Petrochemical raw material production methods

Abstract

To provide a production method of a petrochemical feedstock by which an existing petrochemical refining facility can be used as it is in the case of producing the petrochemical feedstock from a mixture containing a plurality of kinds of resins and the petrochemical feedstock can be efficiently produced regardless of the kinds of resins contained in the mixture.SOLUTION: A production method of a petrochemical feedstock includes a resin dissolving step of obtaining a resin solution by dissolving a resin other than a specific resin without dissolving the specific resin from a mixture containing a plurality of kinds of resins, and a step of treating an oil feedstock containing the resin solution in a petrochemical refining facility. In the resin dissolving step, a solvent is selected in which a relative energy difference based on a Hansen solubility parameter to the specific resin is greater than 1 and a relative energy difference based on a Hansen solubility parameter to a resin other than the specific resin is 1 or less, and the mixture is brought into contact with the solvent to dissolve the resin other than the specific resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing petrochemical feedstocks. [Background technology]

[0002] The development of recycling technology for waste plastics has become an important issue in recent years, in view of the increase in waste and the effective use of limited resources. Methods for recycling waste plastics are broadly divided into three categories: material recycling, which reuses waste plastics as they are, chemical recycling, which chemically decomposes waste plastics to recover basic chemical raw materials such as monomers, and thermal recycling, which recovers thermal energy from waste plastics.

[0003] Among these, material recycling and chemical recycling are desirable from the perspective of reducing the environmental burden, as they can convert waste plastics into raw materials for products and reuse them, thereby curbing consumption of limited natural resources and reducing the amount of waste sent to landfills through circular use of resources.

[0004] In material recycling, waste plastics are turned into raw materials such as flakes or pellets, which are then melted and molded, and reused as resin materials for the same or different plastic products. In order to meet the quality standards for resin materials, it is necessary to remove foreign matter and dirt and basically make the plastics into the same type. In material recycling, if different types of waste plastics are mixed into the collected waste plastics, the properties of the recycled plastics will deteriorate, so technology is required to separate the collected waste plastics with high precision.

[0005] In chemical recycling, waste plastics are converted into other chemical substances and reused, for example by pyrolyzing them at high temperatures to produce chemical raw materials such as synthetic gas or decomposed oil, or by chemically decomposing them to produce monomers. Compared to material recycling, it is often possible to recycle waste plastics even if they contain a mixture of different types of plastics or contain foreign matter or dirt.

[0006] As a chemical recycling method, Patent Document 1 discloses a method for cracking a hydrocarbon polymer (resin) in a fluid catalytic cracking unit. Specifically, the method discloses a resin cracking method characterized in that a mixture of a resin and a hydrocarbon oil selected from fluid catalytic cracking gasoline, light cracked gas oil, heavy cracked gas oil, and cracked residual oil is mixed with a fluid catalytic cracking feedstock oil and supplied to a fluid catalytic cracking unit. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2002-294251 A Summary of the Invention [Problem to be solved by the invention]

[0008] In the method described in Patent Document 1, it is considered that the hydrocarbon oil heated to about 300°C is mixed with a slurry containing resin to melt the resin. This method requires a dedicated dissolving tank for melting the resin at a high temperature of about 300°C and a dedicated line for transferring the high-temperature molten liquid to the fluid catalytic cracking apparatus, making it difficult to use an existing fluid catalytic cracking apparatus as it is. Furthermore, when the slurry contains multiple resins, it is necessary to melt all the resins, which may result in a large amount of resin-derived impurities that adversely affect the fluid catalytic cracking apparatus and fluid catalytic cracking catalyst being mixed in. In this case, it is necessary to separate and select the resin before preparing the slurry, which is not efficient.

[0009] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a method for producing petrochemical raw materials which, when producing petrochemical raw materials from a mixture containing multiple types of resins, allows the use of existing oil refining facilities as they are and enables efficient production of petrochemical raw materials regardless of the types of resins contained in the mixture. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention has the following aspects. [1] A method for producing petrochemical raw materials from a mixture containing multiple types of resins, comprising: a resin dissolving step of obtaining a resin solution by dissolving resins other than the specific resin without dissolving a specific resin from the mixture containing multiple types of resins; and a step of treating a feedstock oil containing the resin solution in an oil refining apparatus, in which the resin dissolving step comprises selecting a solvent having a relative energy difference based on the Hansen solubility parameter of more than 1 for the specific resin and a relative energy difference based on the Hansen solubility parameter of 1 or less for the resins other than the specific resin, and contacting the mixture with the solvent to dissolve the resins other than the specific resin. [2] The method for producing a petrochemical raw material according to [1], wherein the specific resin contains a chlorine element. [3] The method for producing a petrochemical raw material according to [1] or [2], wherein the mixture contains at least one resin selected from the group consisting of polyethylene, polypropylene, polystyrene, and polyvinyl chloride. [4] The method for producing a petrochemical raw material according to any one of [1] to [3], wherein the specific resin is polyvinyl chloride, and the resin other than the specific resin includes at least one resin selected from the group consisting of polyethylene, polypropylene, and polystyrene. [5] The method for producing a petrochemical raw material according to any one of [1] to [4], wherein the solvent contains two or more types of solvents. [6] The method for producing a petrochemical feedstock according to any one of [1] to [5], wherein the oil refinery is a fluid catalytic cracking unit. Effect of the Invention

[0011] According to the present invention, when producing petrochemical raw materials from a mixture containing multiple types of resins, it is possible to provide a method for producing petrochemical raw materials that allows the use of existing oil refining facilities as is and that enables efficient production of petrochemical raw materials regardless of the types of resins contained in the mixture. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram showing how to determine the Hansen solubility parameter value and the interaction radius. [Diagram 2] 1 is a schematic diagram showing the distance between the solubility parameter values ​​of two substances, substance 1 and substance 2. [Diagram 3] FIG. 2 is a schematic diagram showing a case where the relative energy difference between substance 1 and substance 2 based on the Hansen solubility parameters is within 1. [Figure 4] FIG. 2 is a schematic diagram showing a case where the relative energy difference between substance 1 and substance 2 based on the Hansen solubility parameters is greater than 1. [Diagram 5] 1 is a schematic diagram showing the relationship between the Hansen solubility parameter of a solvent L, the Hansen spheres S(PA1) and S(PA2) of resins PA1 and PA2, and the Hansen spheres S(PB1) and S(PB2) of resins PB1 and PB2. [Figure 6] FIG. 1 is a block diagram showing the configuration of an apparatus used in a fluid catalytic cracking reaction for treating a feedstock oil containing a resin-dissolved liquid according to one embodiment of the present invention. [Figure 7] FIG. 1 is a configuration diagram showing the configuration of a refining facility for refining cracked oil according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The following describes in detail the embodiments of the present invention. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to these contents and can be modified and implemented within the scope of its gist.

[0014] The method for producing a petrochemical raw material of the present embodiment is a method for producing a petrochemical raw material from a mixture containing multiple types of resins, and includes a resin dissolving step of obtaining a resin solution from the mixture containing the multiple types of resins by dissolving resins other than the specific resin while not dissolving a specific resin, and a step of treating a raw material oil containing the resin solution in an oil refining unit. The resin dissolving step and the step of treating the feed oil containing the resin solution in an oil refining plant will be described in detail below.

[0015] <Resin melting process> The resin dissolving step of the present embodiment is a step of dissolving a resin from a mixture containing a plurality of types of resins, in which a specific resin is not dissolved, but resins other than the specific resin are dissolved. Specifically, the resin dissolving step includes selecting a solvent having a relative energy difference based on the Hansen solubility parameter for the specific resin of more than 1 and a relative energy difference based on the Hansen solubility parameter for resins other than the specific resin of 1 or less, and contacting the mixture with the solvent to dissolve the resins other than the specific resin. Hereinafter, the method for determining the Hansen solubility parameter and the relative energy difference will be described.

[0016] <Hansen Solubility Parameter> The Hansen solubility parameter (hereinafter simply referred to as "HSP") is based on the idea that two substances with similar intermolecular interactions are likely to dissolve in each other. The HSP is composed of the energy derived from intermolecular dispersion forces (δd), the energy derived from intermolecular dipole interactions (δp), and the energy derived from intermolecular hydrogen bonds (δh). These three parameters can be considered as coordinates in a three-dimensional space (Hansen space).

[0017] The HSP value of an evaluation sample whose HSP value is unknown can be calculated by the following method. HSP value (δd m , δp m , δh m ) in three-dimensional space, multiple pure substances (substances consisting of one type of compound) with known HPS values ​​are plotted in the Hansen Solubility Parameter space. The Hansen Sphere is then specified based on the solubility of the evaluation sample in the pure substances, and the central value of the Hansen Sphere is determined to calculate the HSP value of the evaluation sample (Hansen Sphere method). The HSP value of the evaluation sample can also be calculated from information on the average molecular structure using the atomic group contribution method. In both the Hansen sphere method and the group contribution method, the HSP value of the evaluation sample can be calculated using, for example, computer software Hansen Solubility Parameters in Practice (HSPiP). In the case of the Hansen ball method, the evaluation sample may be a pure substance or a mixture.

[0018] The method of determining the central values ​​of the Hansen sphere, that is, the HSP values ​​(δdm, δpm, δhm), will be described with reference to FIG. First, the HSP values ​​of about 15 to 30 pure substances having known HSP values ​​are plotted in the three-dimensional space illustrated in FIG. 1 (coordinate axes are the dispersion force term δd, the dipole-dipole force term δp, and the hydrogen bond force term δh). At this time, for example, pure substances that show solubility in the evaluation sample are indicated with a circle, and pure substances that do not show solubility in the evaluation sample are indicated with an X, as shown in Figure 1. Next, based on the plotted solubilities of the evaluation samples, the Hansen sphere S (shown as a sphere in Figure 1) is determined to be the one with the smallest radius among the imaginary spheres that include the pure substances that show solubility (shown with a circle in Figure 1) and do not include the pure substances that do not show solubility (shown with an X in Figure 1). The radius of the Hansen sphere S (the above-mentioned minimum radius) becomes the interaction radius R0 that dissolves the pure substance shown by the circle in the figure and indicates compatibility, and the central value (δdm, δpm, δhm) of the obtained Hansen sphere S becomes the HSP value of the evaluation sample. The HSP value of the above pure substance used to calculate the Hansen sphere is, for example, a dispersion force term δd of 10 to 25 MPa. 1 / 2 The dipole-dipole force term δp is 0 to 20 MPa. 1 / 2 The hydrogen bond term δh is about 0 to 20 MPa. 1 / 2 That's about it. In addition, since solubility depends on temperature, when determining the Hansen ball, it is preferable to carry out the solubility test at a temperature at which the resin actually dissolves.

[0019] Next, Figure 2 is a schematic diagram showing the distance between the solubility parameters of two substances, substance 1 and substance 2. First, the Hansen spheres of substance 1 and substance 2 are determined using the method described above. When the HSP values ​​of substance 1 are (δd1, δp1, δh1) and the HSP values ​​of substance 2 are (δd2, δp2, δh2), the distance between the HSP values ​​of the two substances (hereinafter also simply referred to as "Ra") can be calculated using the following formula 1. Ra = {4 × (δd1-δd2) 2 +(δp1-δp2) 2 +(δh1-δh2) 2} 0.5 formula 1

[0020] The relative energy difference (hereinafter, simply referred to as "RED") of substance 1 to substance 2 based on the Hansen solubility parameters can be calculated by the following formula 2, where the interaction radius of substance 2 is R0. RED=Ra / R0Equation 2

[0021] Figure 3 is a schematic diagram showing a case where the RED based on the Hansen solubility parameters of substance 1 for substance 2 is within 1. In this case, as shown in Figure 3, the HSP values ​​(δd1, δp1, δh1) of substance 1 are located inside the Hansen sphere S2 of substance 2 (including the surface of the sphere).

[0022] Figure 4 is a schematic diagram showing a case where RED based on the Hansen solubility parameters of substance 1 in substance 2 exceeds 1. In this case, as shown in Figure 4, the HSP values ​​(δd1, δp1, δh1) of substance 1 are located outside S2 of the Hansen sphere of substance 2 (not including the surface of the sphere).

[0023] The method for dissolving a resin according to the present embodiment is a method for dissolving a resin other than a specific resin from a mixture containing a plurality of types of resins. Specifically, the method for dissolving a resin includes selecting a solvent having a relative energy difference based on the Hansen solubility parameter for the specific resin of more than 1 and a relative energy difference based on the Hansen solubility parameter for the resin other than the specific resin of not more than 1, and contacting the mixture with the solvent to dissolve the resin other than the specific resin. The specific resin may be one or more kinds. The resin other than the specific resin may be one or more kinds. Hereinafter, the specific resin will be referred to as “resin A,” and any resin other than the specific resin will be referred to as “resin B.” In this embodiment, from a mixture containing resin A and resin B, only resin B is dissolved.

[0024] <How to select a solvent> Resin A is Resin P A1 ~P Ax Resin B is made of Resin P B1 ~P By x represents the number of types of resins constituting Resin A and is an integer of 1 or more. y represents the number of types of resins constituting Resin B and is an integer of 1 or more. The value of x is not particularly limited, but from the viewpoint of facilitating the selection of the solvent, it is preferably 1 to 3, and more preferably 1 to 2. The value of y is not particularly limited, but from the viewpoint of facilitating the selection of the solvent, it is preferably 1 to 5, and more preferably 1 to 3. The value of x+y is not particularly limited, but from the viewpoint of facilitating the selection of the solvent, it is preferably 2 to 8, and more preferably 2 to 5.

[0025] By the above-mentioned method, resin P A1 ~P Ax Hansen Ball S (P A1 )~S(P Ax ) are calculated for each of the Hansen spheres S(P A1 )~S(P Ax ) from resin P A1 ~P Ax HSP value [δd(P A1), δp(P A1 ), δh(P A1 )]~[δd(P Ax ), δp(P Ax ), δh(P Ax )] and the interaction radius R0(P A1 )~R0(P Ax ) respectively. Similarly, P B1 ~P By Hansen Ball S (P B1 )~S(P By ) are calculated for each of the Hansen spheres S(P B1 )~S(P By ) from resin P B1 ~P By HSP value [δd(P B1 ), δp(P B1 ), δh(P B1 )]~[δd(P By ), δp(P By ), δh(P By )] and the interaction radius R0(P B1 )~R0(P By ) respectively.

[0026] The HSP values ​​of the selected solvent L are assumed to be [δd(L), δp(L), δh(L)]. Resin P A1 ~P Ax HSP value [δd(P A1 ), δp(P A1 ), δh(P A1 )]~[δd(P Ax ), δp(P Ax ), δh(P Ax )] are substituted into (δd2, δp2, δh2) in the above formula 1, and the HSP values ​​of solvent L [δd(L), δp(L, δh(L)] are substituted into (δd1, δp1, δh1) in the above formula 1, and Ra(P A1 )~Ra(P Ax ) are calculated respectively. A1 )~Ra(P Ax ) is a function of δd(L), δp(L), and δh(L). And, P A1 ~P Ax The interaction radius R0(P A1)~R0(P Ax ) and the obtained Ra(P A1 )~Ra(P Ax ) into the above formula 2, and RED(P A1 )~RED(P Ax ) is calculated. The obtained RED(P A1 )~RED(P Ax ) is a function of δd(L), δp(L), and δh(L).

[0027] Similarly, Resin P B1 ~P By HSP value [δd(P B1 ), δp(P B1 ), δh(P B1 )]~[δd(P By ), δp(P By ), δh(P By )] are substituted into (δd2, δp2, δh2) in the above formula 1, and the HSP values ​​of solvent L [δd(L), δp(L, δh(L)] are substituted into (δd1, δp1, δh1) in the above formula 1, and Ra(P B1 )~Ra(P By ) are calculated respectively. B1 )~Ra(P By ) is a function of δd(L), δp(L), and δh(L). And, P B1 ~P By The interaction radius R0(P B1 )~R0(P By ) and the obtained Ra(P B1 )~Ra(P By ) into the above formula 2, and RED(P B1 )~RED(P By ) is calculated. The obtained RED(P B1 )~RED(P By ) is a function of δd(L), δp(L), and δh(L).

[0028] In this embodiment, RED(P A1 )~RED(P Ax ) are greater than 1 and RED(P B1 )~RED(P By) is less than or equal to 1. Figure 5 shows the HSP value of solvent L when x is 2 and y is 2, and the HSP value of resin P A1 , P A2 Hansen Ball S (P A1 ), S(P A2 ) and Resin P B1 , P B2 Hansen Ball S (P B1 ), S(P B2 5, the HSP value [δd(L), δp(L), δh(L)] of the solvent L is A1 , P A2 Hansen Ball S (P A1 ), S(P A2 ) outside (excluding the surface of the sphere) and resin P B1 , P B2 Hansen Ball S (P B1 ), S(P B2 ) (including the surface of the sphere).

[0029] In this embodiment, RED(P A1 )~RED(P Ax ) are all greater than 1, preferably 2.5 or greater, and more preferably 3 or greater. A1 )~RED(P Ax ) is greater than (or equal to) the lower limit, resin P constituting resin A is A1 ~P Ax The dissolution of RED(P A1 )~RED(P Ax ) is not particularly limited, but is, for example, 10 or less.

[0030] In this embodiment, RED(P B1 )~RED(P By ) are all equal to or less than 1, preferably equal to or less than 0.9, and more preferably equal to or less than 0.8. B1 )~RED(P By ) is not more than the upper limit, the resin P constituting the resin B B1 ~P ByThe dissolution of RED(P B1 )~RED(P By The lower limit of ) is not particularly limited, but is, for example, 0.1 or more.

[0031] HSP value of solvent L and resin P A1 ~P Ax The distance between each HSP value is Ra(P A1 )~Ra(P Ax ) is RED(P A1 )~RED(P Ax ) is not particularly limited as long as it is greater than 1, but for example, 5 MPa 1 / 2 More than 10MPa is preferable. 1 / 2 The above is more preferable.

[0032] HSP value of solvent L and resin P B1 ~P By The distance between each HSP value is Ra(P B1 )~Ra(P By ) is RED(P B1 )~RED(P By ) is not particularly limited as long as it is 1 or less, but for example, 8 MPa 1 / 2 Less than 5MPa is preferable. 1 / 2 The following is more preferred:

[0033] RED(P B1 )~RED(P By In order to select a solvent L having an HSP value [δd(L), δp(L), δh(L)] such that all of the above are 1 or less, when y is 2 or more, B1 ~P By Hansen Ball S (P B1 )~S(P By ) all have overlapping portions. That is, resin P with y=c and y=d is randomly selected from resin B. Bc , P Bd When you select P Bc HSP value [δd(P Bc ), δp(P Bc ), δh(P Bc )] and P Bd HSP value [δd(PBd ), δp(P Bd ), δh(P Bd )] into (δd1, δp1, δh1) and (δd2, δp2, δh2) in the above formula 1, respectively, to obtain Ra(P Bc -P Bd ) and P Bc The interaction radius R0(P Bc ) and P Bd The interaction radius R0(P Bd ) satisfies the following formula 3. {R0(P Bc )+R0(P Bd )}≧Ra(P Bc -P Bd ) Equation 3

[0034] Resin P that does not satisfy formula 3 B1 ~P By In this case, the resin B may be appropriately selected. B1 ~P By An arbitrary resin is removed from the above so as to satisfy the formula 3. In this case, the removed resin constitutes resin A.

[0035] <Resin> The type of resin contained in the mixture of the present embodiment is not particularly limited, and examples thereof include polyolefin resins such as polyethylene, polypropylene, polybutadiene, and polymethylpentene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polystyrene resins such as polystyrene, acrylonitrile-styrene resin, and acrylonitrile-butadiene-styrene resin; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polytrimethylene terephthalate; and polyvinyl triacetate. Examples of suitable resins include: cellulose; polycarbonate; urethane resins such as polyurethane and acrylic-modified polyurethane; polymethylpentene; polysulfone resins such as polyethersulfone, polyphenylsulfone, and polysulfone; polyetheretherketones such as polyetherketone, polyetheretherketone, and polyetherketoneketone; polyphenylene sulfide; polyimide-based resins such as polyetherimide and polyimide; polyamide-based resins such as polyamide 6, polyamide 66, and polyamide 11; acrylic resins; fluorine-based resins; phenolic resins; epoxy resins; melamine resins; urea resins; unsaturated polyester resins; alkyd resins, etc. The mass average molecular weight of the resin contained in the mixture of this embodiment is not particularly limited as long as the effects of the present invention can be obtained, but may be, for example, 10,000 to 100,000 or 100,000 to 1,000,000.

[0036] The resin of this embodiment is solid at 30° C. or less. The form of the resin is not particularly limited as long as the effects of the present invention can be obtained, but examples include a molded body molded into a package such as a PET bottle, a pellet form, a flake form, etc. The size of the resin is not particularly limited as long as the effects of the present invention can be obtained, but the major axis is about 1 to 100 mm. From these resins, resin A and resin B can be arbitrarily selected according to the application described below.

[0037] <Solvent> The solvent in this embodiment is RED(P A1)~RED(P Ax ) are greater than 1 and RED(P B1 )~RED(P By) has an HSP value of 1 or less. Examples of the solvent include esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, benzyl acetate, benzyl benzoate, ethyl benzoate, and butyl benzoate; ketones such as acetone, diisobutyl ketone, ethyl methyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, and N-methyl-2-pyrrolidone; diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, and dimethoxyethane. Ethers such as 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole, and 2-methoxytetrahydropyran; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, and 2,2,2-trifluoroethane. Examples of the organic solvent include alcohols such as ethanol and 2,2,3,3-tetrafluoro-1-propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether; organic solvents having an amide group such as N,N-dimethylformamide, acetamide, and N,N-dimethylacetamide; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate, propylene carbonate, and 1,2-glycerol carbonate; halogenated hydrocarbons such as methylene chloride, chloroform, tetrachloroethane, and chlorobenzene; and hydrocarbons such as n-pentane, cyclohexane, n-hexane, 1-octadecene, benzene, toluene, xylene, 2,2,4-trimethylpentane, cyclohexene, ethylbenzene, d-limonene, and l-limonene.

[0038] The solvent may be used alone or in combination of two or more kinds. That is, the solvent of the present embodiment may be a mixture of two or more kinds of solvents (hereinafter, also referred to as a "mixed solvent"). Examples of the mixed solvent include a mixture of two or more kinds of the solvents listed above.

[0039] Other mixed solvents include petroleum fractions obtained in the refining process of crude oil, such as atmospheric residual oil, vacuum gas oil, vacuum residual oil, desulfurized atmospheric residual oil, desulfurized vacuum gas oil, light cracked gas oil, and heavy cracked gas oil; vegetable oils, such as soybean oil, rapeseed oil, sunflower oil, corn oil, cottonseed oil, peanut oil, olive oil, palm oil, sesame oil, rice oil, and orange oil, and waste oils thereof. The above-mentioned solvents may also be mixed into these mixed solvents.

[0040] When a mixed solvent is used as the solvent in this embodiment, the HSP value of the mixed solvent may be determined by the method described above, or may be determined as a weighted average of the HSP values ​​of the solvents constituting the mixed solvent as described below. The mixed solvent L is composed of solvents L1 to L z The ratio of the volumes of the solvents L1 to L2 to the total volume of all the solvents before mixing the mixed solvent z The content ratios of V(L1) to V(L z ) Solvent L1~L z The HSP values ​​of [δd(L1), δp(L1, δh(L1)]~[δd(L z ), δp(L z ), δh(L z )], then the HSP values ​​of the mixed solvent, [Δd(L), Δp(L), Δh(L)], can be calculated by the following formulas 4 to 6.

[0041]

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[0042]

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[0043]

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[0044] In this embodiment, the HSP value of the mixed solvent is preferably determined by the above formulas 4 to 6.

[0045] The boiling point of the solvent in this embodiment is not particularly limited as long as the effects of the present invention can be obtained, but may be, for example, 80 to 700°C, 150 to 500°C, or 200 to 400°C. The density of the solvent in this embodiment is not particularly limited as long as the effects of the present invention can be obtained, but is, for example, 0.70 to 1.5 g / cm 3 Also, 0.80~1.2g / cm 3 Also, 0.85 to 1.2 g / cm 3 That's fine too.

[0046] <Combination of Resin A, Resin B and Solvent L> In this embodiment, it is preferable that resin A contains a chlorine element. Also, in this embodiment, it is preferable that resin B and solvent L do not contain a chlorine element. When the raw oil containing the resin solution obtained in the resin dissolving step of this embodiment is treated in an oil refinery, if the resin solution contains a chlorine element, hydrogen chloride may be generated during the treatment process in the oil refinery, which may corrode the oil refinery. Since resin A contains a chlorine element and resin B and solvent L do not contain a chlorine element, the resulting solution does not contain a chlorine element, making it possible to prevent corrosion of the oil refinery. The resin contained in the mixture of the present embodiment is preferably at least one resin selected from the group consisting of polyethylene, polypropylene, polystyrene, and polyvinyl chloride.

[0047] When the resins constituting resin A are polystyrene or polyvinyl chloride, and the resins constituting resin B are polyethylene or polypropylene, examples of solvents that have a relative energy difference based on the Hansen solubility parameters with respect to resin A of more than 1 and a relative energy difference based on the Hansen solubility parameters with respect to resin B of 1 or less include benzene, cyclohexane, and ethylbenzene.

[0048] When the resins constituting resin A are polypropylene and polyvinyl chloride, and the resins constituting resin B are polyethylene and polystyrene, examples of solvents that have a relative energy difference based on the Hansen solubility parameters with respect to resin A of more than 1 and a relative energy difference based on the Hansen solubility parameters with respect to resin B of 1 or less include butyl benzoate, benzyl acetate, and orange oil.

[0049] When the resins constituting resin A are polyethylene and polyvinyl chloride, and the resins constituting resin B are polypropylene and polystyrene, an example of a solvent that has a relative energy difference based on the Hansen solubility parameters with respect to resin A of more than 1 and a relative energy difference based on the Hansen solubility parameters with respect to resin B of 1 or less is chlorobenzene.

[0050] When the resins constituting resin A are polyethylene and polypropylene, and the resins constituting resin B are polystyrene and polyvinyl chloride, examples of solvents that have a relative energy difference based on the Hansen solubility parameters with respect to resin A of more than 1 and a relative energy difference based on the Hansen solubility parameters with respect to resin B of 1 or less include N-methylpyrrolidone and N,N-dimethylacetamide.

[0051] When the resin constituting resin A is polypropylene and the resin constituting resin B is polyethylene, polystyrene, or polyvinyl chloride, examples of a solvent having a relative energy difference based on the Hansen solubility parameters of more than 1 with respect to resin A and a relative energy difference based on the Hansen solubility parameters of 1 or less with respect to resin B include a mixed solvent of ethyl benzoate, 2-methoxytetrahydropyran, 81% by mass of d-limonene and 19% by mass of 1,2-glycerol carbonate, a mixed solvent of 64% by mass of d-limonene and 36% by mass of dimethylformamide, a mixed solvent of 58% by mass of tetrahydrofuran and 42% by mass of cyclohexanone, a mixed solvent of 62% by mass of ethyl acetate and 38% by mass of benzyl benzoate, and a mixed solvent of 58% by mass of methyl ethyl ketone and 42% by mass of benzyl benzoate.

[0052] When the resin constituting resin A is polyvinyl chloride and the resin constituting resin B is polyethylene, polypropylene, or polystyrene, examples of solvents that have a relative energy difference based on the Hansen solubility parameters with respect to resin A of more than 1 and a relative energy difference based on the Hansen solubility parameters with respect to resin B of 1 or less include 1,1,1,2-tetrachloroethane, d-limonene, o-xylene, toluene, etc.

[0053] (Conditions for dissolving resin) In the method for dissolving a resin of this embodiment, the ratio of the mixture to the total mass of the solvent is not particularly limited as long as it is capable of dissolving resin B, but may be, for example, 1 to 50 mass %, 1 to 40 mass %, or 1 to 30 mass %. In the method for dissolving a resin of this embodiment, the ratio of resin B to the total mass of the solvent is not particularly limited as long as resin B can be dissolved in the solvent, but may be, for example, 1 to 20 mass%, 1 to 18 mass%, or 1 to 15 mass%. The temperature at which resin B is dissolved is not particularly limited as long as resin B can be dissolved; however, the temperature may be 15 to 100°C, 20 to 90°C, or 30 to 80°C, as long as resin A does not soften or melt. When dissolving Resin B, it is preferable to carry out stirring, ultrasonic treatment, or the like.

[0054] In the method for dissolving a resin according to the present embodiment, it is preferable that the entire resin B is dissolved, but 80 to 100 mass % or 90 to 100 mass % of the total mass of resin B may be dissolved. In the method for dissolving a resin of this embodiment, it is preferable that resin A is not dissolved, but resin A may be dissolved in an amount of 0 mass % or more and less than 1 mass %, or 0 to 0.5 mass %, relative to the total mass of resin A.

[0055] For example, if the resin contains a heteroatom such as a halogen element, the amount of the resin dissolved can be confirmed by measuring the content of the heteroatom in the solution. The amount of the resin dissolved that does not contain a heteroatom can be measured by a conventionally known analysis method, and examples of the analysis method include infrared spectroscopy, gas chromatography mass spectrometry, and gel filtration permeation chromatography.

[0056] <Process of treating raw oil containing resin solution in an oil refining plant> In this embodiment, the feedstock oil containing the resin-dissolved liquid obtained in the above-mentioned resin dissolving step is treated in an oil refining plant to produce petrochemical feedstock.

[0057] The petroleum refining unit is not particularly limited, but examples thereof include atmospheric distillation units, vacuum distillation units, fluid catalytic cracking units, heavy oil thermal cracking units, direct desulfurization units, indirect desulfurization units, kerosene and gas oil desulfurization units, catalytic reforming units, isomerization units, and hydrocracking units. Of these, units that crack hydrocarbons are preferred, and fluid catalytic cracking units, heavy oil thermal cracking units, and hydrocracking units are more preferred, with fluid catalytic cracking units being the most preferred. Hereinafter, a detailed description will be given of a process for treating a feedstock oil containing a resin-dissolved liquid in an oil refinery, taking as an example a case where the oil refinery is a fluid catalytic cracking unit.

[0058] In this embodiment, the feed oil containing the resin solution obtained in the above-mentioned resin dissolution process is supplied to a fluid catalytic cracking unit and subjected to contact treatment with a fluid catalytic cracking catalyst to produce a cracked oil containing a petrochemical feedstock.

[0059] <Fluid catalytic cracking equipment> The fluid catalytic cracking unit (hereinafter also referred to as "FCC unit") of this embodiment includes a riser that produces a cracked oil containing a petrochemical feedstock by contacting a feedstock containing the resin solution with a fluid catalytic cracking catalyst to crack the feedstock, a reaction tower that separates the cracked oil from the fluid catalytic cracking catalyst, a regeneration tower that regenerates the catalyst by burning carbon (coke) deposited on the separated fluid catalytic cracking catalyst, and a refining facility. Hereinafter, an example of the FCC unit of this embodiment will be described with reference to FIG. 6. FIG. 6 is a configuration diagram showing an example of the FCC unit. The FCC unit 1 includes a riser 10, a reaction tower 20, a regeneration tower 30, and a refining facility 40.

[0060] (Riser) The riser 10 is an apparatus for producing a cracked oil containing a petrochemical feedstock by contacting a feedstock containing a resin solution with an FCC catalyst and cracking the feedstock. The riser 10 is connected to, for example, a regenerated catalyst transfer line 34 for supplying a fluid catalytic cracking catalyst regenerated in a regenerator 30, a fluid catalytic cracking feedstock supply line 11 for supplying a feedstock oil (hereinafter also referred to as "fluid catalytic cracking feedstock") to be subjected to a normal fluid catalytic cracking reaction, and a resin solution supply line 51 for supplying a resin solution. In addition, a preheating device 12 and a preheater 52 are provided on the fluid catalytic cracking feedstock supply line and the resin solution supply line, respectively. Furthermore, the upper part of the riser 10 is connected to a reaction tower 20.

[0061] (Reaction tower) The reaction tower 20 is a device for separating the cracked oil from the fluid catalytic cracking catalyst. The reaction tower 20 includes, for example, a cyclone 21, a cracked oil discharge line 22, a stripper 23, and a post-reaction catalyst transfer line 24. The upper part of the cyclone 21 is connected to the cracked oil discharge line 22. Furthermore, the bottom of the stripper 23 and the lower part of the regeneration tower 30 are connected by the post-reaction catalyst transfer line 24.

[0062] (Regeneration Tower) The regenerator 30 is an apparatus for regenerating the catalyst by burning the coke on the fluid catalytic cracking catalyst separated in the reaction tower 20. The regenerator 30 includes, for example, an air blower 31, an air grid 32, a cyclone 33, a regenerated catalyst transfer line 34, and an exhaust gas line 35. The bottom of the regenerator and the air blower 31 are connected via the air grid 32. Furthermore, a cyclone 33 is installed at the top of the regenerator, and the upper part of the cyclone 33 is connected to the exhaust gas line 35.

[0063] (Refining equipment) The refining equipment 40 is an equipment that separates cracked oil containing petrochemical raw materials produced in a fluid catalytic cracking unit into gas components containing a large amount of petrochemical raw materials and heavy components containing uncracked products and polymerized products. As shown in FIG. 7, the refining equipment includes, for example, a distillation tower 41, a line 42, a distillation tower 43, a line 44, a distillation tower 45, a line 46, a distillation tower 47, a line 48, an aromatics extraction unit 60, a line 61, a line 62, a naphtha cracker 70, and a catalytic reforming unit 80. The distillation tower 41 is connected to the reaction tower 20 via a cracked oil discharge line 22 near the middle of the tower. The distillation tower 43 is connected to the top of the distillation tower 41 via a line 42 near the middle of the tower. The distillation tower 45 is connected to the bottom of the distillation tower 43 via a line 44 near the middle of the tower. The distillation tower 47 is connected to the top of the distillation tower 45 via a line 46 near the middle of the tower. The aromatics extraction unit 60 is connected to the bottom of the distillation tower 45 via a line 48. The naphtha cracker 70 is connected to the aromatics extraction unit 60 via line 61. The catalytic reformer 80 is connected to the aromatics extraction unit 60 via line 62.

[0064] The distillation towers 41, 43, 45, and 47 may be distillation towers known in the art depending on the objects to be separated, as described below. The aromatics extraction unit 60 may be aromatics extraction units known in the art depending on the objects to be separated, as described below. Similarly, the naphtha cracker 70 and the catalytic reformer 80 may be naphtha crackers and catalytic reformers known in the art. Although detailed structures of the reflux line, preheater, bottoms withdrawal line, effluent withdrawal line, etc. of the distillation column are not shown in Fig. 7, as described above, the distillation column has a structure known in the art. The same is true for the aromatics extraction unit, naphtha cracker, and catalytic reformer.

[0065] <Resin dissolution tank> The resin dissolving tank 50 is an apparatus for carrying out the above-mentioned resin dissolving step of contacting a mixture containing a plurality of types of resins with a solvent to dissolve the resin B. An oil storage tank can be used as the resin dissolving tank. The resin dissolving tank 50 is connected to the riser 10 through a resin dissolving liquid supply line 51. The resin dissolving tank 50 is preferably equipped with a stirrer, a dissolving tank heater, a solid matter removal device, and the like.

[0066] <Fluid catalytic cracking catalyst> The FCC catalyst of the present embodiment preferably contains a zeolite such as a zeolite having a sodalite cage structure, β zeolite, or ZSM-5 type zeolite, and more preferably contains a zeolite having a sodalite cage structure. The content of the zeolite relative to the total mass of the FCC catalyst is preferably from 25 to 45 mass%, more preferably from 28 to 42 mass%, and further preferably from 30 to 40 mass%.

[0067] In this specification, zeolite having a sodalite cage structure means a zeolite having a sodalite cage structure, i.e., an aluminum and silicon tetrahedron as a basic unit, with each vertex of a three-dimensional regular octahedral crystal structure formed by sharing oxygen at the vertices with aluminum or silicon, and having voids formed by a tetradecahedral crystal structure defined by four-membered rings, six-membered rings, etc., and having various pore structures, skeletal densities, and channel structures by changing the locations and methods at which these sodalite cages are bonded to each other.

[0068] The zeolite having the sodalite cage structure may be one or more selected from sodalite, A-type zeolite, EMT, X-type zeolite, Y-type zeolite, stabilized Y-type zeolite, etc., and is preferably stabilized Y-type zeolite.

[0069] Stabilized Y-type zeolite is synthesized using Y-type zeolite as a starting material, and is more resistant to deterioration of crystallinity than Y-type zeolite. It is generally produced by subjecting Y-type zeolite to steam treatment at high temperatures several times, and then, if necessary, treating it with a mineral acid such as hydrochloric acid, a base such as sodium hydroxide, a salt such as calcium fluoride, or a chelating agent such as ethylenediaminetetraacetic acid. The stabilized Y-type zeolite obtained by the above method can be used in a form that has been ion-exchanged with a cation selected from hydrogen, ammonium, or polyvalent metals. Also, as the stabilized Y-type zeolite, a heat shock crystalline aluminosilicate zeolite (see Japanese Patent No. 2544317), which has a higher stability, can be used.

[0070] The FCC catalyst of the present embodiment preferably further contains a binder, a clay mineral, and the like. An example of the binder is silica sol. By using silica sol, the moldability during granulation of the FCC catalyst is improved, and it is possible to easily form the catalyst into a spherical shape. In addition, the flowability and abrasion resistance of the granulated FCC catalyst can be easily improved. The content of the binder relative to the total mass of the FCC catalyst is preferably 15 to 35 mass%, more preferably 18 to 32 mass%, and even more preferably 20 to 30 mass%.

[0071] Examples of clay minerals include montmorillonite, kaolinite, halloysite, bentonite, attapulgite, bauxite, etc. In the FCC catalyst of this embodiment, known inorganic oxide fine particles used in normal FCC catalysts, such as silica, silica-alumina (excluding the above-mentioned zeolite), alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, and silica-magnesia-alumina, can be used in combination with the above clay minerals. The sum of the contents of the clay mineral and the inorganic oxide relative to the total mass of the FCC catalyst is preferably 35 to 55 mass%, more preferably 38 to 52 mass%, and further preferably 40 to 50 mass%. The content of the clay mineral relative to the total mass of the FCC catalyst is preferably 25 to 50 mass %, more preferably 30 to 45 mass %, and even more preferably 32 to 42 mass %.

[0072] The FCC catalyst of the present embodiment may also contain a zeolite stability improver. The zeolite stability improver has a function of suppressing the collapse of zeolite crystals. Examples of the zeolite stability improver include phosphorus-based zeolite stability improvers such as phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, aluminum monophosphate, and other water-soluble phosphates, and rare earth metal-based zeolite stability improvers such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, and holmium. When the FCC catalyst contains a zeolite stability improver, the content of the zeolite stability improver relative to the total mass of the FCC catalyst is preferably 0.1 to 5 mass%.

[0073] The FCC catalyst is granulated to a certain size and then used in the fluid catalytic cracking reaction. The particle size of the FCC catalyst is not particularly limited as long as it is a particle size that can be used in a normal fluid catalytic cracking reaction, but the particle size is preferably within the range of 20 to 150 μm. The particle size of the FCC catalyst can be measured, for example, by using a micro-type electromagnetic vibration sieve, Model M-2, manufactured by Tsutsui Rikagaku Kikai Co., Ltd.

[0074] <Method of manufacturing fluid catalytic cracking catalyst> The FCC catalyst of the present embodiment can be produced by a conventionally known method. When the FCC catalyst contains zeolite, a binder, a clay mineral, and a zeolite stability improver, it can be produced by drying a slurry containing a predetermined amount of each of the zeolite, the binder, the clay mineral, and the zeolite stability improver.

[0075] In this production method, first, an aqueous slurry containing zeolite, a binder, a clay mineral, and a zeolite stability improver is prepared. The solid content of the aqueous slurry is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. When the solid content of the aqueous slurry is within the above range, the amount of water evaporated during drying of the aqueous slurry becomes appropriate, and drying can be easily performed. In addition, the slurry can be easily transported without increasing its viscosity.

[0076] The aqueous slurry is then dried to obtain the microspheres. The aqueous slurry is preferably dried using a spray dryer under conditions of a gas inlet temperature of 200 to 600°C and a gas outlet temperature of 100 to 300°C.

[0077] In the present production method, the microspheres obtained by the above-mentioned drying treatment may be further subjected to washing treatment and ion exchange treatment by known methods, if necessary, to remove excess alkali metals and soluble impurities, etc., carried over from the various raw materials.

[0078] Specifically, the washing treatment can be carried out with water or aqueous ammonia. By washing with water or aqueous ammonia, the content of soluble impurities can be reduced.

[0079] Specifically, the ion exchange treatment can be carried out using an aqueous solution of an ammonium salt such as ammonium sulfate or ammonium sulfite, and this ion exchange can reduce the amount of alkali metals such as sodium and potassium remaining in the microspheres.

[0080] The above-mentioned washing treatment is usually carried out prior to the ion exchange treatment, but the ion exchange treatment may be carried out first, so long as the washing treatment and the ion exchange treatment are carried out suitably.

[0081] The above-mentioned washing treatment and ion exchange treatment are preferably carried out until the content of alkali metals and the content of soluble impurities are reduced to the desired levels or less. By reducing the content of alkali metals and the content of soluble impurities to the desired levels or less, the catalytic activity can be improved.

[0082] The microspheres preferably have an alkali metal content of 1.0% by mass or less, more preferably 0.5% by mass or less, and a soluble impurity content of 2.0% by mass or less, more preferably 1.5% by mass or less, based on the dry catalyst.

[0083] The microspheres that have been subjected to the above-mentioned washing and ion exchange treatments are preferably dried again at a temperature of 100 to 500° C. until the moisture content of the microspheres reaches 1 to 25% by mass. In this manner, the FCC catalyst of this embodiment can be produced.

[0084] <Fluid catalytic cracking reaction> In this embodiment, the fluid catalytic cracking reaction can be carried out by a method known in the art. The fluid catalytic cracking reaction can be carried out in an FCC unit by contacting a feedstock containing a resin solution with an FCC catalyst at a high temperature.

[0085] In this embodiment, the feedstock oil to be cracked contains a resin solution. Only the resin solution may be used as the feedstock oil, or the resin solution may be mixed with a fluid catalytic cracking feedstock oil to obtain the feedstock oil. The fluid catalytic cracking feedstock oil to be mixed with the resin solution is not particularly limited, and examples thereof include hydrocarbon oils (hydrocarbon mixtures) that are liquid at normal temperature and pressure.

[0086] Examples of the hydrocarbon oil include one or more selected from light oil fractions obtained by atmospheric or reduced pressure distillation of crude oil, atmospheric distillation residual oils, and reduced pressure distillation residual oils, and also include one or more selected from coker light oil, solvent deasphalted oil, solvent deasphalted asphalt, tar sands oil, shale oil, coal liquefied oil, GTL (Gas to Liquids) oil, vegetable oil, waste lubricating oil, waste edible oil, etc.

[0087] Furthermore, the fluid catalytic cracking feedstock oil used in the present embodiment may also include hydrotreated oil obtained by subjecting the above-mentioned hydrocarbon oil to hydrotreatment well known to those skilled in the art, i.e., hydrodesulfurization under high temperature and pressure in the presence of a hydrotreatment catalyst such as a Ni-Mo based catalyst, a Co-Mo based catalyst, a Ni-Co-Mo based catalyst, or a Ni-W based catalyst.

[0088] The cracking reaction of the feedstock oil in this embodiment can be carried out by continuously circulating an FCC catalyst in an FCC unit 1, which is usually composed of a vertically installed riser 10, a reaction tower 20, and a regenerator 30. In this specification, the term "fluid catalytic cracking unit" (FCC unit) also includes a residual oil fluid catalytic cracking unit (RFCC unit). That is, in this specification, the term "fluid catalytic cracking reaction" also includes a residual oil fluid catalytic cracking reaction.

[0089] The fluid catalytic cracking reaction carried out by the FCC unit will now be described in detail. A pumping fluid flows upward in the riser 10, and the FCC catalyst supplied from the regenerated catalyst transfer line 34 flows upward in the riser 10 together with the pumping fluid. The resin solution is heated to a predetermined temperature by the preheating device 52, steam is added, and then the resin solution is supplied to the riser 10 from the resin solution supply line 51. Similarly, fluid catalytic cracking feedstock may be heated to a predetermined temperature by the preheating device 12 and supplied to the riser 10 from the fluid catalytic cracking feedstock supply line 11. The feedstock containing the resin solution supplied to the riser 10 comes into contact with the FCC catalyst, and a cracking reaction occurs. The cracked oil and the FCC catalyst produced by the cracking reaction are transferred to the reaction tower 20. The concentration of the resin relative to the total mass of the resin solution supplied is not particularly limited as long as the effects of the present invention can be obtained, but may be, for example, 1 to 50 mass%, 5 to 40 mass%, or 5 to 30 mass%.

[0090] As the operating conditions of the riser 10, the reaction temperature is preferably 490 to 530°C, and more preferably 500 to 520°C. When the reaction temperature in the riser 10 is equal to or higher than the lower limit of the above range, the cracking reaction of the feedstock oil containing the resin solution proceeds, and the yield of the petrochemical feedstock is improved. When the reaction temperature in the riser 10 is equal to or lower than the upper limit of the above range, the amount of light gas such as dry gas produced by thermal cracking and the amount of coke produced can be reduced, and the yield of the petrochemical feedstock can be relatively easily increased, which is economical.

[0091] The reaction pressure is from normal pressure to 0.49MPa (5kg / cm2 ), and normal pressure to 0.29 MPa (3 kg / cm 2 Since the decomposition reaction is a reaction in which the number of moles of the product increases relative to the number of moles of the reactants, it is thermodynamically (equilibrium-wise) advantageous for the reaction pressure in the riser 10 to be 0.49 MPa or less.

[0092] The mass ratio of FCC catalyst / (resin dissolved solution + fluid catalytic cracking feedstock) is preferably 3 to 7, and more preferably 4 to 6. When the mass ratio of FCC catalyst / (resin dissolved solution + fluid catalytic cracking feedstock) in the riser 10 is equal to or higher than the lower limit of the above range, the catalyst concentration in the riser 10 can be kept at an appropriate level, and the cracking efficiency of the feedstock oil is improved. Even when the mass ratio of FCC catalyst / (resin dissolved solution + fluid catalytic cracking feedstock) in the riser 10 is equal to or lower than the upper limit of the above range, the cracking reaction of the feedstock oil proceeds effectively, and it becomes easier to proceed with the cracking reaction commensurate with the increase in catalyst concentration.

[0093] The ratio of the flow rate (KL / H) of the resin dissolved solution to the total flow rate [KL / H] of the resin dissolved solution supplied from the resin dissolved solution supply line 51 and the fluid catalytic cracking feed oil supplied from the fluid catalytic cracking feed oil supply line 11 ((resin dissolved solution / (fluid catalytic cracking feed oil+resin dissolved solution))×100%) is preferably 5 to 100%, more preferably 10 to 95%, and even more preferably 20 to 80%.

[0094] The cracked oil produced by the cracking of the feed oil in the riser 10 is supplied to the cyclone 21. The cyclone 21 separates the cracked oil from the FCC catalyst by using centrifugal force. The cracked oil is then discharged from the reaction tower 20 through the cracked oil discharge line 22 and transferred to the distillation tower 41.

[0095] The FCC catalyst separated by the cyclone 21 is supplied to a stripper 23. Steam, nitrogen, etc. are supplied to the stripper 23. In the stripper 23, the hydrocarbons on the FCC catalyst are removed by the steam, nitrogen, etc. Then, the FCC catalyst is discharged from the reaction tower 20 through a post-reaction catalyst transfer line 24 and transferred to a regeneration tower 30.

[0096] The temperature during the stripping treatment in the stripper 23 is usually 470 to 530° C., preferably 480 to 520° C., and more preferably 490 to 510° C. As the gas used for stripping, steam generated by a boiler, an inert gas such as nitrogen pressurized by a compressor, etc., and the like are used.

[0097] Air is supplied from an air blower 31 to an air grid 32, and then from the air grid 32 into the regenerator 30, whereby the coke on the FCC catalyst after stripping transferred to the regenerator 30 is burned, and the FCC catalyst is regenerated. The regenerated FCC catalyst and the exhaust gas generated by the combustion of the coke are separated by a cyclone 33. The regenerated FCC catalyst is discharged from the regenerator 30 through a regenerated catalyst transfer line 34 and supplied to the riser 10. The exhaust gas is discharged from the regenerator 30 through an exhaust gas line 35.

[0098] As for the operating conditions of the catalyst regenerator, the regeneration temperature is preferably 600 to 800°C, and more preferably 700 to 750°C. If the regeneration temperature in the catalyst regeneration tower is 600°C or higher, the coke is burned sufficiently and the catalyst activity is sufficiently restored. Also, if the regeneration temperature in the catalyst regeneration tower is 800°C or lower, the adverse effect on the equipment material is low.

[0099] The cracked oil is transferred from the reaction tower 20 to the distillation tower 41 via the cracked oil discharge line 22, and in the distillation tower 41, a fraction containing compounds having about 1 to 13 carbon atoms is distilled from the top of the tower, heavy cracked gas oil (HCO) and light cracked gas oil (LCO) are distilled from the middle of the tower, and fluid catalytic cracking residual oil (SLO) is distilled from the bottom of the tower. The fraction containing compounds having carbon numbers of about 1 to 13 is transferred from distillation column 41 to distillation column 43 via line 42, in which gas components are removed from the top of distillation column 43, and a fraction mainly composed of liquefied petroleum gas (LPG) and gasoline is obtained at the bottom of the column. The fraction mainly composed of LPG and gasoline is transferred from distillation tower 43 to distillation tower 45 via line 44, and in distillation tower 45, the fraction mainly composed of LPG is distilled from the top of the tower, and the fraction mainly composed of gasoline is obtained from the bottom of the tower. The fraction mainly composed of LPG is transferred from distillation column 45 to distillation column 47 via line 46. In distillation column 47, a fraction mainly composed of propylene, a petrochemical feedstock, is distilled from the top of the column, and a fraction mainly composed of butene, a petrochemical feedstock, is obtained from the bottom of the column. The fraction mainly composed of gasoline is transferred from the distillation tower 45 via line 48 to the aromatics extraction unit 60, where it is separated into a fraction mainly composed of aromatic compounds, which are petrochemical feedstocks, and a fraction mainly composed of gasoline from which the aromatic compounds have been removed. The fraction containing mainly gasoline from which the aromatic compounds have been removed is transferred via line 61 to a naphtha cracker 70, which produces a fraction containing mainly the petrochemical raw materials ethylene, propylene, and aromatic compounds. In addition, the fraction mainly composed of gasoline from which the aromatic compounds have been removed is transferred via line 62 to a catalytic reformer 80, which produces a fraction mainly composed of aromatic compounds, which are petrochemical feedstocks.

[0100] <Petrochemical raw materials> Examples of the petrochemical raw materials produced by the method for producing a petrochemical raw material of this embodiment include olefins having 3 to 8 carbon atoms, aromatic compounds, etc. Examples of the olefins having 3 to 8 carbon atoms include propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene, etc. Examples of the aromatic compounds include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, etc. EXAMPLES

[0101] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[0102] <Resin> · Polyvinyl chloride (Product name: KVC 933J-N, manufactured by Showa Chemical Industry Co., Ltd., density: 1.325 g / cm 3 ) · Polystyrene (Product name: Toyo Styrene GP G201C, manufactured by Toyo Styrene Co., Ltd., density: 1.040 g / cm 3 ) · Low-density polyethylene (Product name: Novatech LD LJ802, manufactured by Japan Polyethylene Corporation, density: 0.918 g / cm 3 ) Hereinafter, polyvinyl chloride will be represented as PVC, polystyrene as PS, and low-density polyethylene as LDPE (the same applies in Table 1). Since PVC, PS, and LDPE have different shapes and colors, in the examples described later, it is possible to visually determine which resin has dissolved.

[0103] <Solvent> The following solvents were used as solvents for dissolving the resin. · Light cracked light oil Light cracked light oil is a light fraction of the light oil fraction obtained by fluid catalytic cracking reaction (boiling point range: 175 to 365 °C). Hereinafter, light cracked light oil will be represented as LCO (the same applies in Table 1).

[0104] <Calculation of HPS value, R0, etc.> For the above resins, Hansen spheres were determined by the Hansen sphere method using HSPiP, and HSP values and R0 were obtained. Similarly, for the above solvents, Hansen spheres were determined by the Hansen sphere method using HSPiP, and HSP values were obtained. Note that the determination of solubility when obtaining Hansen spheres was based on 80 °C.

[0105] <Measurement of chlorine content> The chlorine concentration in the solutions obtained in Examples 1 and 2 described later was measured using a trace chlorine and sulfur analyzer (TCL-2100V, manufactured by Mitsubishi Chemical Analytic).

[0106] <Fluid catalytic cracking reaction> The FCC equilibrium catalyst containing stabilized Y-type zeolite as an active component, which was obtained by a long-term reaction in an actual fluid catalytic cracking apparatus, was packed into a boiling bed micro activity test apparatus (ACE-Model R+, manufactured by Kayser Technology). Using the feedstock oils of Examples 1 and 2 and Comparative Example 1 described below, a fluid catalytic cracking reaction was carried out at a reaction temperature of 510°C, a reaction time of 75 seconds, a mass ratio of FCC catalyst / feedstock oil of 6, and a regeneration temperature of the FCC catalyst of 700°C. The obtained cracked oil was analyzed by gas chromatographic distillation using an AC Simdis Analyzer manufactured by Agilent Technologies, and dry gas (C1, The amounts of products were analyzed: C2 compounds, LPG (C3, C4 compounds), gasoline (boiling point 27-190°C), LCO and HCO (boiling point over 190°C and up to 350°C), and SLO (boiling point over 350°C). The amount of coke produced was analyzed and calculated from the CO and CO2 concentrations in the regeneration tower. Furthermore, the components contained in dry gas, LPG, and gasoline were quantified by gas chromatography. The conversion rate was calculated by: (100%-yields (mass%) of LCO and HCO-yields (mass%)-yield (mass%) of SLO.

[0107] [Example 1] PVC was selected as resin A, LDPE was selected as resin B, and LCO was selected as the solvent. The HSP value of PVC and the HSP value of LCO were respectively substituted into (δd2, δp2, δh2) and (δd1, δp1, δh1) in the above formula 1 to obtain the HSP value distance (Ra(A)) between PVC and LCO. Furthermore, the relative energy difference RED(A) based on the Hansen solubility parameter of LCO for PVC was obtained from R0 and Ra(A) of PVC. Similarly, the HSP value of LDPE and the HSP value of LCO were respectively substituted into (δd2, δp2, δh2) and (δd1, δp1, δh1) in the above formula 1 to obtain the HSP value distance (Ra(B)) between LDPE and LCO. Furthermore, the relative energy difference RED(B) based on the Hansen solubility parameter of LCO for LDPE was obtained from R0 and Ra(B) of LDPE. As a result, RED(A) was greater than 1 and RED(B) was less than 1. 90g of LCO was added to a mixture of 10g of PVC and 10g of LDPE, and the mixture was stirred at 80°C for 60 minutes. Visual inspection of the dissolved state confirmed that the LDPE had completely dissolved, with the PVC remaining as a solid. The amount of chlorine in the solution is shown in Table 1. The solid PVC was subjected to solid-liquid separation, and the resulting resin solution was used as the feedstock for a fluid catalytic cracking reaction. The conversion rate, olefin yield, and aromatic compound yield are shown in Table 1. In the table, "yield" means mass %, and "Cn" means that the number of carbon atoms is n.

[0108] [Example 2] PVC was selected as resin A, PS was selected as resin B, and LCO was selected as the solvent. The HSP value of PVC and the HSP value of LCO were respectively substituted into (δd2, δp2, δh2) and (δd1, δp1, δh1) in the above formula 1 to obtain the HSP value distance (Ra(A)) between PVC and LCO. Furthermore, RED(A), which is the relative energy difference based on the Hansen solubility parameter of LCO for PVC, was obtained from R0 and Ra(A) of PVC. Similarly, the HSP value of PS and the HSP value of LCO were respectively substituted into (δd2, δp2, δh2) and (δd1, δp1, δh1) in the above formula 1 to obtain the HSP value distance (Ra(B)) between PS and LCO. Furthermore, RED(B), which is the relative energy difference based on the Hansen solubility parameter of LCO for PS, was obtained from R0 and Ra(B) of PS. As a result, RED(A) was greater than 1 and RED(B) was less than 1. 90g of LCO was added to a mixture of 10g of PVC and 10g of PS, and the mixture was stirred at 80°C for 60 minutes. Visual inspection of the dissolution state confirmed that the PS had completely dissolved, with the PVC remaining as a solid. The amount of chlorine in the solution is shown in Table 1. The solid PVC was separated into solid and liquid, and the resulting resin solution was used as feedstock for a fluid catalytic cracking reaction. The conversion rate, olefin yield, and aromatic compound yield are shown in Table 1.

[0109] [Comparative Example 1] A fluid catalytic cracking reaction was carried out using 100 g of LCO as the feedstock without using Resin A or Resin B. The conversion rate, olefin yield, and aromatic compound yield are shown in Table 1.

[0110] [Table 1]

[0111] In Examples 1 and 2, in which a solvent with a RED based on the Hansen solubility parameters for resin A of more than 1 and a RED based on the Hansen solubility parameters for resin B of 1 or less was selected, it was possible to dissolve only the target resin B without dissolving the PVC containing chlorine, which is thought to have a negative effect on the device. In addition, it became possible to dissolve the resin at a very low temperature of 80°C.

[0112] In Examples 1 and 2, in which a resin solution was used as the feedstock oil, the yields of olefins and aromatic compounds, which are petrochemical feedstocks, were higher than in Comparative Example 1, in which only LCO was used as the feedstock oil. In Example 1, in which LDPE was used as the resin, the yield of olefins having 3 to 7 carbon atoms was higher. In Example 2, in which PS was used as the resin, the yield of aromatic compounds was higher, and in particular the yield of ethylbenzene was higher. [Explanation of symbols]

[0113] 1...Fluid catalytic cracking unit, 10...Riser, 11...Fluid catalytic cracking feed oil supply line, 12...Preheater, 20...Reactor, 21...Cyclone, 22...Cracked oil discharge line, 23...Stripper, 24...Post-reaction catalyst transfer line, 30...Regenerator, 31...Air blower, 32...Air grid, 33...Cyclone, 34...Regenerated catalyst transfer line, 35...Exhaust gas line, 40...Refining equipment, 41...Distillation tower, 42...Line, 43...Distillation tower, 44...Line, 45...Distillation tower, 46...Line, 47...Distillation tower, 48...Line, 60...Aromatic extraction unit, 61...Line, 62...Line, 70...Naphtha cracker, 80...Catalytic reformer

Claims

1. A method for producing a petrochemical raw material, comprising the steps of: producing a petrochemical raw material from a mixture containing a plurality of types of resins, a resin dissolving step of not dissolving a specific resin containing a chlorine element from the mixture containing the plurality of types of resins, and dissolving resins other than the specific resin to obtain a resin solution; and treating the raw oil containing the resin solution in an oil refining apparatus. The resin dissolving step includes selecting a solvent having a relative energy difference based on the Hansen solubility parameter for the specific resin of more than 1 and a relative energy difference based on the Hansen solubility parameter for resins other than the specific resin of not more than 1, and contacting the mixture with the solvent to dissolve the resins other than the specific resin.

2. 2. The method for producing a petrochemical feedstock according to claim 1, wherein the mixture contains at least one resin selected from the group consisting of polyethylene, polypropylene, polystyrene, and polyvinyl chloride.

3. 3. The method for producing a petrochemical raw material according to claim 1, wherein the specific resin is polyvinyl chloride, and the resin other than the specific resin includes at least one resin selected from the group consisting of polyethylene, polypropylene, and polystyrene.

4. The method for producing a petrochemical feedstock according to any one of claims 1 to 3, wherein the solvent comprises two or more solvents.

5. The method for producing a petrochemical raw material according to any one of claims 1 to 4, wherein the oil refining unit is a fluid catalytic cracking unit, a heavy oil thermal cracking unit, a direct desulfurization unit, an indirect desulfurization unit, a kerosene desulfurization unit, or a hydrocracking unit.

6. The method for producing a petrochemical feedstock according to any one of claims 1 to 5, wherein the oil refining unit is a fluid catalytic cracking unit.

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