Processes and systems for producing fuels and petrochemical raw materials from mixed plastic flows.

Abstract

A method and system for producing pyrolysis products from a mixed plastic stream is described herein. The method may include the steps of: pyrolyzing a plastic feedstock to produce a stream of plastic pyrolysis oil; feeding a catalytic cracking feed stream including the plastic pyrolysis oil and a catalyst from a catalyst regenerator to a fluidized bed reactor; cracking the catalytic cracking feed stream in the fluidized bed reactor to produce a product stream and spent catalyst; and transferring the spent catalyst to a catalyst regenerator and regenerating the catalyst in the catalyst regenerator. The product stream includes olefins having carbon numbers from C2 to C4 and distillate fuels.

Description

Priority

[0001] This application claims to benefit from U.S. Patent Application No. 17 / 588476, filed on 31 January 2022, the full disclosure of which is herein by reference. [Technical Field]

[0002] This disclosure broadly relates to processes and systems for chemically decomposing pyrolysis products generated from mixed plastic flows, and more particularly to processes and systems for preparing plastic pyrolysis products as distillate fuels and light olefins by fluid catalytic cracking of plastic pyrolysis oil. [Background technology]

[0003] Plastics are synthetic or semi-synthetic organic polymers composed primarily of carbon and hydrogen. Furthermore, plastics tend to decompose slowly and are durable; therefore, they remain in the environment for extended periods and do not decompose rapidly upon disposal. Pure plastics are generally insoluble in water and non-toxic. However, additives used in the preparation of plastics can be toxic and leach into the environment. Examples of toxic additives include phthalates. Other types of additives include fillers, colorants, plasticizers, stabilizers, antioxidants, flame retardants, ultraviolet (UV) absorbers, antistatics, foaming agents, and lubricants used during preparation to alter the composition and properties.

[0004] Plastics decompose at high temperatures, and the polymers can be converted back into their original monomers or smaller polymers as a gas or liquid, and thus recovered. However, additives added to plastics during production pose a challenge to the effective utilization of the products recovered from thermal decomposition. During thermal decomposition, the additives become decomposition products, and therefore require further processing to produce useful products. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Therefore, there has clearly been a long-standing need to provide solutions for utilizing the pyrolysis products generated by the thermal decomposition of plastics. To utilize such pyrolysis products, residues left from additives in the pyrolysis products must be removed, or the pyrolysis products must be utilized in a manner that the residues are not harmful. This disclosure addresses such long-standing needs for the utilization of pyrolysis products generated by the thermal decomposition of plastics and for the disposal of plastics by utilizing the generated plastic pyrolysis oil as a raw material for fluid catalytic cracking (FCC). [Means for solving the problem]

[0006] Crude oil is traditionally refined to produce transport fuels and petrochemical feedstocks, but as demonstrated by this disclosure, plastic pyrolysis oil can instead be used as a feedstock to produce such transport fuels and petrochemical feedstocks. Transport fuels are typically produced by processing and blending distillation fractions from crude oil to meet the specifications of a particular end use. After initial atmospheric and / or vacuum distillation, the fractions are converted into products by various catalytic and non-catalytic processes. One such process is the fluid catalytic cracking (FCC) process. In the FCC process, the feedstock is catalytically cracked on a fluid catalyst bed. The main product from such a process is conventionally gasoline, although other products such as liquefied petroleum gas and cracked diesel are also produced in small amounts in the FCC process, but light olefins useful as petrochemical feedstocks are further produced according to the methods of this disclosure. The coke deposited on the catalyst is burned off at relatively high temperatures in a regeneration area, if air is present, before being returned to the reaction area.

[0007] According to one embodiment of the present disclosure, plastic raw materials may be converted into transport fuels and petrochemical raw materials by plastic pyrolysis and fluid catalytic cracking. A method for producing pyrolysis products from a mixed plastic flow includes: (a) pyrolysis of the plastic raw materials to produce a flow of plastic pyrolysis oil; (b) supplying a catalytic cracking feed stream containing the plastic pyrolysis oil and a catalyst from a catalyst regenerator to a fluidized bed reactor; (c) cracking the catalytic cracking feed stream in the fluidized bed reactor to produce a product flow and spent catalyst; and (d) transferring the spent catalyst to a catalyst regenerator and regenerating the catalyst in the catalyst regenerator. The product flow includes olefins having C2 to C4 carbon atoms and distillate fuels. Furthermore, the plastic pyrolysis oil includes a naphtha fraction representing hydrocarbons with boiling points from 36 to 180°C, a diesel fraction representing hydrocarbons with boiling points from 180 to 370°C, and a vacuum light oil fraction representing hydrocarbons with boiling points higher than 370°C.

[0008] According to another embodiment of the present disclosure, a system for processing mixed plastics into plastic pyrolysis products comprising transport fuel and petrochemical raw materials may include: an inlet flow containing the mixed plastics; a plastic pyrolysis unit fluidly communicating with the inlet flow and functioning to generate a flow of plastic pyrolysis oil from the inlet flow at a plastic pyrolysis oil outlet; a fluidized bed reactor including a catalyst inlet and a catalytic cracking feed inlet; a catalyst regenerator fluidly communicating with the catalyst inlet of the fluidized bed reactor; a catalyst circulating from the catalyst regenerator to the fluidized bed reactor and back to the catalyst regenerator; and a catalytic cracking feed inlet located within the fluidized bed reactor that reacts with the catalyst. The catalytic cracking feed inlet is fluidly communicating with the plastic pyrolysis oil outlet so that the catalytic cracking feed inlet, which reacts with the catalyst to produce a product flow, is located within the fluidized bed reactor. Furthermore, the catalytic cracking feed inlet contains plastic pyrolysis oil, which comprises a naphtha fraction representing hydrocarbons with boiling points from 36 to 180°C, a diesel fraction representing hydrocarbons with boiling points from 180 to 370°C, and a vacuum light oil fraction representing hydrocarbons with boiling points higher than 370°C.

[0009] Additional features and advantages of the technologies disclosed herein are described in the following detailed description, some of which will be readily apparent to those skilled in the art from that description, or will be recognized by carrying out the technologies described herein, including the following detailed description, claims, and accompanying drawings.

[0010] Both the general description above and the detailed description below present embodiments of the aforementioned technology and are intended to provide an overview or framework for understanding the nature and features of the technology as described in the claims. The accompanying drawings are included to provide a further understanding of the technology and are incorporated herein and constitute part thereof. The drawings illustrate various embodiments and, together with the description, serve to illustrate the principles and operation of the technology. In addition, the drawings and description are for illustrative purposes only and are not intended to limit the scope of the claims in any way. [Brief explanation of the drawing]

[0011] The following detailed description of specific embodiments of this disclosure can be best understood when read in conjunction with the following drawings, in which similar structures are shown by similar reference numbers. [Figure 1] A schematic diagram of one or more embodiments of the present disclosure, in which plastic raw materials are thermally decomposed to produce plastic pyrolysis oil, which is then converted by fluid catalytic cracking into olefins having C2-C4 carbon atoms and distillate fuel. [Figure 2] Schematic diagram in Figure 1, showing the plastic pyrolysis oil mixed with the secondary hydrocarbon flow before fluid catalytic cracking. [Figure 3] Schematic diagram in Figure 1: Before fluid catalytic cracking, the plastic pyrolysis oil undergoes a demetallation process. [Figure 4] A general diagram of a Downer FCC reactor according to one or more embodiments described herein. [Figure 5]Generalized diagram of a riser FCC reactor according to one or more embodiments described herein For the purposes of this simplified schematic illustration and explanation, many valves, temperature sensors, electronic control devices, etc. that are commonly used and known to those of ordinary skill in the technical field of certain purification operations are not included. Further, for example, components associated with conventional purification operations including the FCC process such as air supply, catalyst hoppers, flue gas handling, etc. are not necessarily shown.

[0012] Further, it should be noted that the arrows in the drawings refer to pipes, conduits, passages, or other physical transfer lines that fluidly connect one or more system devices to one or more other system devices. In addition, the arrows connecting to the system devices define the inlets and outlets at each given system device.

Embodiments for Carrying Out the Invention

[0013] Here, various embodiments are described in detail with reference to the accompanying drawings, some of which embodiments are shown in the accompanying drawings. Whenever possible, the same reference numbers are used throughout the drawings to refer to the same or similar parts. Generally, various embodiments of systems and methods for producing pyrolysis products from a mixed plastic stream by thermal decomposition of plastic feedstock in an integrated FCC unit to produce plastic pyrolysis oil and decomposition of the plastic pyrolysis oil are disclosed herein. Generally, the FCC unit includes a fluidized bed reactor. The catalyst and the plastic pyrolysis oil are fed into the fluidized bed reactor, and the plastic pyrolysis oil is decomposed to form the desired products. The spent catalyst is separated from the products, regenerated, and fed back into the fluidized bed reactor together with additional plastic pyrolysis oil.

[0014] As used herein, "fuel" may include solid carbonaceous compositions such as coal, coal liquefied oil, tar, oil shale, oil sand, tar sand, biomass, wax, and coke; liquid carbonaceous compositions such as gasoline, oil, petroleum, diesel, jet fuel, and ethanol; and gaseous compositions such as synthesis gas, carbon monoxide, hydrogen, methane, gaseous hydrocarbon gas (C1 - C4), and hydrocarbon vapor.

[0015] As used herein, the term "downer" refers to a reactor such as a fluidized bed reactor in which the reactants generally flow in a downward direction, e.g., entering from the top of the reactor and exiting from the bottom. A downer may be used in the embodiments of the downflow FCC reactor described herein. Similarly, the term "riser" refers to a reactor such as a fluidized bed reactor in which the reactants generally flow in an upward direction, e.g., entering from the bottom of the reactor and exiting from the top. A riser may be used in the upflow FCC reactor described herein.

[0016] As used herein, "spent catalyst" refers to a catalyst that has experienced a reaction with fuel and is at least partially coked. Also, as used herein, "regenerated catalyst" refers to a catalyst that exits from a catalyst regenerator and contains at least partially or substantially no coke, and "fresh catalyst" refers to a catalyst that newly enters the system and contains at least partially or substantially no coke.

[0017] A method for producing pyrolysis products from a mixed plastic flow includes the steps of: pyrolysis of plastic raw materials to generate a flow of plastic pyrolysis oil; supplying a catalytic cracking feed stream containing the plastic pyrolysis oil and a catalyst from a catalyst regenerator to a fluidized bed reactor; cracking the plastic pyrolysis oil in the fluidized bed reactor to generate a product flow and spent catalyst; and transferring the spent catalyst to a catalyst regenerator and regenerating the catalyst in the catalyst regenerator. The product flow generated in the fluidized bed reactor contains olefins having C2 to C4 carbon atoms and distillate fuels. Furthermore, the plastic pyrolysis oil produced by the pyrolysis of plastic raw materials includes a naphtha fraction representing hydrocarbons with boiling points from 36 to 180°C, a diesel fraction representing hydrocarbons with boiling points from 180 to 370°C, and a vacuum light oil fraction representing hydrocarbons with boiling points higher than 370°C.

[0018] The associated system for processing mixed plastics into plastic pyrolysis products includes an inlet stream containing the mixed plastics, a plastic pyrolysis unit, a fluidized bed reactor, a catalyst regenerator, a catalytic cracking feed stream, and a catalyst. The plastic pyrolysis unit is configured to be in fluid communication with the inlet stream and operates to produce a flow of plastic pyrolysis oil that forms at least a portion of the catalytic cracking feed stream. The fluidized bed reactor includes a catalyst inlet and a catalytic cracking feed inlet. The catalytic cracking feed inlet is in fluid communication with the plastic pyrolysis oil outlet so that the catalytic cracking feed stream is located within the fluidized bed reactor for reaction with the catalyst to produce a product stream. Furthermore, a catalyst regenerator is configured to be in fluid communication with the fluidized bed reactor so that the catalyst circulates from the catalyst regenerator to the fluidized bed reactor and back to the catalyst regenerator.

[0019] Various embodiments of systems and methods for producing pyrolysis products from a mixed plastic flow by generating plastic pyrolysis oil in an integrated FCC unit and decomposing the plastic pyrolysis oil have been described extensively, and these embodiments will be described in more detail with reference to various drawings.

[0020] Referring to Figure 1, a schematic diagram of one or more generalized embodiments of the present disclosure is shown. An inlet flow 101 containing a mixed plastic is supplied to a plastic pyrolysis unit 50. The plastic pyrolysis unit 50 is in fluid communication with the inlet flow 101 and functions to generate a flow of plastic pyrolysis oil 102 from the inlet flow 101 at a plastic pyrolysis oil outlet 52. An FCC unit 130 is in fluid communication with the plastic pyrolysis oil outlet 52 of the plastic pyrolysis unit 50 and functions to decompose a catalytic cracking feed flow 103 containing the plastic pyrolysis oil 102 into a product flow 110. Note that in embodiments in which the flow of plastic pyrolysis oil 102 is supplied to the FCC unit 130 without any further processing, the catalytic cracking feed flow 103 is synonymous with the flow of plastic pyrolysis oil 102. The product flow 110 generally contains olefins having C2 to C4 carbon atoms and distillate fuels.

[0021] Plastic raw materials In one or more embodiments, the inlet flow 101 contains plastic raw materials, including mixed plastics of different compositions. The plastic raw materials supplied to the plastic pyrolysis unit 50 may be a mixture of plastics from various polymers. In various embodiments, the plastic raw materials may include plastics representing one or more of the polymers disclosed in Table 1. Specifically, the plastic raw materials may include plastics representing one or more of the following: olefins, carbonate esters, aromatic polymers, sulfones, fluorinated hydrocarbon polymers, chlorinated hydrocarbon polymers, and acrylonitriles. Furthermore, the plastic raw materials supplied to the plastic pyrolysis unit 50 may include high-density polyethylene (HDPE), for example, about 0.93 to 0.97 grams (g / cm³) per cubic centimeter. 3 (density of low-density polyethylene (LDPE), for example, about 0.910 g / cm³) 3 From 0.940 g / cm³ 3It may be a mixture of polypropylene (PP), linear low-density polyethylene (LLDPE), polystyrene (PS), and polyethylene terephthalate (PET). It is recognized that by using mixed plastic raw materials, it is possible to recycle plastics without the need to further classify them.

[0022] [Table 1]

[0023] The plastics in inlet flow 101 may be supplied in a variety of different forms. In smaller operations, the plastics may be in the form of a powder. In larger operations, the plastics may be in the form of pellets, such as pellets with a particle size of 1 to 5 millimeters (mm). In further embodiments, the plastics may be supplied as shredded or ground products. Furthermore, the plastics in inlet flow 101 may be natural, synthetic, or semi-synthetic polymers. In various embodiments, the plastics in inlet flow 101 may include waste plastics, off-specification manufacturing products, new plastic products, unused plastic products, and combinations thereof.

[0024] Plastic thermal decomposition The plastic pyrolysis unit 50 converts the plastic inlet stream 101 into gaseous products, liquid products, and solid products. The liquid products are provided as an outflow from the plastic pyrolysis unit 50 through the plastic pyrolysis oil outlet 52 as a flow of plastic pyrolysis oil 102. The flow of gaseous products is widely shown in various drawings as an exhaust gas flow 106. The gaseous products in the exhaust gas flow 106 may include various species such as hydrogen and hydrocarbon gases (C1-C4), carbon monoxide (CO), carbon dioxide (CO2), and other acidic gases. The generated solid material is widely shown in various drawings as a solid flow 108.

[0025] The specific reactor used as the plastic pyrolysis unit 50 may be of a different type and is not limited for the purposes of this disclosure. Those skilled in the art will recognize that typical types of reactors that can be used to perform the function of the plastic pyrolysis unit 50 include tank reactors, rotary furnaces, packed bed reactors, bubbling reactors, and circulating fluidized bed reactors. In one or more embodiments, the pyrolysis of the plastic raw material in the inlet flow 101 is carried out at a temperature of 300 to 1000°C, with or without a pyrolysis catalyst. In various further embodiments, the plastic pyrolysis unit 50 may operate with low severity at temperatures below 450°C, with high severity at temperatures above 450°C, with temperatures of 300 to 450°C, with temperatures of 450 to 1000°C, with temperatures of 450 to 750°C, with temperatures of 600 to 1000°C, or with temperatures of 750 to 1000°C. In various embodiments, the plastic pyrolysis unit 50 may operate at pressures ranging from 1 to 100 bar (0.1 to 10 MPa), 1 to 50 bar (0.1 to 5 MPa), 1 to 25 bar (0.1 to 2.5 MPa), or 1 to 10 bar (0.1 to 1 MPa). Furthermore, in various embodiments, the residence time of the plastic raw material in the plastic pyrolysis unit 50 may be 1 to 3600 seconds, 60 to 1800 seconds, or 60 to 900 seconds.

[0026] Catalytic cracking feed stream In one or more embodiments, the flow of plastic pyrolysis oil 102 from the plastic pyrolysis unit 50 may be mixed with a refined fraction. Referring to Figure 2, schematic diagrams of one or more generalized embodiments of the present disclosure are presented in which a secondary hydrocarbon flow 104 is mixed with the plastic pyrolysis oil 102 before being introduced into the FCC unit 130. Specifically, the composition of the plastic pyrolysis oil in the catalytic cracking feed flow 103 supplied to the FCC unit 130 may vary from 0.1 mass percent (mass%) to 100 mass%, with the remainder being the secondary hydrocarbon flow 104. In various embodiments, the composition of the plastic pyrolysis oil in the catalytic cracking feed stream 103 supplied to the FCC unit 130 may include 0.l to 100% by mass of plastic pyrolysis oil, 20 to 100% by mass of plastic pyrolysis oil, 40 to 100% by mass of plastic pyrolysis oil, 60 to 100% by mass of plastic pyrolysis oil, 80 to 100% by mass of plastic pyrolysis oil, or substantially 100% by mass of plastic pyrolysis oil. In one or more embodiments, the secondary hydrocarbon stream 104 may be a conventional FCC feedstock stream such as hydrogenation cracker bottom, virgin or hydrotreated vacuum diesel, dehisced oil (DAO), coker diesel, circulating oil, vis-breaking oil, atmospheric residue, etc.

[0027] Referring to Figure 3, in one or more embodiments, the plastic pyrolysis oil 102 may be supplied to a demetallation operation 60 to remove metallic components from the plastic pyrolysis oil 102 and generate a flow of demetallated plastic pyrolysis oil 105. Therefore, the catalytic cracking feed flow 103 would contain demetallated plastic pyrolysis oil 105 instead of plastic pyrolysis oil 102. In one or more embodiments, it will be further recognized that the demetallation operation 60 may be positioned after the confluence of the plastic pyrolysis oil 102 and the secondary hydrocarbon flow 104, such that both components of the plastic pyrolysis oil 102 and the secondary hydrocarbon flow 104 undergo demetallation before being introduced into the FCC unit 130.

[0028] In one or more embodiments, the demetallation operation 60 may be catalytic hydrogenation demetallation. U.S. Patent No. 8,491,779, cited herein, teaches the integration of catalytic hydrogenation demetallation (HDM) into a purification process. The HDM process is carried out in the presence of a catalyst and hydrogen. Furthermore, in one or more embodiments, the hydrogen used may be derived from a downstream process. HDM is generally carried out at 370 to 450°C and a pressure of 30 to 200 bar (3 to 20 MPa). See also U.S. Patent No. 5,417,846, cited herein, and U.S. Patents No. 4,976,848, 4,657,664, 4,166,026, and 3,891,541, all cited herein, which teach HDM.

[0029] In one or more embodiments, the demetallation operation 60 may be solvent demetallation. The solvent demetallation process converts the metal-containing hydrocarbons in the treated flow into an asphaltene flow of the solvent demetallation unit. Details of the solvent demetallation process are taught in U.S. Patent No. 7,566,394, which is herein by reference.

[0030] fluidized bed reactor Herein, embodiments of the FCC unit 130 and processes and methods incorporating the FCC unit 130 are described. In the exemplary embodiments, the FCC unit 130 may be a downer FCC unit 130a, as described below with reference to Figure 4, or a riser FCC unit 130b, as described below with reference to Figure 5. Both the downer FCC unit 130a and the riser FCC unit 130b include a fluidized bed reactor 113 such that a catalytic cracking feed stream 103 is at least partially cracked to produce a product stream 110.

[0031] Referring to the process diagram in Figure 4, a Downer FCC unit 130a may be used in the process described herein. The Downer FCC unit 130a comprises a reactor-separator unit 111, which includes a fluidized bed reactor 113 and a separation area 115. The Downer FCC unit 130a also comprises a catalyst regenerator 117 for regenerating spent catalyst. The catalyst will generally pass through the catalyst regenerator 117, circulate back to the fluidized bed reactor 113, and return to the catalyst regenerator 117.

[0032] During operation of the Downer FCC unit 130a, the catalytic cracking feed stream 103 is introduced into the fluidized bed reactor 113 as feed through the transfer line 119. In some embodiments, the catalytic cracking feed stream 103 may be introduced into the fluidized bed reactor 113 along with steam or other suitable gas to atomize the feed. A certain amount of heated new or high-temperature regenerated solid cracking catalyst particles from the catalyst regenerator 117 may also be transferred to a withdrawal well or hopper (not shown) at the top of the fluidized bed reactor 113. The new catalyst may be heated by an energy source or by contact with the regenerated catalyst particles. The regenerated catalyst may be heated by the heat generated from the oxidation reaction during coke removal. The amount of catalyst may be sufficient to decompose the catalytic cracking feed stream 103 to the desired product profile. The catalyst particles may be transferred to the catalyst inlet of the fluidized bed reactor 113 through a downward transfer line 121, such as a conduit or pipe, commonly referred to as a transfer line or standpipe. The high-temperature catalyst flow will be stable and ensure that the high-temperature catalyst is uniformly directed to the mixing area or feed injection area of ​​the fluidized bed reactor 113. In some embodiments, transfer lines 121, 119, or both are directed relative to the fluidized bed reactor 113 to introduce the catalyst and catalytic cracking feed flows 103 to the upper or top of the fluidized bed reactor 113, respectively.

[0033] The catalytic cracking feed stream 103 may be injected into the mixing area of ​​the fluidized bed reactor 113. For example, the catalytic cracking feed stream 103 may enter the fluidized bed reactor 113 through feed injection nozzles. In some embodiments, the feed injection nozzles may be positioned close to where the regenerated catalyst particles are introduced into the fluidized bed reactor 113. In some embodiments, for example, multiple injection nozzles may be used to assist in the complete and uniform mixing of the catalytic cracking feed stream 103 and the catalyst. The cracking reaction begins when the catalytic cracking feed stream 103 comes into contact with the high-temperature catalyst in the fluidized bed reactor 113. The reaction vapors of hydrocarbon cracking products, unreacted feed, and catalyst mixture flow rapidly through the rest of the fluidized bed reactor 113 into the rapid separation area 115 at the bottom of the reactor separator unit 111. The cracked and uncracked hydrocarbons of the product stream 110 may be directed through conduits or pipes 123 to conventional product recovery sections known in the art.

[0034] If temperature control is required, a rapid cooling injection may be provided near the bottom of the fluidized bed reactor 113, just before the separation zone 115. This rapid cooling injection can be used to rapidly reduce or stop the decomposition reaction and to control the decomposition severity, for example, to increase process flexibility.

[0035] The reaction temperature inside the fluidized bed reactor 113, which is the outlet temperature of the fluidized bed reactor 113, may be controlled by opening and closing a catalyst sliding valve (not shown) that controls the flow of regenerated catalyst from the catalyst regenerator 117 to the top of the fluidized bed reactor 113. At least some of the heat required for the endothermic decomposition reaction may be supplied by a regenerated catalyst that has heat acquired in the regeneration process in the catalyst regenerator 117. By changing the flow rate of the high-temperature regenerated catalyst, the operating severity or decomposition conditions inside the fluidized bed reactor 113 can be controlled to produce fuel products such as light olefin hydrocarbons and gasoline in desired yields.

[0036] For example, a downer FCC unit 130a in a reactor separator unit 111 may include a stripper 131 for separating fuel from spent catalyst. After passing through the stripper 131, the spent catalyst may be transferred to a catalyst regenerator 117. The catalyst from the separation area 115 flows into the lower section of the stripper 131, which includes a catalyst removal section into which a suitable stripping gas, such as vapor, is introduced via a transfer line 133. The stripper 131 may include several baffles or structured packing (not shown) through which the spent catalyst flowing downwards passes in counterflow with the flowing stripping gas. The upward-flowing stripping gas, typically vapor, is used to “strip” or remove any additional hydrocarbons remaining in the catalyst pores or between catalyst particles.

[0037] In the downer FCC unit 130a, the stripped or spent catalyst may be transported through transfer line 125, for example, by lift from combustion air supplied to the bottom of the catalyst regenerator 117 via transfer line 127. This spent catalyst may also be brought into contact with additional combustion air, undergoing controlled combustion, which burns off any coke accumulated on the spent catalyst. Flue gas is removed from the catalyst regenerator 117 through conduit 129. In the catalyst regenerator 117, the heat generated by the combustion of by-product coke may be transferred to the fluidized bed reactor 113 through the catalyst in transfer lines 121 and 122. This means that at least some of the thermal energy required for the endothermic decomposition reaction in the fluidized bed reactor 113 may be provided from the heat generated during catalyst regeneration in the catalyst regenerator 117.

[0038] Downer reactors generally have feed introduced at the top of the reactor and operate in a downward flow manner, resulting in shorter residence times compared to upward flow reactors (risers).

[0039] Generally, the operating conditions of the fluidized bed reactor 113 of the appropriate downer FCC unit 130a include a reaction temperature of from about 450°C to about 700°C, in certain embodiments from about 500°C to about 675°C, and in further embodiments from about 550°C to about 650°C; a reaction pressure of from about 1 kg / cm 2 to about 20 kg / cm 2 (from about 98 kPa to about 1.96 MPa), in certain embodiments from about 1 kg / cm 2 to about 10 kg / cm 2 (from about 98 kPa to about 980 kPa), and in further embodiments from about 1 kg / cm 2 to about 3 kg / cm 2 (from about 98 kPa to about 294 kPa); a contact time (in the reactor) of from about 0.1 second to about 30 seconds, in certain embodiments from about 0.1 second to about 20 seconds, and in further embodiments from about 0.1 second to about 10 seconds; and a catalyst-to-feed ratio on a mass basis of from about 3:1 to about 60:1, in certain embodiments from about 4:1 to about 50:1, and in further embodiments from about 6:1 to about 40:1. It should be noted that the flow rate of the catalyst entering the fluidized bed reactor 113 from the catalyst regenerator 117 divided by the flow rate of the catalytic cracking feed stream 103 entering the fluidized bed reactor 113 defines the catalyst-to-feed ratio of the downer FCC unit 130a.

[0040] Referring to the generalized process flow diagram of FIG. 5, a riser FCC unit 130b may be used in the system and process according to the present disclosure. The riser FCC unit 130b includes a reactor separator 211 having a fluidized bed reactor zone 213 and a separation zone 215. The fluidized bed reactor zone 213 includes a riser reactor 313 and a solid separation zone 314. It will be appreciated that the separation zone 215 further separates solids and reduces the likelihood of solids remaining in the product stream 110. The solid separation zone 314 may include a cyclone. The riser FCC unit 130b also includes a catalyst regenerator 217 for regenerating the spent catalyst.

[0041] The catalytic cracking feed stream 103 may be transported as feed through a transfer line 219 to the fluidized bed reactor area 213. In some embodiments, the catalytic cracking feed stream 103 may be encompassed in the transfer line 219 by steam or other suitable gas to atomize the feed. Atomizing the feed will facilitate mixing and close contact of the catalytic cracking feed stream 103 with heated new or regenerated solid cracking catalyst particles in a quantity sufficient for the desired cracking of the catalytic cracking feed stream 103 in the fluidized bed riser reactor 313. The catalyst particles may be transported from a catalyst regenerator 217 through a transfer line 221 to the fluidized bed reactor area 213. The catalytic cracking feed stream 103 and the cracking catalyst are brought into contact under conditions that form a suspension to be introduced into the fluidized bed reactor 312.

[0042] In a continuous process using riser FCC unit 130b, a mixture of cracking catalyst and catalytic cracking feed stream 103 moves upward through the fluidized bed riser reactor 313. In the fluidized bed riser reactor 313, high-temperature cracking catalyst particles catalytically crack hydrocarbon molecules by cleaving carbon-carbon bonds. The reaction vapors of hydrocarbon cracking products, unreacted feed, and catalyst mixture flow rapidly through the rest of the fluidized bed reactor area 213. As the reaction progresses, the reactants move upward through the riser.

[0043] During the reaction in the fluidized bed reactor area 213, more specifically in the riser reactor 313, the cracking catalyst may coke, as is common in the FCC process. In a coked catalyst, access to the active catalyst site is limited or absent. The reaction products from the riser FCC unit 130b may be separated from the coked catalyst using any suitable configuration known in the FCC unit, generally referred to as the separation area 215 within the riser FCC unit 130b. The separation area 215 may be located at the top of the reactor separator 211 above the solid separation area 314. The separation area 215 may include any suitable apparatus known to those skilled in the art, such as a cyclone. The reaction products may be drawn out as a product stream 110 through the transfer line 123.

[0044] Catalyst particles containing coke deposits from the fluid cracking of hydrocarbon feedstocks pass from the solid separation area 314, separation area 215, or both, through the transfer line 225 to the catalyst regenerator 217. In the catalyst regenerator 217, the coked catalyst comes into contact with a flow of oxygen-containing gas, such as pure oxygen or air, which enters the catalyst regenerator 217 through the transfer line 227. The catalyst regenerator 217 may be operated under known conditions and in known configurations in a typical FCC process. For example, the catalyst regenerator 217 may function as a fluidized bed generating regenerated exhaust gas containing combustion products discharged through the transfer line 229. The high-temperature regenerated catalyst may be transferred from the catalyst regenerator 217 through the transfer line 221 to the bottom of the fluidized bed reactor area 213 in the riser reactor 313 for mixing with the catalytic cracking feed flow 103 as described above.

[0045] Generally, the operating conditions for a suitable riser FCC unit 130b fluidized bed riser reactor 313 are a reaction temperature of approximately 450°C to approximately 700°C, in certain embodiments, approximately 500°C to approximately 675°C, and in further embodiments, approximately 550°C to approximately 650°C; approximately 1 kg / cm³ 2 From approximately 20 kg / cm 2 (Approximately 98 kPa to approximately 1.96 MPa), in a specific embodiment, approximately 1 kg / cm² 2 From approximately 10 kg / cm 2 (Approximately 98 kPa to approximately 980 kPa), in a further embodiment, approximately 1 kg / cm² 2 From approximately 3 kg / cm 2Examples include reaction pressures of approximately 98 kPa to 294 kPa; contact times (in the reactor) of approximately 0.1 seconds to 30 seconds, in certain embodiments, approximately 2 seconds to 20 seconds, and in further embodiments, approximately 5 seconds to 10 seconds; and catalyst-to-feed ratios of approximately 3:1 to 20:1, in certain embodiments, approximately 4:1 to 10:1, and in further embodiments, approximately 6:1 to 8:1. Note that the flow rate of catalyst from the catalyst regenerator 217 into the fluidized bed reactor area 213, divided by the flow rate of the catalytic cracking feed stream 103 entering the fluidized bed reactor area 213, defines the catalyst-to-feed ratio of the riser FCC unit 130b.

[0046] A catalyst suitable for a specific quantity and the desired product may be delivered to a fluid catalytic cracking reactor. In certain embodiments, an FCC catalyst mixture, including an FCC base cracking catalyst (fluid cracking base catalyst) and an FCC catalyst additive (catalyst additive), is used in the FCC unit to promote olefin formation and minimize olefin consumption reactions, such as hydrogen transition reactions.

[0047] Specifically, substrates for FCC base cracking catalysts include natural or synthetic zeolites containing one or more Y-type zeolites, clays such as kaolin, montmorillonite, halloysite, and bentonite, and / or one or more inorganic porous oxides such as alumina, silica, boria, chromia, magnesia, zirconia, titania, and silica-alumina. In one or more embodiments, the FCC base cracking catalyst contains a superstable Y-type (USY) zeolite. A suitable FCC base cracking catalyst has a bulk density of 0.5 g / mL to 1.0 g / mL, an average particle size of 50 μm to 90 μm, and 50 m 2 / g to 350m 2 It may have a surface area of ​​0.05 mL / g and a pore volume of 0.5 mL / g.

[0048] A suitable FCC catalyst mixture may contain an FCC catalyst additive containing a shape-selective zeolite in addition to the FCC base cracking catalyst. The shape-selective zeolite referred to herein means a zeolite having a pore diameter smaller than that of a Y-type zeolite, so that only shape-restricted hydrocarbons can enter the zeolite through its pores. Examples of suitable shape-selective zeolite components include ZSM-5 zeolite, beta-zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO34 zeolite, and pentacyl-type aluminosilicates. Zeolites may be post-modified by incorporating one or more atoms into the backbone or into the zeolite cavities. These incorporated atoms may be titanium, zirconium, gallium, hafnium, boron, or a combination thereof. A combination of one or more of the shape-selective zeolites described in detail may also be used. The content of shape-selective zeolite in the FCC catalyst additive is generally in the range of about 20% to 70% by mass, and in certain embodiments, about 30% to 60% by mass.

[0049] Suitable FCC catalyst additives have a bulk density of 0.5 g / mL to 1.0 g / mL, an average particle size of 50 μm to 90 μm, and 10 m 2 / g to 200m 2 It may have a surface area of ​​0.01 mL / g and a pore volume of 0.3 mL / g.

[0050] In some embodiments, the FCC catalyst mixture may contain 60% to 95% by mass of FCC base cracking catalyst, based on the total mass of the FCC catalyst mixture. The FCC catalyst mixture may also contain 5% to 40% by mass of FCC catalyst additives, based on the total mass of the FCC catalyst mixture. If the mass fraction of the FCC base cracking catalyst in the FCC catalyst mixture is lower than 60% by mass, or if the mass fraction of the FCC catalyst additive in the FCC catalyst mixture is higher than 40% by mass, the conversion rate of the catalytic cracking feed stream 103 will be low, resulting in suboptimal yields of olefins with C2-C4 carbon atoms and distillate fuels. If the mass fraction of the FCC base cracking catalyst in the FCC catalyst mixture is higher than 95% by mass, or if the mass fraction of the FCC catalyst additive in the FCC catalyst mixture is lower than 5% by mass, the conversion rate of the catalytic cracking feed stream 103 may be high, but the yields of olefins with C2-C4 carbon atoms and distillate fuels may be suboptimal. [Examples]

[0051] Various embodiments of methods and systems for preparing plastic pyrolysis products as distillate fuels and light olefins by fluid catalytic cracking of plastic pyrolysis oil will become more apparent from the following examples. The examples are substantially illustrative and should not be understood as limiting the subject matter of this disclosure.

[0052] Example 1 A plastic feed 101 containing a mixture of HDPE, LDPE, PP, LLDPE, PS, and PET was fed into a plastic pyrolysis unit 50 and processed to produce gaseous, liquid, and solid fractions. The gaseous fraction contained C1-C4 hydrocarbon gases, as well as other polluting gases. For example, sulfur-containing polymers may release hydrogen sulfide, nitrogen-containing polymers may release ammonia and nitrogen, and oxygen-containing polymers may release water and oxygen. The solid fraction was produced from additives added to the plastics during the manufacturing process and generally produced as metallic components in parts per billion. The liquid fraction from the plastic pyrolysis unit 50 was provided as a stream of plastic pyrolysis oil 102. The concentrations of metallic components in the plastic pyrolysis oil are given in Table 2, where, for clarity, "<" means "less than". Further properties and composition of the plastic pyrolysis oil 102 are shown in Tables 3A and 3B.

[0053] [Table 2]

[0054] [Table 3A]

[0055] [Table 3B]

[0056] Example 2 The plastic pyrolysis oils whose properties are given in Tables 3A and 3B were fluids catalytically cracked in an ACE unit. These plastic pyrolysis oils were cracked at 520°C, 600°C, and 650°C in repeated trials with a residence time of 30 seconds and a nominal catalyst-to-oil ratio of 6. The catalysts used were CAN-FCC3 (USY zeolite post-modified with Ti and Zr, alumina binder, clay, and kaolin) and ZSM-5 zeolite additive. The catalyst-to-additive ratio was 9:1 on a mass%:mass% basis. Operating conditions and product yields are summarized in Table 4. Note that the catalysts and additives were deactivated before testing by steam treatment at 810°C for 6 hours in a separation unit.

[0057] [Table 4]

[0058] As can be seen from Table 4, as the decomposition temperature increased, the pyrolysis oil showed an increase in light olefins such as ethylene, propylene, and butylene, and a decrease in gasoline in the product stream. Specifically, the gasoline fraction decreased from 57.71% by mass to 33.50% by mass when the decomposition temperature was increased from 520°C to 650°C. Similarly, total light olefins (measured as the sum of ethylene, propylene, and butylene) increased from 25.41% by mass to 47.51% by mass when the decomposition temperature was increased from 520°C to 650°C. Thus, it was demonstrated that the products produced from plastic pyrolysis oil can be adjusted to obtain the desired products, at least in part, by adjusting the catalytic decomposition temperature.

[0059] Example 3 The plastic pyrolysis oil obtained in Example 1 was blended with the bottom flow of a hydrogenation cracker, a conventional FCC raw material. The composition and properties of the hydrogenation cracker bottom flow and the plastic pyrolysis oil are given in Table 5. Two blends were prepared with 5% by mass and 20% by mass of the plastic pyrolysis oil. These blends were the fluids catalytically cracked in an ACE unit. Tests were conducted at 520°C with a residence time of 30 seconds and a catalyst-to-oil ratio in the range of 5.6 to 6.1 (nominal 6). The catalysts used were CAN-FCC3 and ZSM-5 catalyst additives. The catalyst-to-additive ratio was 9:1 on a mass%:mass% basis. The operating conditions and product yields are summarized in Table 6. Note that the catalysts and additives were inactivated by steam treatment at 810°C for 6 hours in a separation unit before testing. For comparison, additional trials were completed with pure hydrogenation cracker bottom flow under the same operating conditions.

[0060] [Table 5]

[0061] [Table 6]

[0062] As can be seen from Table 6, the pyrolysis oil contributes to the production of ethylene, propylene, and butylene, as well as gasoline. While the production of ethylene, propylene, and butylene as mass percent of the resulting products is fairly stable, the production of gasoline increases significantly when plastic pyrolysis oil is used. Specifically, the gasoline fraction increased from 37.4% by mass to 57.7% by mass when the feed stream was changed from pure hydrogenation cracking bottom to pure plastic pyrolysis oil.

[0063] Based on the foregoing, it should be understood that various aspects of methods and systems for producing fuels and petrochemical raw materials from mixed plastic flows are now disclosed.

[0064] According to a first aspect of the present disclosure, a method for producing pyrolysis products from a mixed plastic flow includes the steps of (a) pyrolysis of plastic raw materials to produce a flow of plastic pyrolysis oil; (b) supplying a catalytic cracking feed stream containing the plastic pyrolysis oil and a catalyst from a catalyst regenerator to a fluidized bed reactor; (c) cracking the catalytic cracking feed stream in the fluidized bed reactor to produce a product flow and spent catalyst; and (d) transferring the spent catalyst to a catalyst regenerator and regenerating the catalyst in the catalyst regenerator, wherein the product flow comprises olefins having C2 to C4 carbon atoms and distillate fuel, and the plastic pyrolysis oil comprises a naphtha fraction representing hydrocarbons with boiling points from 36 to 180°C, a diesel fraction representing hydrocarbons with boiling points from 180 to 370°C, and a vacuum light oil fraction representing hydrocarbons with boiling points higher than 370°C.

[0065] A second embodiment includes a method according to the first embodiment, wherein the plastic pyrolysis oil contains oxygen, sulfur, nitrogen, and chlorine-containing compounds.

[0066] A third embodiment includes the method of the first or second embodiment, further comprising the step of supplying plastic pyrolysis oil to a demetallation step to remove metallic components from the plastic pyrolysis oil and generate a flow of demetallated plastic pyrolysis oil, wherein the catalytic cracking feed flow contains demetallated plastic pyrolysis oil instead of plastic pyrolysis oil.

[0067] A fourth embodiment includes any of the first to third embodiments, wherein the catalytic cracking feed stream further comprises a conventional FCC feed stream.

[0068] The fifth embodiment includes any of the first to fourth embodiments, wherein the distillate fuel includes gasoline.

[0069] A sixth embodiment includes any of the first to fifth embodiments of the method, wherein the method further includes a step of atomizing the catalytic cracking feed stream before supplying the catalytic cracking feed stream to a fluidized bed reactor.

[0070] The seventh aspect includes any method of the first to sixth aspects, wherein the spent catalyst is separated from the product stream within a separation area.

[0071] The eighth aspect includes any method of the first to seventh aspects, wherein the spent catalyst includes coke deposits.

[0072] The ninth aspect includes any method of the first to eighth aspects, wherein the fluidized bed reactor is operated at a reaction temperature of 450 to 700°C.

[0073] The tenth aspect includes any method of the first to ninth aspects, wherein the fluidized bed reactor is operated at a reaction pressure of 1 to 3 bar (0.1 to 0.3 MPa).

[0074] The eleventh embodiment includes any of the first to tenth embodiments, wherein the catalytic cracking feed stream has a residence time of 0.1 to 30 seconds in the fluidized bed reactor.

[0075] A twelfth aspect includes any of the first to eleventh aspects, wherein the flow rate of catalyst entering the fluidized bed reactor from the catalyst regenerator, divided by the flow rate of catalytic cracking feed entering the fluidized bed reactor, defines the catalyst-to-feed ratio, and the catalyst-to-feed ratio is in the range of 3:1 to 60:1.

[0076] The thirteenth embodiment includes any method of the first to twelfth embodiments, wherein the catalyst comprises a liquid cracking base catalyst and a catalytic additive.

[0077] A fourteenth aspect includes the method of the thirteenth aspect, wherein the liquid cracking base catalyst comprises USY zeolite.

[0078] The 15th aspect is a liquid cracking base catalyst having a bulk density of 0.5 g / ml to 1.0 g / ml, an average particle size of 50 micrometers to 90 micrometers, and 50 m 2 / g to 350m 2 The method comprises a 13th or 14th embodiment having a surface area of ​​ / g and a pore volume of 0.05 ml / g to 0.5 ml / g.

[0079] The sixteenth aspect includes any method of the thirteenth to fifteenth aspects, wherein the catalyst additive comprises a shape-selective zeolite.

[0080] The 17th aspect includes the method of the 16th aspect, wherein the shape-selective zeolite has an average pore diameter smaller than the average pore diameter of the Y-type zeolite.

[0081] The 18th aspect includes a method according to the 16th or 17th aspect, wherein the shape-selective zeolite is selected from the group consisting of ZSM-5 zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO34 zeolite, pentacyl-type aluminosilicate, and combinations thereof.

[0082] The 19th aspect is a shape-selective zeolite having a bulk density of 0.5 g / ml to 1.0 g / ml, an average particle size of 50 micrometers to 90 micrometers, and 10 m 2 / g to 200m 2 The method comprises any of the 16th to 18th embodiments, having a surface area of ​​ / g and a pore volume of 0.01 ml / g to 0.3 ml / g.

[0083] The 20th embodiment includes any method of the 13th to 19th embodiments, wherein the catalyst comprises 5% to 40% by mass of a catalyst additive.

[0084] A 21st embodiment includes the method of the 20th embodiment, wherein the catalyst additive comprises about 20% by mass to about 70% by mass of shape-selective zeolite.

[0085] The 22nd aspect includes any method of the first to 21st aspects, wherein the fluidized bed reactor is a downer.

[0086] The 23rd embodiment includes any method of the first to 21 embodiments, wherein the fluidized bed reactor is a riser.

[0087] The 24th embodiment includes any method of the first to 23 embodiments, wherein the plastic raw material includes a mixture of plastics of different compositions.

[0088] The 25th embodiment includes any of the first to 24 embodiments, wherein the thermal decomposition of the plastic raw material is carried out at a temperature of 300°C to 1000°C in the presence of a catalyst.

[0089] According to the 26th aspect, a system for processing a mixed plastic into plastic pyrolysis products includes an inlet flow containing the mixed plastic; a plastic pyrolysis unit fluidly communicating with the inlet flow and functioning to generate a flow of plastic pyrolysis oil from the inlet flow at a plastic pyrolysis oil outlet; a fluidized bed reactor including a catalyst inlet and a catalytic cracking feed inlet; a catalyst regenerator fluidly communicating with the catalyst inlet of the fluidized bed reactor; a catalyst circulating from the catalyst regenerator to the fluidized bed reactor and returning to the catalyst regenerator; and a catalytic cracking feed inlet located within the fluidized bed reactor that reacts with the catalyst, the catalytic cracking feed inlet being fluidly communicating with the plastic pyrolysis oil outlet such that the catalytic cracking feed inlet is located within the fluidized bed reactor and reacts with the catalyst to generate a product flow, the catalytic cracking feed inlet containing plastic pyrolysis oil, the plastic pyrolysis oil comprising a naphtha fraction representing hydrocarbons having a boiling point from 36 to 180°C, a diesel fraction representing hydrocarbons having a boiling point from 180 to 370°C, and a vacuum light oil fraction representing hydrocarbons having a boiling point higher than 370°C.

[0090] A 27th aspect includes a system of the 26th aspect, wherein the fluidized bed reactor is a riser.

[0091] A 28th embodiment includes a system of the 26th embodiment in which the fluidized bed reactor is a downer.

[0092] The 29th embodiment includes a system of any of the 26th to 28th embodiments, wherein the system further includes, in fluid communication with, a demetallation unit designed to remove metallic components from plastic pyrolysis oil and generate a flow of demetallated plastic pyrolysis oil, and the catalytic cracking feed flow contains demetallated plastic pyrolysis oil instead of plastic pyrolysis oil.

[0093] The 30th embodiment includes any system of the 26th to 29th embodiments, wherein the catalytic cracking feed inlet is in further fluid communication with the conventional FCC feed stream so that the conventional FCC feed stream and the plastic pyrolysis oil stream are mixed before entering the fluidized bed reactor.

[0094] The 31st embodiment includes a system of any of the 26th to 30th embodiments, wherein the spent catalyst is separated from the product stream in a separation area.

[0095] The 32nd embodiment includes a system of any of the 26th to 31st embodiments, wherein the fluidized bed reactor is operated at a reaction temperature of 450 to 700°C.

[0096] The 33rd embodiment includes any system of the 26th to 32nd embodiments, wherein the fluidized bed reactor is operated at a reaction pressure of 1 to 3 bar (0.1 to 0.3 MPa).

[0097] The 34th embodiment includes a system of any of the 26th to 33rd embodiments, wherein the catalytic cracking feed stream has a residence time of 0.1 to 30 seconds in the fluidized bed reactor.

[0098] The 35th embodiment includes a system of any of the 26th to 34th embodiments, wherein the catalyst comprises a liquid cracking base catalyst and a catalytic additive.

[0099] The 36th aspect includes the system of the 35th aspect, wherein the fluid cracking base catalyst comprises USY zeolite.

[0100] The 37th aspect is a liquid cracking base catalyst having a bulk density of 0.5 g / ml to 1.0 g / ml, an average particle size of 50 micrometers to 90 micrometers, and 50 m 2 / g to 350m 2 The system comprises a 35th or 36th embodiment having a surface area of ​​ / g and a pore volume of 0.05 ml / g to 0.5 ml / g.

[0101] The 38th embodiment includes a system of any of the 35th to 37th embodiments, wherein the catalyst additive comprises a shape-selective zeolite.

[0102] The 39th aspect includes a system of the 38th aspect, wherein the shape-selective zeolite has an average pore diameter smaller than the average pore diameter of the Y-type zeolite.

[0103] The 40th embodiment includes a system of the 38th or 39th embodiment in which the shape-selective zeolite is selected from the group consisting of ZSM-5 zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO34 zeolite, pentacyl-type aluminosilicate, and combinations thereof.

[0104] The 41st aspect is a shape-selective zeolite having a bulk density of 0.5 g / ml to 1.0 g / ml, an average particle size of 50 micrometers to 90 micrometers, and 10 m 2 / g to 200m 2 The system comprises any of the 38th to 40th embodiments, having a surface area of ​​ / g and a pore volume of 0.01 ml / g to 0.3 ml / g.

[0105] The 42nd embodiment includes a system of any of the 35th to 41st embodiments, wherein the catalyst comprises 5% to 40% by mass of a catalyst additive.

[0106] The 43rd embodiment includes any system of the 42nd embodiment, wherein the catalyst additive comprises about 20% by mass to about 70% by mass of shape-selective zeolite.

[0107] It should be apparent to those skilled in the art that various modifications and alterations can be made to the embodiments described without departing from the spirit and scope of the subject matter of the claims. Therefore, this specification is intended to encompass various modifications and alterations to the embodiments described, provided that such modifications and alterations fall within the scope of the accompanying claims and their equivalents.

[0108] Nouns include multiple objects unless the context clearly indicates otherwise.

[0109] Throughout this disclosure, ranges are given. It is also assumed that each discrete value encompassed by those ranges is included. In addition, the ranges that would be formed by each discrete value encompassed by the explicitly disclosed ranges are also assumed. For brevity, the same is not explicitly shown after each disclosed range, and a current general notation is given.

[0110] As used in this disclosure and the accompanying claims, the words “comprise,” “has,” and “include,” and all their grammatical variations, are intended to have an open, non-restrictive meaning, each without precluding any additional elements or steps. Preferred embodiments of the present invention are described below in separate sections. Embodiment 1 In a method for producing thermal decomposition products from a mixed plastic flow, (a) A process of generating a flow of plastic pyrolysis oil by thermally decomposing plastic raw materials, (b) A step of supplying the catalytic cracking feed stream containing the plastic pyrolysis oil and the catalyst from the catalyst regenerator to the fluidized bed reactor, (c) A step of decomposing the catalytic cracking feed stream in the fluidized bed reactor to produce a product stream and a spent catalyst, and (d) A step of transferring the used catalyst to the catalyst regenerator and regenerating the catalyst in the catalyst regenerator, Includes, The aforementioned product flow is C 2 ~C 4 It includes olefins having the number of carbon atoms and distillate fuels, The method for producing the plastic pyrolysis oil comprises a naphtha fraction representing hydrocarbons having a boiling point of 36 to 180°C, a diesel fraction representing hydrocarbons having a boiling point of 180 to 370°C, and a vacuum light oil fraction representing hydrocarbons having a boiling point higher than 370°C. Embodiment 2 The method further includes a step of supplying the plastic pyrolysis oil to a demetallation step to remove metal components from the plastic pyrolysis oil and generate a flow of demetallated plastic pyrolysis oil, The method according to Embodiment 1, wherein the catalytic cracking supply flow includes the demetallized plastic cracking oil instead of the plastic cracking oil. Embodiment 3 The method according to Embodiment 1 or 2, wherein the catalytic cracking feed stream further includes a conventional fluid catalytic cracking feed stream. Embodiment 4 The method according to any one of Embodiments 1 to 3, wherein the fluidized bed reactor is operated at a reaction temperature of 450 to 700°C, the fluidized bed reactor is operated at a reaction pressure of 1 to 3 bar (0.1 to 0.3 MPa), and the catalytic cracking feed stream has a residence time of 0.1 to 30 seconds in the fluidized bed reactor. Embodiment 5 The method according to any one of Embodiments 1 to 4, wherein the flow rate of the catalyst entering the fluidized bed reactor from the catalyst regenerator, divided by the flow rate of the catalytic cracking feed flow entering the fluidized bed reactor, defines the catalyst-to-feed ratio, and the catalyst-to-feed ratio is in the range of 3:1 to 60:1. Embodiment 6 The method according to any one of Embodiments 1 to 3, wherein the catalyst comprises a liquid cracking base catalyst and a catalytic additive. Embodiment 7 The method according to Embodiment 6, wherein the fluid cracking base catalyst comprises USY zeolite. Embodiment 8 The method according to Embodiment 6 or 7, wherein the catalyst additive comprises a shape-selective zeolite. Embodiment 9 In a system for processing mixed plastics into plastic pyrolysis products, Inlet flow containing mixed plastics, A plastic pyrolysis unit that is in fluid communication with the inlet flow and functions to generate a flow of plastic pyrolysis oil from the inlet flow at the plastic pyrolysis oil outlet, Fluidized bed reactor including catalyst inlet and catalytic cracking feed inlet, A catalyst regenerator that is in fluid communication with the catalyst inlet of the fluidized bed reactor, The catalyst that is circulated from the catalyst regenerator to the fluidized bed reactor and returns to the catalyst regenerator, A catalytic cracking feed stream, which is arranged in the fluidized bed reactor and reacts with the catalyst, Includes, The catalytic cracking supply inlet is in fluid communication with the plastic pyrolysis oil outlet such that the catalytic cracking supply flow, which reacts with the catalyst to generate a product flow, is located inside the fluidized bed reactor. The catalytic decomposition supply stream includes the plastic pyrolysis oil, The plastic pyrolysis oil system comprises a naphtha fraction representing hydrocarbons with boiling points from 36 to 180°C, a diesel fraction representing hydrocarbons with boiling points from 180 to 370°C, and a vacuum diesel fraction representing hydrocarbons with boiling points higher than 370°C. Embodiment 10 The system according to embodiment 9, wherein the fluidized bed reactor is a riser. Embodiment 11 The system according to embodiment 9, wherein the fluidized bed reactor is a downer. Embodiment 12 The system according to any one of embodiments 9 to 11, further comprising in fluid communication a demetallation unit configured to remove metallic components from the plastic pyrolysis oil and generate a flow of demetallated plastic pyrolysis oil, wherein the catalytic cracking feed flow comprises the demetallated plastic pyrolysis oil instead of the plastic pyrolysis oil. Embodiment 13 The system according to any one of Embodiments 9 to 12, wherein the catalyst comprises a fluid cracking base catalyst and a catalytic additive. Embodiment 14 The system according to Embodiment 13, wherein the aforementioned fluid cracking base catalyst comprises USY zeolite. Embodiment 15 The system according to embodiment 13 or 14, wherein the catalyst additive comprises a shape-selective zeolite. [Explanation of Symbols]

[0111] 50 Plastic Pyrolysis Units 52 Plastic pyrolysis oil outlet 60 Demetallization process 101 Inlet flow 102 Plastic pyrolysis oil 103 Catalytic Cracking Feed Stream 104 Secondary hydrocarbon flow 105 Demetallized plastic pyrolysis oil 106 Exhaust gas flow 108 Solid flow 110 Product logistics 111 Reactor Separator Unit 113 Fluidized bed reactor 115, 215 separation area 117, 217 Catalyst regenerator Transfer lines 119, 121, 122, 125, 127, 133, 219, 221, 225 123 Conduits, pipes 130 FCC units 130a Downer FCC Unit 130b Riser FCC Unit 131 Stripper 213 Fluidized Bed Reactor Area 313 Fluidized Bed Riser Reactor 314 Solids Separation Area

Claims

1. In a method for producing thermal decomposition products from a mixed plastic flow, (a) A step of performing thermal decomposition of unclassified mixed plastic raw materials to produce a flow of plastic thermal decomposition oil containing at least one type of metal component, (b) A step of supplying a catalytic cracking feed stream and a catalyst from a catalyst regenerator to a fluidized bed reactor, wherein the catalytic cracking feed stream includes plastic pyrolysis oil supplied directly from a plastic pyrolysis unit without removing the at least one metal component from the plastic pyrolysis oil. (c) A step of decomposing the catalytic cracking feed stream in the fluidized bed reactor to produce a product stream and a spent catalyst, and (d) A step of transferring the used catalyst to the catalyst regenerator and regenerating the catalyst in the catalyst regenerator, Includes, The product flow is C ２ ~C ４ It includes olefins having the number of carbon atoms and distillate fuels, The method for producing the plastic pyrolysis oil comprises a naphtha fraction representing hydrocarbons having a boiling point of 36 to 180°C, a diesel fraction representing hydrocarbons having a boiling point of 180 to 370°C, and a vacuum light oil fraction representing hydrocarbons having a boiling point higher than 370°C.

2. The method according to claim 1, wherein the plastic pyrolysis oil contains oxygen, sulfur, nitrogen, and chlorine-containing compounds.

3. The method according to claim 1, wherein the catalytic cracking feed stream further comprises a conventional fluid catalytic cracking raw material stream.

4. The method according to any one of claims 1 to 3, wherein the fluidized bed reactor is operated at a reaction temperature of 450 to 700°C, the fluidized bed reactor is operated at a reaction pressure of 1 to 3 bar (0.1 to 0.3 MPa), and the catalytic cracking feed stream has a residence time of 0.1 to 30 seconds in the fluidized bed reactor.

5. The method according to any one of claims 1 to 3, wherein the flow rate of the catalyst entering the fluidized bed reactor from the catalyst regenerator, divided by the flow rate of the catalytic cracking feed flow entering the fluidized bed reactor, defines the catalyst-to-feed ratio, and the catalyst-to-feed ratio is in the range of 3:1 to 60:

1.

6. The method according to any one of claims 1 to 3, wherein the catalyst comprises a liquid cracking base catalyst and a catalytic additive.

7. The method according to claim 6, wherein the fluid cracking base catalyst comprises USY zeolite.

8. The method according to claim 6, wherein the catalyst additive comprises a shape-selective zeolite selected from the group consisting of ZSM-5 zeolite, beta zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO34 zeolite, pentacyl-type aluminosilicate, and combinations thereof.

9. In a system for processing mixed plastics into plastic pyrolysis products, Inlet stream containing unclassified mixed plastics, A plastic pyrolysis unit that is in fluid communication with the inlet flow and functions to generate a flow of plastic pyrolysis oil containing at least one metal component from the inlet flow at the plastic pyrolysis oil outlet, Fluidized bed reactor including catalyst inlet and catalytic cracking feed inlet, A catalyst regenerator that is in fluid communication with the catalyst inlet of the fluidized bed reactor, The catalyst that is circulated from the catalyst regenerator to the fluidized bed reactor and returns to the catalyst regenerator, A catalytic cracking feed stream, which is arranged in the fluidized bed reactor and reacts with the catalyst, Includes, The catalytic cracking supply inlet is in fluid communication with the plastic pyrolysis oil outlet such that the catalytic cracking supply flow, which reacts with the catalyst to generate a product flow, is located inside the fluidized bed reactor. The catalytic cracking supply stream includes the plastic pyrolysis oil supplied directly from the plastic pyrolysis unit without removing the at least one metal component from the plastic pyrolysis oil. The plastic pyrolysis oil system comprises a naphtha fraction representing hydrocarbons with a boiling point of 36 to 180°C, a diesel fraction representing hydrocarbons with a boiling point of 180 to 370°C, and a vacuum diesel fraction representing hydrocarbons with a boiling point higher than 370°C.

10. The system according to claim 9, wherein the fluidized bed reactor is a riser.

11. The system according to claim 9, wherein the fluidized bed reactor is a downer.

12. The system according to any one of claims 9 to 11, wherein the catalyst comprises a liquid cracking base catalyst and a catalytic additive.

13. The system according to claim 12, wherein the fluid cracking base catalyst comprises USY zeolite.

14. The system according to claim 12, wherein the catalyst additive comprises a shape-selective zeolite selected from the group consisting of ZSM-5 zeolite, beta zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO-34 zeolite, pentacyl-type aluminosilicate, and combinations thereof.

15. The shape-selective zeolite has a bulk density of 0.5 g / ml to 1.0 g / ml, an average particle size of 50 micrometers to 90 micrometers, and 10 m ２ / g to 200m ２ The system according to claim 14, having a surface area of ​​0.01 ml / g and a pore volume of 0.01 ml / g to 0.3 ml / g.

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