiculite, wollastonite, wood fiber, wood powder, zinc borate, zinc oxide, zirconium silicate or a combination thereof.

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

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

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

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

28. The method of claim 1, wherein the catalyst in the fluidized bed comprises a catalytic molecular sieve, wherein the catalytic molecular sieve accounts for 30 to 90 weight % or 40 to 70 weight % of the composition of the catalyst particles.

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

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

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

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

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

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

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

37. The process 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 alkaline material, or some combination thereof, is fed to the thermal treatment reactor.

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

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

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

41. 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 mass of the polymer feed.

42. The process 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. The process of claim 1 wherein benzene, toluene or xylenes are separated or recovered from the product vapor mixture.

44. The process of claim 38 wherein at least a portion of the aromatic products in the product vapor mixture are hydrogenated to produce cycloalkanes.

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

46. ​​A process as claimed in claim 1, wherein the product vapor mixture is subjected to a separation process to produce a gas stream rich in CH4, CO and H2; and at least a portion of the gas stream rich in CH4, CO and H2 is conveyed to a regenerator where they are combusted.

47. The process of claim 1, wherein the product vapor mixture comprises CH4 and C2-C4 paraffins; and wherein 50 to 100 mass % of the CH4 and C2-C4 paraffins are combusted in the regenerator.

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

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

50. The method of claim 48, wherein at least a portion of the gases in the product mixture are combusted in a regenerator.

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

52. The method of claim 48, wherein heat generated by regenerating the catalyst provides energy for a thermal treatment or pyrolysis or catalytic pyrolysis step.

53. A method as claimed in claim 49 or 50, wherein the heat recovered from the catalyst regenerator is used to heat the feed, a thermal treatment reactor, or a pyrolysis reactor, or a catalytic pyrolysis fluidized bed reactor, or some combination thereof.

54. A method as claimed in claim 48, wherein the combustion product gases (flue gases) produced in the catalyst regenerator or the packing regenerator or both are conveyed to a solid separation system or separate multiple solid separation systems, wherein the one or more solid separation systems include a series of cyclone separators (optionally classified cyclone separators) followed by one or more high efficiency multi-cyclone separators.

55. The method of claim 1, wherein the flow velocity at the inlet of the low efficiency classifying cyclone separator 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.

56. The method of claim 1, wherein in any one of the classifying cyclones, the ratio of the vortex diameter to the barrel diameter may be 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 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, or the ratio of the vortex length to the barrel length may be 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or in the range of 0.3 to 0.95, or 0.5 to 0.95, or 0.8 to 0.95, or 0.85 to 0.95, or the ratio of the underflow diameter to the vortex diameter may be 0.02, or 0.1, or 0.15, or 0.2, or 0.2 5, or 0.3, or 0.5, or 1.0, or 1.25, or in the range of 0.02 to 1.25, or 0.02 to 0.5, or 0.1 to 0.3, or 0.15 to 0.25, or the ratio of inlet height to inlet width can be 0.75, or 1, or 1.5, or 2, or 2.4, or 3, or 4, or 5, or can be in the range of 0.75 to 5, or 1.5 to 4, or 2 to 3, or 2.2 to 2.6, or the ratio of vortex length (S) to total height (H) can be 0.1, or 0.2, or 0.3, or 0.36, or 0.4, or 0.5, or 0.6, or 0.8, or in the range of 0.1 to 0.8, or 0.2 to 0.6, or 0.3 to 0.4, or 0.34 to 0.

38.

57. The method of claim 2, wherein the one or more recovery cyclones comprise at least one multi-cyclone separator.

58. The method of claim 1 wherein one or more of the cyclonic separators are devoid of vortex finders.

59. The method of claim 2, wherein for each of the plurality of small diameter cyclones within any multi-cyclone separator, the ratio of the vortex diameter to the barrel diameter may be 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 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, or the ratio of the vortex length to the barrel length may be 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or in the range of 0.3 to 0.95, or 0.5 to 0.95, or 0.8 to 0.95, or 0.85 to 0.95, or the ratio of the underflow diameter to the vortex diameter may be 0.02, or 0.1, or 0.1 5, or 0.2, or 0.25, or 0.3, or 0.5, or 1.0, or 1.25, or in the range of 0.02 to 1.25, or 0.02 to 0.5, or 0.1 to 0.3, or 0.15 to 0.25, or the ratio of inlet height to inlet width can be 0.75, or 1, or 1.5, or 2, or 2.4, or 3, or 4, or 5, or can be in the range of 0.75 to 5, or 1.5 to 4, or 2 to 3, or 2.2 to 2.6, or the ratio of vortex length to total height can be 0.1, or 0.2, or 0.3, or 0.36, or 0.4, or 0.5, or 0.6, or 0.8, or in the range of 0.1 to 0.8, or 0.2 to 0.6, or 0.3 to 0.4, or 0.34 to 0.

38.

60. The method of claim 2, wherein the flow velocity at the inlet of any one of the recovery cyclones is no more than 25, or 20, or 15, or 10, or 5, or 3, or 3 to 20, or 5 to 15, or 6 to 12 m / s.

61. The method of any one of claims 57 to 60, wherein the number of small cyclone separators in any multi-cyclone separator may be 4, 9, 16, 25, 36, 49 or 64, or 4 to 64, or 9 to 49, or 16 to 36 cyclone separators.

62. The method of claim 2, wherein the efficiency of the low efficiency classifying cyclone separator or combination of cyclone separators is no more than 95%, or 90%, or 85%, or 80%, or 75%.

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

64. The process of claim 2 wherein the concentration of particles in the vapor product discharged from the recovery cyclone is no more than 200, or 300, or 400, or 500 μg per cubic meter of vapor product.

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

66. The method of claim 65, wherein a purge gas of lithium such as H2O, N2, Ar, CO2, or some combination thereof is fed to the thermal processing reactor and vapor is vented.

67. A process as claimed in claim 65 or 66 wherein the plastic feed stream is heated to a temperature between 250 and 300°C in the thermal treatment reactor and the product is conveyed to a pyrolysis reactor.

68. The process of any one of claims 65 to 67, wherein an inert gas is fed to the thermal processing reactor and vapor is vented.

69. The process 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. The process 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 a major portion of the products.

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

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

73. The method of claim 72, wherein hot flue gas exhausted from a solid co-reactant material regenerator is conveyed to a catalyst heater to heat a catalyst for use in the catalytic pyrolysis reactor.

74. The process of any one of claims 65 to 73, wherein the thermal treatment is carried out by heating the feed to a temperature between 250 and 300°C, maintaining it at that temperature while removing steam, and then sending the condensed phase to the catalytic pyrolysis reactor or further pyrolyzing it at a higher temperature in the pyrolysis reactor.

75. A process as claimed in claim 48, wherein the catalyst removed from the catalytic reactor or the catalyst recovered in the solid separation system, or both, is freed of volatile materials by passing a stream of steam, nitrogen, CO, CO2, CH4, He, or some combination of these, or a recycle stream from the product gas, through the catalyst particles, condensing the stream, separating the organic and aqueous phases, sending the liquid organic phase to product recovery, sending the aqueous phase to waste water recovery, and sending the catalyst from which the volatile organic compounds have been removed to a catalyst regenerator or returned to the catalytic reactor or discarded, or some combination of these.

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

77. A method as claimed in claim 76, wherein the packing recovered from the solid separation system is freed of volatile materials by passing a stream of steam, nitrogen, CO, CO2, CH4, He or some combination of these or a recycle stream from the product gas through the packing particles, condensing the stream, separating the organic and aqueous phases, sending the liquid organic phase to product recovery, sending the aqueous phase to waste water recovery, and sending the packing from which the volatile organic compounds have been removed to a packing regenerator or discarded, or some combination of these.

78. The process 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, or 0.1 to 50, 0.5 to 30, or 5 to 20.

79. The process 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, or 30 to 5,000, or 50 to 1000.

80. The process of claim 1 wherein the mass ratio of catalyst particles to filler particles in the overflow of the classifying cyclone is no more than 10, 5, 2, 1, 0.2, or 0.1, or 0.0001 to 10, 0.001 to 5, or 0.01 to 1.

81. The process of claim 1 wherein the mass ratio of catalyst particles to filler particles in the recovery cyclone overflow is no more than 0.1, 0.001, 0.00001, or 0.0000001 to 0.1, 0.00001 to 0.01, or 0.0001 to 0.

001.

82. The process of claim 1 wherein the mass ratio of catalyst particles to filler particles in the recovery cyclone bottoms is no more than 0.1, 0.001, 0.00001, or 0.0000001 to 0.1, 0.00001 to 0.01, or 0.0001 to 0.001.

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