JP2021161284A - Petroleum product manufacturing method and petroleum product manufacturing system - Google Patents

Abstract

To provide a method for producing a petroleum product, which processes a raw oil in petroleum-refining equipment and can prevent a larger amount of fossil fuel from being consumed than conventional production methods, and to provide a system therefor.SOLUTION: A method for producing a petroleum product by processing a raw oil in petroleum-refining equipment includes using, as an energy necessary for the processing, an energy obtained by combusting one or both of: a combustible containing a waste; and methane obtained from the waste.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a petroleum product and a system for producing a petroleum product.

From the perspective of forming a recycling-oriented society, it is required to effectively use recycled resources while curbing the consumption of limited natural resources. For the purpose of curbing the consumption of natural resources, it is required to curb the consumption of non-renewable natural resources (reduce) and recycle used natural resources (reuse, recycling).

From this point of view, the development of waste recycling technology is one of the important issues from the viewpoint of increasing waste and curbing consumption of natural resources in recent years. Among waste recycling, there is a strong need for recycling technology for waste plastic produced from fossil fuel, which is a natural resource.

Waste plastic recycling methods include material recycling that reuses waste plastic as it is, chemical recycling that chemically decomposes waste plastic to recover basic chemical raw materials such as monomers, and thermal recycling that recovers thermal energy from waste plastic. It is roughly divided into three.

In chemical recycling, waste plastic is thermally decomposed at a high temperature to produce chemical raw materials such as syngas and decomposed oil, or chemically decomposed to produce a monomer, which is converted into other chemical substances and reused. Compared to material recycling, there is an advantage that different types of plastics are mixed, and even if there are foreign substances or dirt, they are often recyclable.

As chemical recycling, Patent Document 1 discloses a method of decomposing a hydrocarbon-based polymer (resin) with a fluidized catalytic cracking apparatus. Specifically, a mixture of a hydrocarbon-based polymer and a hydrocarbon oil selected from fluid cracking gasoline, light cracked gas oil, heavy cracked gas oil, and cracked residual oil is mixed with the fluid cracking raw material oil, and fluid catalytic cracking is performed. A method for cracking a hydrocarbon-based polymer, which comprises supplying to an apparatus, is disclosed.

Japanese Unexamined Patent Publication No. 2002-294251

The energy such as electric power and steam required for the decomposition treatment described in Patent Document 1 is still produced from fossil fuel, which is a natural resource. Therefore, even the method described in Patent Document 1 is not sufficient from the viewpoint of suppressing the consumption of natural resources.

The present invention has been made in view of the above circumstances, and is a method for producing a petroleum product by processing a raw material oil in a petroleum refining facility, which can suppress the consumption of fossil fuels as compared with a conventional production method, and a method for producing a petroleum product. The challenge is to provide a petroleum product manufacturing system.

In order to solve the above problems, the present invention has the following aspects.
[1] A method for producing petroleum products by processing raw material oil in a petroleum refining facility, which is obtained from combustibles including waste and waste as energy required for the processing. A method for producing petroleum products using the energy obtained by burning either or both of methane.
[2] The method for producing a petroleum product according to [1], wherein the raw material oil contains a resin derived from waste plastic.
[3] Manufacture of petroleum products according to [1] or [2], wherein one or both of the combustibles including the waste and the methane obtained from the waste are burned outside the refinery facility. Method.
[4] The method for producing a petroleum product according to any one of [1] to [3], wherein the waste is general waste.
[5] An oil refining facility, a combustion facility that burns one or both of combustibles including waste and methane obtained from the waste, and the combustion facility between the combustion facility and the petroleum refining facility. A petroleum product manufacturing system equipped with means for transmitting the energy obtained by.

According to the present invention, it is possible to provide a method for producing a petroleum product by processing a raw material oil in a petroleum refining facility and a system for producing a petroleum product, which can suppress the consumption of fossil fuels as compared with the conventional production method. can.

It is a block diagram which shows the structure of the manufacturing system of the petroleum product which concerns on one Embodiment of this invention. It is a block diagram which shows the structure of the petroleum refining facility which concerns on one Embodiment of this invention. It is a block diagram which shows the structure of the refining equipment which refines the cracked oil which concerns on one Embodiment of this invention. It is a schematic diagram which shows the method of obtaining the Hansen solubility parameter value and the interaction radius. It is a schematic diagram which shows the distance between the solubility parameter values of two substances of substance 1 and substance 2. It is a schematic diagram which shows the case where the relative energy difference based on the Hansen solubility parameter of substance 1 with respect to substance 2 is within 1. It is a schematic diagram which shows the case where the relative energy difference based on the Hansen solubility parameter of substance 1 with respect to substance 2 is more than 1. And Hansen parameters of the solvent L, Hansen sphere _S of the resin _{P A1, P A2 (P A1} ), and _{S (P A2), P B1} , P B2 Hansen sphere _S (P B1), S the _{(P B2)} It is a schematic diagram which shows the relationship.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents, and is modified and implemented within the scope of the gist thereof. can do.

As used herein, the term "raw material oil" means a fraction derived from crude oil, a resin derived from waste, and a mixture thereof, which are usually processed in various petroleum refining facilities.
As used herein, the term "petroleum product" refers to liquefied petroleum gas, gasoline, naphtha, kerosene, jet fuel oil, light oil, lubricating oil base oil, heavy oil, asphalt, and aromatic compounds and olefins produced in various petroleum refining facilities. It means petroleum chemical products such as.
"Waste" herein includes both general waste and industrial waste. There are 20 types of industrial waste defined by laws and regulations (Waste Disposal and Public Cleansing Law), and general waste means waste other than industrial waste. However, the "waste" in this specification does not include waste such as waste liquid generated in the oil refining process of refinery equipment. That is, the term "waste" as used herein means general waste and industrial waste excluding waste generated in the oil refining process of refinery facilities.

In the method for producing a petroleum product of the present embodiment, the petroleum product is produced by processing the raw material oil in a petroleum refining facility. In the method for producing a petroleum product of the present embodiment, as the energy required for the treatment, energy obtained by burning either one or both of combustibles including waste and methane obtained from the waste is used. First, the petroleum product manufacturing system used in the petroleum product manufacturing method of the present embodiment will be described.

≪Petroleum product manufacturing system≫
The petroleum product manufacturing system of the present embodiment includes an oil refining facility, a combustion facility that burns one or both of combustibles including waste and methane obtained from the waste, and the combustion facility and the petroleum refining system. It is provided with a means for transmitting the energy obtained by the combustion equipment to and from the equipment.
The means for transmitting energy include the form of energy (steam, electric power) for transmitting the energy obtained by the combustion equipment, and the combustion equipment and the petroleum for transmitting the energy obtained by the combustion equipment. It means piping between refining equipment.

FIG. 1 is a configuration diagram showing a configuration of a petroleum product manufacturing system according to an embodiment of the present invention. The petroleum product manufacturing system 100 of the present embodiment includes a petroleum refining facility 101 and a combustion facility 102. The petroleum product manufacturing system 100 of the present embodiment may further include a microbial treatment facility 103 and a power generation facility 104.

<Combustion equipment>
The combustion equipment 102 is an equipment that burns one or both of combustibles including waste and methane obtained from waste, and uses the obtained heat to produce steam. The combustion equipment 102 is connected to the oil refining equipment 101 via the steam supply line L201. The combustion equipment 102 is connected to the power generation equipment 104 via the steam supply line L204. The combustion equipment 102 is connected to the microbial treatment equipment 103 via the methane supply line L302.
As the combustion equipment, conventionally known combustion equipment can be used. An example of a combustion facility is a combustion facility equipped with a waste pit, a crane, an incinerator, a waste heat boiler, an economizer, an ash pit, a dust collector, and a denitration reaction tower. The functions of the above-mentioned devices provided in the combustion equipment will be described later.

<Power generation equipment>
The power generation facility 104 is a facility that generates electricity using the steam produced by the combustion facility 103. The power generation facility 104 is connected to the oil refining facility 101 via the power supply line L401.
As the power generation equipment, conventionally known power generation equipment can be used. An example of a power generation facility is a steam turbine type power generation facility.

<Microbial treatment equipment>
The microbial treatment facility 103 is a facility for producing methane by fermenting food waste with methane. The microbial treatment facility 103 is connected to the petroleum refining facility 101 via the methane supply line L301.
As the microbial treatment equipment, conventionally known microbial treatment equipment can be used. An example of the microbial treatment equipment is a microbial treatment equipment equipped with a sorting machine, a slurry tank, a methane fermentation tank, and a desulfurization tower. The functions of the above-mentioned devices provided in the microbial treatment equipment will be described later.

<Oil refining equipment>
The petroleum refining facility 101 is a facility for manufacturing petroleum products by processing raw material oil. The oil refining equipment 101 is not particularly limited, but is not particularly limited, but is atmospheric pressure distillation equipment, vacuum distillation equipment, fluid cracking equipment, heavy oil thermal cracking equipment, direct desulfurization equipment, indirect desulfurization equipment, kerosene desulfurization equipment, contact reforming equipment. , Iisomerization equipment, hydrocracking equipment, etc., preferably equipment that decomposes hydrocarbons, more preferably fluid cracking equipment, heavy oil cracking equipment, hydrocracking equipment, and fluid cracking equipment. Is the most preferable.
The fluidized catalytic cracking equipment (hereinafter, also referred to as “FCC equipment”) is a riser that produces cracked oil including petroleum products by contacting the raw material oil with a fluidized catalytic cracking catalyst to decompose the raw material oil, and the cracked oil and fluidity. It is equipped with a reaction tower that separates the catalytic cracking catalyst, a regeneration tower that regenerates the catalyst by burning carbon (cork) deposited on the separated fluid cracking catalyst, and purification equipment.

Hereinafter, an example of the FCC equipment will be described with reference to FIG. FIG. 2 is a configuration diagram showing an example of FCC equipment. The FCC facility 1 includes a riser 10, a reaction tower 20, a regeneration tower 30, and a purification facility 40.

(Riser)
The riser 10 is a device that produces cracked oil containing petroleum products by bringing the raw material oil into contact with a fluidized catalytic cracking catalyst and decomposing the raw material oil. The riser 10 is connected to, for example, a regeneration catalyst transfer line 34 for supplying the fluidized catalytic cracking catalyst regenerated in the regeneration tower 30 and a fluidized cracking feedstock oil supply line 11 for supplying the fluid cracking feedstock oil. When a raw material oil containing a resin solution described later is used as the raw material oil, the riser 10 is preferably connected to a resin solution supply line 51 that supplies the resin solution. Further, a preheating device 12 and a preheating device 52 are provided on the fluidized cracking raw material oil supply line and the resin solution supply line, respectively. Further, the upper part of the riser 10 is connected to the reaction tower 20.

(Reaction tower)
The reaction column 20 is a device that separates the cracked oil and the fluidized catalytic cracking catalyst. The reaction column 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. Further, the bottom of the stripper 23 and the lower part of the regeneration tower 30 are connected by a catalyst transfer line 24 after the reaction.

(Regeneration tower)
The regeneration tower 30 is a device that regenerates the catalyst by burning the cork on the fluid cracking catalyst separated by the reaction tower 20. The regeneration tower 30 includes, for example, an air blower 31, an air grid 32, a cyclone 33, a regeneration catalyst transfer line 34, and an exhaust gas line 35. The bottom of the regeneration tower and the air blower 31 are connected via an air grid 32. Further, a cyclone 33 is installed in the upper part of the regeneration tower, and the upper part of the cyclone 33 is connected to the exhaust gas line 35.

(Refining equipment)
The refining facility 40 is a facility that separates cracked oil containing petroleum products produced by a fluidized catalytic cracking apparatus for each product. As shown in FIG. 3, the purification equipment includes, for example, a distillation column 41, a line 42, a distillation column 43, a line 44, a distillation column 45, a line 46, a distillation column 47, a line 48, an aromatic extraction device 60, and a line 61. A line 62, a naphtha cracker 70, and a catalytic reformer 80 are provided. The distillation column 41 is connected to the reaction column 20 via a cracked oil discharge line 22 near the middle stage of the column. The distillation column 43 is connected to the top of the distillation column 41 via a line 42 near the middle stage of the column. The distillation column 45 is connected to the bottom of the distillation column 43 via a line 44 near the middle stage of the column. The distillation column 47 is connected to the top of the distillation column 45 via a line 46 near the middle stage of the column. The aromatic extraction device 60 is connected to the bottom of the distillation column 45 via a line 48. The naphtha cracker 70 is connected to the aromatic extraction device 60 via a line 61. The catalytic reformer 80 is connected to the aromatic extractor 60 via a line 62.

As the distillation column 41, the distillation column 43, the distillation column 45, and the distillation column 47, a distillation column known in the art can be used depending on the object to be separated described later. As the aromatic extraction device 60, an aromatic extraction device known in the art can be used depending on the object to be separated, which will be described later. Similarly, the naphtha cracker 70 and the catalytic reformer 80 can also use the naphtha cracker and the catalytic reformer known in the art.
The detailed structure of the reflux line of the distillation column, the preheater, the can discharge liquid extraction line, the outflow liquid extraction line, etc. is not shown in FIG. 3, but as described above, the distillation column is used in this field. It has a known distillation column structure. The same applies to aromatic extractors, naphtha crackers, and catalytic reformers.

(Resin dissolution tank)
When a raw material oil containing a resin solution described later is used as the raw material oil, the method for producing a petroleum product of the present embodiment may include a resin solution manufacturing process in which the resin is dissolved in advance to obtain a resin solution. preferable. In the resin dissolution liquid manufacturing step, the resin dissolution tank 50 for producing a resin dissolution liquid by dissolving a resin other than the specific resin without dissolving a specific resin from a mixture containing a plurality of types of resins will be described later. This is an apparatus for performing a resin dissolution liquid manufacturing process in which a specific resin is not dissolved from a mixture containing a plurality of types of resins, but a resin other than the specific resin is dissolved to produce a resin dissolution liquid.
As the resin melting tank, an oil storage tank can be used.
The resin dissolution tank 50 is connected to the riser 10 through the resin dissolution liquid supply line 51. The resin melting tank 50 is preferably provided with a stirring device, a melting tank heater, a solid matter separating device, and the like.

<Fluid catalytic cracking catalyst>
The FCC equipment includes a flow contact catalyst (hereinafter, also referred to as "FCC catalyst").
The FCC catalyst of the present embodiment preferably contains zeolite having a sodalite cage structure, β-zeolite, ZSM-5 type zeolite, and the like, and more preferably contains a zeolite having a sodalite cage structure.
The content of zeolite with respect to the total mass of the FCC catalyst is preferably 25 to 45% by mass, more preferably 28 to 42% by mass, and even more preferably 30 to 40% by mass.

In the present specification, the zeolite having a sodalite cage structure is a sodalite cage structure, that is, a three-dimensional octahedron formed by sharing apex oxygen with aluminum or silicon with aluminum and silicon tetrahedron as basic units. It has a void composed of a tetrahedral crystal structure defined by a four-membered ring, a six-membered ring, etc., with each vertex of the crystal structure of the facet cut off, and the place and method in which the sodalite cages are bonded to each other are defined. By changing, it means those having various pore structures, skeletal densities, and channel structures.

Examples of the zeolite having the sodalite cage structure include one or more selected from sodalite, A-type zeolite, EMT, X-type zeolite, Y-type zeolite, stabilized Y-type zeolite, and the like, and the stabilized Y-type zeolite can be mentioned. Is preferable.

Stabilized Y-zeolite is synthesized using Y-zeolite as a starting material, and is more resistant to deterioration of crystallinity than Y-zeolite. Generally, it is higher than Y-zeolite at high temperature. Is produced by treating with a mineral acid such as hydrochloric acid, a base such as sodium hydroxide, a salt such as calcium fluoride, and a chelating agent such as ethylenediamine tetraacetic acid, if necessary, after performing the steam treatment of the above several times. ..
The stabilized Y-zeolite obtained by the above method can be used in a form ion-exchanged with a cation selected from hydrogen, ammonium or a polyvalent metal. Further, as the stabilized Y-type zeolite, a heat shock crystalline aluminosilicate zeolite having more excellent stability (see Japanese Patent No. 25444317) can also be used.

The FCC catalyst of the present embodiment preferably further contains a binder, a clay mineral and the like.
Examples of the binder include silica sol. By using the silica sol, the moldability at the time of granulating the FCC catalyst is improved, and it is possible to easily spheroidize the FCC catalyst. In addition, the fluidity and wear resistance of the FCC catalyst after granulation can be easily improved. The content of the binder with respect to the total mass of the FCC catalyst is preferably 15 to 35% by mass, more preferably 18 to 32% by mass, and further preferably 20 to 30% by mass.

Examples of clay minerals include montmorillonite, kaolinite, halloysite, bentonite, attaparghite, bauxite and the like. Further, in the FCC catalyst of the present embodiment, silica, silica-alumina (excluding the above-mentioned zeolite), alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina and the like are usually used. Fine particles of known inorganic oxides used in the FCC catalyst of No. 1 can be used in combination with the above-mentioned clay mineral.
The sum of the contents of the clay mineral and the inorganic oxide with respect to the total mass of the FCC catalyst is preferably 35 to 55% by mass, more preferably 38 to 52% by mass, and further preferably 40 to 50% by mass. preferable.
The content of the clay mineral with respect to the total mass of the FCC catalyst is preferably 25 to 50% by mass, more preferably 30 to 45% by mass, and even more preferably 32 to 42% by mass.

Further, the FCC catalyst of the present embodiment may contain a zeolite stability improver. The zeolite stability improver has a function of suppressing the collapse of zeolite crystals. Phosphoric zeolite stability improvers such as phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, aluminum monobasic phosphate and other water-soluble phosphates, scandium, yttrium, lantern , Cerium, placeodium, neodymium, samarium, gadrinium, disprosium, formium and other rare earth metal-based zeolite stability improvers. When the FCC catalyst contains a zeolite stability improver, the content of the zeolite stability improver with respect to the total mass of the FCC catalyst is preferably 0.1 to 5% by mass.

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

<Manufacturing method of 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, binder, clay mineral, and zeolite stability improver, it is produced by drying a slurry containing a predetermined amount of zeolite, binder, clay mineral, and zeolite stability improver. Can be done.

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

Then, the aqueous slurry is dried to obtain microspheres.
The aqueous slurry is preferably dried by a spray drying device under the conditions of a gas inlet temperature of 200 to 600 ° C. and a gas outlet temperature of 100 to 300 ° C.

In this production method, the microspheres obtained by the above-mentioned drying treatment are further washed and ion-exchanged by a known method as necessary, and excess alkali metals and soluble substances brought in from various raw materials are carried out. Impurities and the like may be removed.

Specifically, the washing treatment can be carried out with water or aqueous ammonia, and the content of soluble impurities can be reduced by washing with water or aqueous ammonia.

Specifically, the ion exchange treatment can be carried out with an aqueous solution of an ammonium salt such as ammonium sulfate or ammonium sulfate, and the ion exchange can reduce alkali metals such as sodium and potassium remaining in the microspheres.

The above-mentioned cleaning treatment is usually performed prior to the ion exchange treatment, but as long as the cleaning treatment and the ion exchange treatment are preferably performed, the ion exchange treatment may be performed first.

The cleaning treatment and the ion exchange treatment are preferably carried out until the content of the alkali metal and the content of soluble impurities are equal to or less than a desired amount. When the content of the alkali metal and the content of soluble impurities are not more than the desired amount, the catalytic activity can be improved.

The content of the alkali metal in the microspheres is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on the drying catalyst. The content of soluble impurities is preferably 2.0% by mass or less, and more preferably 1.5% by mass or less.

It is preferable to perform the drying treatment again on the microspheres that have been subjected to the above-mentioned washing treatment and ion exchange treatment. The drying treatment is preferably carried out at a temperature of 100 to 500 ° C. until the water content of the microspheres reaches 1 to 25% by mass.
In this way, the FCC catalyst of the present embodiment can be produced.

≪Manufacturing method of petroleum products≫
In the method for producing a petroleum product of the present embodiment, the petroleum product is produced by processing the raw material oil in a petroleum refining facility. Further, as the energy required for the treatment, the energy obtained by burning either one or both of combustibles including waste and methane obtained from the waste is used.
Hereinafter, the process of processing the raw material oil in the petroleum refining facility and the process of obtaining energy derived from waste will be described.

<Process of processing raw material oil in petroleum refining equipment>
Hereinafter, the process of processing the raw material oil in the petroleum refining facility will be described in detail by taking the case where the petroleum refining facility is an FCC facility as an example. The step of treating the feedstock with the FCC facility includes a fluid catalytic cracking reaction step of treating the feedstock with the FCC facility.
As the raw material oil, a raw material oil that is subjected to a normal fluid cracking reaction (hereinafter, also referred to as "fluid catalytic cracking raw material oil"), a resin derived from waste, and a mixture thereof can be used and discarded. It is preferable to contain a resin derived from a substance. Further, as the resin derived from waste, a resin derived from waste plastic is preferable. Since the raw material oil contains a resin derived from waste plastic, the waste plastic can be recycled into petroleum products, and the consumption of fossil fuel can be further suppressed.
Hereinafter, the description will be made on the premise that the raw material oil contains a resin derived from waste plastic, but the raw material oil may be only a fluid cracking raw material oil or only a resin derived from waste plastic.

In the step of treating the raw material oil of the present embodiment with the FCC facility, the specific resin is not dissolved from the mixture containing a plurality of types of resins contained in the waste plastic before the flow contact decomposition reaction step, and the specific resin is specified. It is preferable to have a resin solution manufacturing process in which a resin other than the above resin is dissolved to obtain a resin solution.

(Resin solution manufacturing process)
In the resin solution manufacturing process of the present embodiment, a resin solution is produced by dissolving a resin other than the specific resin from a mixture containing a plurality of types of resins without dissolving the specific resin. In the present embodiment, the solvent has a relative energy difference of more than 1 based on the Hansen solubility parameter for the specific resin and a relative energy difference of 1 or less based on the Hansen solubility parameter for resins other than the specific resin. Is selected, and the mixture is contact-treated with the solvent to dissolve a resin other than the specific resin, and a resin solubility solution is preferably produced.
Hereinafter, the Hansen solubility parameter and the method for obtaining the relative energy difference will be described.

〇 Hansen solubility parameter The Hansen solubility parameter (hereinafter, also simply referred to as “HSP”) is based on the idea that two substances having similar intramolecular interactions are easily dissolved in each other. HSP is composed of energy derived from the dispersive force between molecules (δd), energy derived from bipolar interaction between molecules (δp), and energy derived from hydrogen bond between molecules (δh). The three parameters of can be regarded as the coordinates in the three-dimensional space (Hansen space).

The HSP value in the evaluation sample whose HSP value is unknown can be calculated by the following method.
HSP value _{(δd m, δp m, δh} m) in Hansen solubility parameter space specified by plotting the three-dimensional space, a plurality of pure substance having a known HPS value (substance consisting of one compound) The HSP value of the evaluation sample can be calculated by plotting and specifying the Hansen sphere based on the solubility of the evaluation sample in the pure substance and obtaining the center value of the Hansen sphere (Hansen sphere method).
The HSP value of the evaluation sample can also be calculated using the atomic group contribution method from the information on the average molecular structure.
In both the Hansen sphere method and the atomic group contribution method, the HSP value of the evaluation sample can be calculated using, for example, the computer software Hansen Solubility Parameters in Practice (HSPiP).
In the case of the Hansen sphere method, the evaluation sample may be a pure substance or a mixture.

The method of obtaining the center value of the Hansen sphere, that is, the HSP value (δdm, δpm, δhm) will be described with reference to FIG.
First, about 15 to 30 pure substances HSPs having known HSP values in the three-dimensional space illustrated in FIG. 4 (with the dispersion force term δd, the dipole force term δp, and the hydrogen bond force term δh as coordinate axes) Plot the values.
At this time, as shown in FIG. 4, for example, a pure substance showing solubility in the evaluation sample is marked with a circle, and a pure substance not showing solubility in the evaluation sample is marked with a cross. Then, based on the solubility of the plotted evaluation samples, the pure substances showing solubility (marked with a circle in FIG. 4) were included and the pure substances showing no solubility (marked with a cross in FIG. 4) were included. ) Is not included, and the one having the minimum radius is obtained as a Hansen sphere S (shown spherically in FIG. 4).
The radius forming the Hansen sphere S (minimum radius) becomes the interaction radius R ₀ indicating compatibility by dissolving the pure substance indicated by the circle in the figure, and the center value (δ dm, δ dm) of the obtained Hansen sphere S. δpm, δhm) is the HSP value of the evaluation sample.
The HSP value of the pure substance to be used for determining the Hansen spheres example, dispersion force term δd is about ^1/2 10～25MPa, polar term δp is about ^1/2 0～20MPa, The hydrogen bonding force term δh is about 0 ^{to 20 MPa 1/2.}
Further, since the solubility depends on the temperature, it is preferable to carry out the solubility test at the temperature at which the resin is actually melted when obtaining the Hansen sphere.

Next, FIG. 5 is a schematic diagram showing the distance between the solubility parameters of the two substances, substance 1 and substance 2. First, the Hansen spheres of substance 1 and substance 2 are obtained by the above method. When the HSP value of substance 1 is (δd ₁ , δp ₁ , δh ₁ ) and the HSP value of substance 2 is (δd ₂ , δp ₂ , δh ₂ ), the distance between the two substances (hereinafter, simply (Also referred to as "Ra") can be calculated by the following equation 1.
Ra = {4 × (δd _{1 − δd 2} ) ² + (δp _{1 − δp 2} ) ² + (δh _{1 − δh 2} ) ² } ^0.5 Equation 1

The relative energy difference of the substance 1 based on the Hansen solubility parameter (hereinafter, also simply referred to as “RED”) can be calculated by the following equation 2 when _{the interaction radius of the substance 2 is R 0.} ..
RED = Ra / R ₀ formula 2

FIG. 6 is a schematic diagram showing a case where the RED of the substance 1 based on the Hansen solubility parameter for the substance 2 is within 1. In this case, as shown in FIG. 6, the HSP values (δd ₁ , δp ₁ , δh ₁ ) of the substance 1 are located inside the Hansen sphere S2 of the substance 2 (including the surface of the sphere).

FIG. 7 is a schematic diagram showing a case where the RED of the substance 1 based on the Hansen solubility parameter for the substance 2 is more than 1. In this case, as shown in FIG. 7, the HSP values (δd ₁ , δp ₁ , δh ₁ ) of the substance 1 are located outside S2 of the Hansen sphere of the substance 2 (the surface of the sphere is not included).

In the resin solution manufacturing process of the present embodiment, a resin solution is produced by dissolving a resin other than the specific resin from a mixture containing a plurality of types of resins without dissolving the specific resin.
The specific resin may be one kind or a plurality. The resin other than the specific resin may be one kind or a plurality.
Hereinafter, the specific resin is referred to as "resin A", and a resin other than the specific resin is referred to as "resin B". In the present embodiment, only the resin B is dissolved from the mixture containing the resin A and the resin B.

〇 Solvent selection method Resin A is composed of resins P _{A1 to} P _Ax , and resin B is composed of resins P _{B1 to} P _By . x represents the number of types of resin constituting the resin A, and is an integer of 1 or more. y represents the number of types of resin constituting the resin B, and is an integer of 1 or more.
The value of x is not particularly limited, but is preferably 1 to 3 and more preferably 1 to 2 from the viewpoint of facilitating the selection of the solvent. The value of y is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3 from the viewpoint of facilitating the selection of the solvent. The value of x + y is not particularly limited, but is preferably 2 to 8 and more preferably 2 to 5 from the viewpoint of facilitating the selection of the solvent.

By the method described above, obtaining the resin _P A1 _{to P Ax} Hansen sphere _S (P A1) ~S the _{(P Ax),} respectively. Then, from the obtained Hansen sphere _{S (P A1) ~S (P} Ax), HSP value of the resin _{P A1 ~P Ax [δd (P} A1), δp (P A1), δh (P A1)] ~ [ δd ( _PAx ), δp ( _PAx ), δh ( _PAx )] and the interaction radii R ₀ ( _PA1 ) to R ₀ ( _PAx ) are obtained, respectively.
Similarly determine _P B1 _{to P By A} Hansen sphere _S (P B1) ~S the _{(P By A),} respectively. Then, from the obtained Hansen spheres S (P _B1 ) to S (P _By ), the HSP values of the _{resins P B1 to} P _{By [δd (P B1} ), δp (P _B1 ), δh (P _B1 )] to [ δd (P _By ), δp (P _By ), δh (P _By )] and the interaction radii R ₀ (P _B1 ) to R ₀ (P _By ) are obtained, respectively.

Let the HSP value of the solvent L to be selected be a tentative value [δd (L), δp (L), δh (L)].
HSP value of the resin _{P A1 ~P Ax [δd (P} A1), δp (P A1), δh (P A1)] ~ [δd (P Ax), δp (P Ax), δh (P Ax)] , respectively _{Substituting into (δd 2} , δp ₂ , δh ₂ ) of the above formula 1, the HSP values [δd (L), δp (L), δh (L)] of the solvent L are substituted into (δd ₁ , δp _{1) of the above formula 1.} It is substituted into .delta.h _1), obtaining Ra of _{(P A1) ~Ra (P Ax} ) , respectively. The resulting _{Ra (P A1) ~Ra (P} Ax) is a function of δd (L), δp (L ), δh (L). _Then, by substituting P A1 _{to P Ax} interaction radius _R 0 of _{(P A1) ~R 0 (P} Ax) and the resulting _Ra (P A1) _~Ra the _{(P Ax)} in each of the formulas 2, RED ( P _A1 ) to RED ( _PAx ) are obtained. The obtained RED ( _PA1 ) to RED ( _PAx ) are functions of δd (L), δp (L), and δh (L).

Similarly, the HSP values of the resins P _{B1 to} P _By [δd (P _B1 ), δp (P _B1 ), δh (P _B1 )] to [δd (P _By ), δp (P _By ), δh (P _By )) _{] Are substituted into (δd 2} , δp ₂ , δh ₂ ) of the above formula 1, and the HSP values [δd (L), δp (L), δh (L)] of the solvent L are substituted into (δd _{1) of the above formula 1.} , Δp ₁ , δh ₁ ) to obtain Ra (P _B1 ) to _{Ra (P By} ), respectively. The obtained Ra (P _{B1 ) to Ra (P By} ) are functions of δd (L), δp (L), and δh (L). _Then, by substituting P B1 _{to P By A} of interaction radius _{R 0 (P B1) ~R 0} (P By) and the resulting _Ra (P B1) _~Ra the _{(P By A)} to each of the formulas 2, RED ( P _B1 ) to RED (P _By ) are obtained. The obtained RED (P _B1 ) to RED (P _By ) are functions of δd (L), δp (L), and δh (L).

In the present _embodiment, RED (P A1) is all greater than 1 ~RED _{(P Ax),} and all _{RED (P B1) ~RED (P} By) is less than 1, HSP value [.delta.d ( L), δp (L), δh (L)] is selected.
And HSP value of the solvent L when x is 2, y is 2 in FIG. 8, Hansen sphere _S (P A1) of the resin _{P A1, P A2,} and S _{(P A2),} Hansen resin _{P B1, P B2} The relationship between the spheres S (P _B1 ) and S (P _{B2) is shown.} As shown in FIG. 8, HSP value of the solvent L [δd (L), δp (L), δh (L)] is the Hansen sphere _S (P A1) of the resin _{P A1, P A2, S (} P A2 ) (The surface of the sphere is not included), and inside the Hansen spheres S (P _B1 ) and S (P _{B2 ) of the resins P B1} and P _B2 (including the surface of the sphere).

In this _embodiment, all the _{RED (P A1) ~RED (P} Ax) is greater than 1, is preferably 2.5 or more, and more preferably 3 or more. If it is _{RED (P A1) ~RED (P} Ax) all the lower limit greater than (or more), lysis with solvents L of resin _P A1 _{to P Ax} constituting the resin A can be suppressed. Upper limit of _{RED (P A1) ~RED (P} Ax) is not particularly limited, for example, 10 or less.

In the present embodiment, all of RED (P _B1 ) to RED (P _By ) are 1 or less, preferably 0.9 or less, and more preferably 0.8 or less. When all of RED (P _B1 ) to RED (P _By ) are not more than the above upper limit values, _{dissolution of the resins P B1 to} P _By constituting the resin B by the solvent L is promoted. The lower limit of RED (P _B1 ) to RED (P _By ) is not particularly limited, but is, for example, 0.1 or more.

The distance HSP value and the resin _P A1 _{to P Ax} each HSP value of the solvent _{L Ra (P A1) ~Ra (} P Ax) _, all of _{RED (P A1) ~RED (P} Ax) is 1 greater As long as it is not particularly limited, for example, 5 MPa ^1/2 or more is preferable, and 10 MPa ^1/2 or more is more preferable.

_{For Ra (P B1} ) to _{Ra (P By} ), which is the distance between the HSP value of the solvent L and the HSP values of the resins P _{B1 to} P _By , all of RED (P _B1 ) to RED (P _By ) are 1 or less. Although unless specifically limited, for example, ^{8 MPa 1/2} or less are preferred, ^{5 MPa 1/2} or less is more preferable.

In order to select the solvent L having an HSP value [δd (L), δp (L), δh (L)] such that all of RED (P _B1 ) to RED (P _{By) are 1 or less, y} When is 2 or more, it means that all of the Hansen spheres S (P _B1 ) to S (P _{By ) of the resins P B1 to} P _By have overlapping portions.
That is, at random from the resin B, y = c, the resin _P Bc is y = _d, when selecting the _{P Bd,} HSP value of _{P Bc [δd (P Bc)} , δp (P Bc), δh ( P _Bc )] and _{HSP values of P Bd} [δd (P _Bd ), δp (P _Bd ), δh (P _Bd )] are set to (δd ₁ , δp ₁ , δh ₁ ) and (δd ₂ , δp) of the above formula 1. _2, and _Ra obtained by substituting each _{δh 2) (P Bc -P Bd} ), and _{P Bc} interaction radius _R 0 _{(P Bc),} the interaction of _{P Bd} radius _R 0 and _{(P Bd)} Relationship satisfies the following equation 3.
{R ₀ (P _Bc ) + R ₀ (P _Bd )} ≧ Ra (P _{Bc −} P _Bd ) Equation 3

_{When there is a combination of resins P B1 to} P _By that does not satisfy the above formula 3, the resin of the resin B may be appropriately selected again. That is, any resin is removed _{from P B1 to P By} constituting the resin B so as to satisfy the above formula 3. In this case, the removed resin constitutes the resin A.

〇 Resin The type of resin contained in the mixture of the present embodiment is not particularly limited, but for example, polyolefin resins such as polyethylene, polypropylene, polybutadiene, and polymethylpentene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and ethylene-acetic acid. Vinyl resins such as vinyl copolymers and ethylene-vinyl alcohol copolymers; polystyrene resins such as polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytri Polyester resin such as methylene terephthalate; cellulose triacetate; polycarbonate; urethane resin such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfone resin such as polyethersulfone, polyphenylsulfone, polysulfone; polyetherketone, polyetheretherketone Polyetheretherketone such as polyetherketoneketone; polyphenylenesulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin such as polyamide 6, polyamide 66 and polyamide11; acrylic resin; fluororesin; phenol resin; Examples thereof include epoxy resin; melamine resin; urea resin; unsaturated polyester resin; and alkyd resin.
The mass average molecular weight of the resin contained in the mixture of the present 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. ..

The resin of the present embodiment is solid at 30 ° C. or lower. The form of the resin is not particularly limited as long as the effects of the present invention can be obtained, and examples thereof include a molded body molded into a package such as a PET bottle, pellets, and flakes. 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 thereof is about 1 to 100 mm.
From such resins, resin A and resin B can be arbitrarily selected according to the uses described later.

The 〇 solvent solvent of the present _embodiment, RED (P A1) _~RED all _{(P Ax)} is 1 greater, and _RED (P B1) _~RED HSP value all becomes 1 or less _{(P By A)} As long as it has, it is not particularly limited. 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, acetone, diisobutylketone and ethyl. Ketones such as methyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, N-methyl-2pyrrolidone, diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane. , 1,3-Dioxolane, 4-Methyldioxolane, tetrahydrofuran, methyl tetrahydrofuran, anisole, phenetol, 2-methoxytetrahydropyrane and other ethers, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol , Ether-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3 -Alcohols such as tetrafluoro-1-propanol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, N, N-dimethyl Organic solvents with amide groups such as formamide, acetamide, N, N-dimethylacetamide, organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, methoxynitrile, ethylene carbonate, propylene carbonate, 1, 2 -Organic solvent having a carbonate group such as glycerol carbonate, halogenated hydrocarbons such as methylene chloride, chloroform, tetrachloroethane, chlorobenzene, n-pentane, cyclohexane, n-hexane, 1-octadecene, benzene, toluene, xylene, 2, Examples thereof include hydrocarbons such as 2,4-trimethylpentane, cyclohexene, ethylbenzene, d-lymonen, and l-lymonen.

One type of solvent may be used alone, or two or more types may be used in combination. That is, the solvent of this embodiment may be a mixture of two or more kinds of solvents (hereinafter, also referred to as "mixed solvent"). Examples of the mixed solvent include a mixture of two or more kinds of solvents listed above.

Other mixed solvents include petroleum distillates obtained in the refining process of crude oils such as normal pressure residual oil, reduced pressure light oil, reduced pressure residual oil, desulfurized atmospheric pressure residual oil, desulfurized reduced pressure light oil, lightly decomposed light oil, and heavy cracked light 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, orange oil, and waste oils thereof may be used. Further, the above-mentioned solvent may be further mixed with these mixed solvents.

When the mixed solvent is used as the solvent of the present embodiment, the HSP value of the mixed solvent may be obtained by the above-mentioned method, or the HSP value of the solvent constituting the mixed solvent may be obtained by weighted averaging as described below. good.
Mixed solvent L is composed of the solvent _L 1 ~L _z, respectively content ratio of the solvent _L 1 ~L _z to the total volume of all solvents before mixing of the mixed _{solvent, V (L 1) ~V (} L z ). Each HSP value of the solvent _{L 1 ~L z, [δd (} L 1), δp (L 1), δh (L 1)] ~ [δd (L z), δp (L z), δh (L z) ], The HSP values of the mixed solvent [δd (L), δp (L), δh (L)] can be obtained by the following equations 4 to 6.

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

The boiling point of the solvent of the present embodiment is not particularly limited as long as the effect 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 of the present embodiment is not particularly limited as long as the effect of the present invention can be obtained, but may be, for example, 0.70 to 1.5 g / cm ³ or 0.80 to 1.2 g / cm ³ . It may be 0.85 to 1.2 g / cm ^3.

〇 Combination of resin A, resin B and solvent L In the present embodiment, the resin A preferably contains a chlorine element. Further, in the present embodiment, it is preferable that the resin B and the solvent L do not contain a chlorine element. When the raw material oil containing the resin solution obtained in the resin dissolution step of the present embodiment is processed by the petroleum refining apparatus, if the resin solution contains chlorine elements, the process is in the process of processing by the petroleum refinery. Hydrogen chloride may be generated and corrode oil refineries. Since the resin A contains a chlorine element and the resin B and the solvent L do not contain a chlorine element, the obtained solution does not contain a chlorine element, and it is possible to prevent corrosion of the petroleum refining equipment. Become.
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.

When the resin constituting the resin A is polystyrene or polyvinyl chloride and the resin constituting the resin B is polyethylene or polypropylene, the relative energy difference based on the Hansen solubility parameter with respect to the resin A is more than 1, and the resin B is used. Examples of the solvent in which the relative energy difference based on the Hansen solubility parameter with respect to the resin is 1 or less include benzene, cyclohexane, and ethylbenzene.

When the resin constituting the resin A is polypropylene or polyvinyl chloride and the resin constituting the resin B is polyethylene or polystyrene, the relative energy difference based on the Hansen solubility parameter with respect to the resin A is more than 1, and the resin B is Examples of the solvent having a relative energy difference of 1 or less based on the Hansen solubility parameter with respect to butyl benzoate, benzyl acetate, and orange oil can be mentioned.

When the resin constituting the resin A is polyethylene or polyvinyl chloride and the resin constituting the resin B is polypropylene or polystyrene, the relative energy difference based on the Hansen solubility parameter with respect to the resin A is more than 1, and the resin B is used. Examples of the solvent in which the relative energy difference based on the Hansen solubility parameter with respect to the resin is 1 or less include chlorobenzene and the like.

When the resin constituting the resin A is polyethylene or polypropylene and the resin constituting the resin B is polystyrene or polyvinyl chloride, the relative energy difference based on the Hansen solubility parameter with respect to the resin A is more than 1, and the resin B is used. Examples of the solvent in which the relative energy difference based on the Hansen solubility parameter with respect to the resin is 1 or less include N-methylpyrrolidone, N, N-dimethylacetamide and the like.

When the resin constituting the resin A is polypropylene and the resin constituting the resin B is polyethylene, polystyrene, or polyvinyl chloride, the relative energy difference based on the Hansen solubility parameter with respect to the resin A is more than 1, and the resin B is used. As a solvent having a relative energy difference of 1 or less based on the Hansen solubility parameter with respect to , 64% by mass of% d-lymonen and 36% by mass of dimethylformamide, 58% by mass of tetrahydrofuran and 42% by mass of cyclohexanone, 62% by mass of ethyl acetate and 38% by mass of benzyl benzoate. Examples include a solvent, a mixed solvent of 58% by mass of methyl ethyl ketone and 42% by mass of benzyl benzoate.

When the resin constituting the resin A is polyvinyl chloride and the resin constituting the resin B is polyethylene, polypropylene, or polystyrene, the relative energy difference based on the Hansen solubility parameter with respect to the resin A is more than 1, and the resin B is used. Examples of the solvent in which the relative energy difference based on the Hansen solubility parameter with respect to the resin is 1 or less include 1,1,1,2-tetrachloroethane, d-limonene, o-xylene, toluene and the like.

(Conditions for resin dissolution)
In the method for dissolving the resin of the present embodiment, the ratio of the mixture to the total mass of the solvent is not particularly limited as long as the resin B can be dissolved, but may be, for example, 1 to 50% by mass or 1 to 40% by mass. It may be 1 to 30% by mass.
In the method for dissolving the resin of the present embodiment, the ratio of the resin B to the total mass of the solvent is not particularly limited as long as the resin B can be dissolved, but may be, for example, 1 to 20% by mass or 1 to 18% by mass. , 1 to 15% by mass may be used.
The temperature at which the resin B is melted is not particularly limited as long as the resin B can be melted, but as long as the resin A does not soften or melt, the temperature may be 15 to 100 ° C., 20 to 90 ° C., 30 to 30 to 90 ° C. It may be 80 ° C.
When the resin B is dissolved, it is preferable to perform stirring, ultrasonic treatment, or the like.

In the method for dissolving the resin of the present embodiment, it is preferable that all of the resin B is dissolved, but 80 to 100% by mass may be dissolved with respect to the total mass of the resin B, and 90 to 100% by mass may be dissolved. It may be dissolved.
In the method for dissolving the resin of the present embodiment, it is preferable that the resin A is not dissolved, but 0% by mass or more and less than 1% by mass may be dissolved with respect to the total mass of the resin A, from 0 to 0.5% by mass. % May dissolve.

The dissolved amount of the resin can be confirmed, for example, in the case of a resin containing a hetero atom such as a halogen element, by measuring the content of the hetero atom in the solution. The amount of dissolved resin containing no hetero atom can be measured by a conventionally known analytical method, and examples of the analytical method include infrared spectroscopy, gas chromatograph mass spectrometry, and gel filtration permeation chromatography. Take as an example.

<Fluid catalytic cracking reaction process>
In the step of treating the raw material oil containing the resin solution of the present embodiment with the FCC facility, the raw material oil containing the resin solution produced in the above-mentioned resin solution manufacturing process is treated with the FCC facility. Specifically, raw material oil containing a resin solution is supplied to FCC equipment and contact-treated with an FCC catalyst to carry out a fluid cracking reaction to produce cracked oil containing petroleum products.

In this embodiment, the flow catalytic cracking reaction can be carried out by a method known in the art. The fluid cracking reaction can be carried out in an FCC facility by bringing a raw material oil containing a resin solution into contact with an FCC catalyst at a high temperature.

In the present embodiment, the raw material oil to be decomposed contains a resin solution. Only the resin solution may be used as the raw material oil, or the resin solution and the fluid cracking raw material oil may be mixed and used as the raw material oil.
The fluid catalytic cracking raw material oil mixed with the resin solution is not particularly limited, and examples thereof include hydrocarbon oils (hydrocarbon mixtures) that are liquid at room temperature and pressure.

Examples of the hydrocarbon oil include one or more selected from a light oil distillate obtained by atmospheric pressure or vacuum distillation of crude oil, atmospheric distillation residual oil, vacuum distillation residual oil and the like, and include coker light oil and solvent demolding oil. , Solvent decalcified asphalt, tar sand oil, shale oil oil, coal liquefied oil, GTL (Gas to Liquids) oil, vegetable oil, waste lubricating oil, waste cooking oil and the like.

Further, as the fluid cracking raw material oil used in the present embodiment, the above-mentioned hydrocarbon oil is hydrogenated, that is, a Ni-Mo-based catalyst, a Co-Mo-based catalyst, and a Ni-Co-Mo. Hydrodesulfurized oils that are hydrodesulfurized at high temperature and high pressure in the presence of hydrogenation catalysts such as system catalysts and Ni-W catalysts can also be mentioned.

The fluid cracking reaction of the feedstock of the present embodiment is usually carried out by continuously circulating the FCC catalyst in the FCC facility 1 including the riser 10, the reaction tower 20 and the regeneration tower 30 installed vertically. can. In the present specification, the fluidized catalytic cracking equipment (FCC equipment) also includes the residual oil fluidized cracking equipment (RFCC equipment). That is, in the present specification, the fluidized catalytic cracking reaction also includes the residual oil fluid cracking reaction.

Hereinafter, the fluid cracking reaction carried out by the FCC facility will be specifically described.
The lifting fluid flows upward in the riser 10, and the FCC catalyst supplied from the regeneration catalyst transfer line 34 flows upward in the riser 10 together with the lifting fluid. The resin solution is heated to a predetermined temperature by the preheating device 52, steamed, and then supplied to the riser 10 from the resin solution supply line 51. Further, in the same manner, the fluidized cracking raw material oil may be heated to a predetermined temperature by the preheating device 12 and supplied to the riser 10 from the fluidized cracking raw material oil supply line 11. The raw material oil containing the resin solution supplied into the riser 10 comes into contact with the FCC catalyst and a decomposition reaction occurs. The decomposed oil produced by the decomposition reaction and the FCC catalyst are transferred to the reaction tower 20.
The concentration of the resin with respect to the total mass of the supplied resin solution is not particularly limited as long as the effects of the present invention can be obtained, but may be, for example, 1 to 50% by mass, 5 to 40% by mass, or 5 to 30% by mass. But it may be.

As the operating conditions of the riser 10, the reaction temperature is preferably 490 to 530 ° C, 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 decomposition reaction of the raw material oil containing the resin solution proceeds, and the yield of petroleum products is improved. Further, when the reaction temperature in the riser 10 is not more than the upper limit value in the above range, the amount of light gas such as dry gas generated by thermal decomposition and the amount of cork produced can be reduced, and the yield of petroleum products is relatively high. It is economical because it is easy to increase.

The reaction pressure is preferably from normal pressure to 0.49 MPa (5 kg / cm ² ), more preferably from 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 with respect to the number of moles of the reactant, a reaction pressure of 0.49 MPa or less in the riser 10 is thermodynamically (equilibrium) advantageous. ..

The mass ratio of the FCC catalyst / raw material oil is preferably 3 to 7, and more preferably 4 to 6. When the mass ratio of the FCC catalyst / raw material oil 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 maintained at an appropriate level, and the decomposition efficiency of the raw material oil is improved. Even when the mass ratio of the FCC catalyst / raw material oil in the riser 10 is equal to or less than the upper limit of the above range, the decomposition reaction of the raw material oil proceeds effectively, and the decomposition reaction corresponding to the increase in the catalyst concentration can easily proceed.

The flow rate of the resin solution (KL /) with respect to the total flow rate [KL / H] of the resin solution supplied from the resin solution supply line 51 and the flow contact cracking raw material oil supplied from the flow contact cracking raw material oil supply line 11. The ratio of H) ((resin solution / (fluid cracking raw material oil + resin solution)) × 100%) is preferably 5 to 100%, more preferably 10 to 95%, and 20 It is more preferably ~ 80%.

The decomposed oil produced by the decomposition of the raw material oil in the riser 10 is supplied to the cyclone 21. The cyclone 21 uses centrifugal force to separate the cracked oil from the FCC catalyst. Then, the cracked oil is discharged from the reaction column 20 by the cracked oil discharge line 22 and transferred to the distillation column 41.

The FCC catalyst separated by the cyclone 21 is supplied to the stripper 23. Steam, nitrogen and the like are supplied to the stripper 23. The stripper 23 removes hydrocarbons on the FCC catalyst with steam, nitrogen, or the like. Then, the FCC catalyst is discharged from the reaction tower 20 by the catalyst transfer line 24 after the reaction and transferred to the regeneration tower 30.

The temperature of the stripper 23 during the stripping treatment is usually 470 to 530 ° C, preferably 480 to 520 ° C, and more preferably 490 to 510 ° C. As the gas used for stripping, an inert gas such as nitrogen generated by a boiler or boosted by a compressor or the like is used.

Air is supplied from the air blower 31 to the air grid 32, air is supplied from the air grid 32 into the regeneration tower 30, and the cork on the stripping-treated FCC catalyst transferred to the regeneration tower 30 is burned and the FCC catalyst is burned. Is played. The regenerated FCC catalyst and the exhaust gas generated by the combustion of cork are separated by the cyclone 33. The regenerated FCC catalyst is discharged from the regeneration tower 30 by the regeneration catalyst transfer line 34 and supplied to the riser 10. The exhaust gas is discharged from the regeneration tower 30 by the exhaust gas line 35.

As the operating conditions of the catalyst regeneration tower, the regeneration temperature is preferably 600 to 800 ° C, more preferably 700 to 750 ° C.
When the regeneration temperature in the catalyst regeneration tower is 600 ° C. or higher, the combustion of cork proceeds sufficiently and the catalytic activity is sufficiently restored. Further, when the regeneration temperature in the catalyst regeneration tower is 800 ° C. or lower, the adverse effect on the device material is low.

The cracked oil transferred from the reaction tower 20 to the distillation column 41 by the cracked oil discharge line 22 is distilled from the top of the distillation column 41 a distillate containing a compound having about 1 to 13 carbon atoms. Heavy cracked gas oil (HCO) and light cracked gas oil (LCO) are distilled from the middle stage, and fluid contact cracked gas oil (SLO) is distilled from the bottom of the column to produce petroleum products.

The fraction containing a compound having about 1 to 13 carbon atoms is transferred from the distillation column 41 to the distillation column 43 by the line 42, the gas component is removed from the top of the distillation column 43, and the liquefied petroleum gas is placed on the bottom of the distillation column 43. A distillate containing (LPG) and gasoline as main components can be obtained.
The fraction containing LPG and gasoline as a main component is transferred from the distillation column 43 to the distillation column 45 by the line 44, and in the distillation column 45, the fraction containing LPG as a main component is distilled from the top of the column. A fraction containing gasoline as the main component can be obtained from the bottom.
The fraction containing LPG as a main component is transferred from the distillation tower 45 to the distillation tower 47 by the line 46, and the fraction containing propylene as a main component of petrochemical raw material is distilled from the top of the distillation tower 47. Then, a distillate containing butene, which is a petrochemical raw material, as a main component can be obtained from the bottom of the tower.
The fraction containing gasoline as a main component is transferred from the distillation column 45 to the aromatic extraction device 60 by the line 48, and in the aromatic extraction device 60, the fraction containing an aromatic compound as a main component of a petrochemical raw material is used. It is separated into a gasoline-based distillate from which aromatic compounds have been removed.
The fraction containing the main component of gasoline from which the aromatic compound has been removed is transferred to the naphtha cracker 70 by the line 61, and the distillate containing the petrochemical raw materials ethylene, propylene and the aromatic compound as the main components by the naphtha cracker 70. You get a minute.
Further, the fraction containing gasoline as the main component from which the aromatic compound has been removed is transferred to the catalytic reforming device 80 by the line 62, and the aromatic compound which is a petrochemical raw material is used as the main component by the catalytic reforming device 80. A distillate is obtained.

<Petrochemical raw materials>
Examples of the petrochemical raw material produced by the method for producing a petrochemical raw material of the present embodiment include olefins having 3 to 8 carbon atoms, aromatic compounds, and the like. Examples of the olefin having 3 to 8 carbon atoms include propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene and the like. Examples of the aromatic compound include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene and the like.

<Process to obtain energy derived from waste>
In the present embodiment, the energy required for the process of processing the raw material oil in the petroleum refining facility is the energy obtained by burning either one or both of combustibles including waste and methane obtained from the waste. Is used.
As the waste, general waste is preferable.

Combustible wastes including wastes include waste plastics, food wastes such as food residues and swill, and other combustible wastes (hereinafter, other combustible wastes are also referred to as "combustible wastes". ), And it is preferable that the above three types are sorted in advance.

Take as an example the case where the combustion equipment 102 is the above-mentioned combustion equipment including a waste pit, a crane, an incinerator, a waste heat boiler, an economizer, an ash pit, a dust collector, and a denitration reaction tower, and the power generation equipment 104 is a turbine type power generation equipment. , The production of energy derived from waste in the combustion equipment 102 and the power generation equipment 104 will be described.

Combustible waste is put into the garbage pit and stored. The combustibles stored in the garbage pit are put into the incinerator by a crane or the like. Combustibles are incinerated in an incinerator, and the heat of the exhaust gas generated by the incinerator is recovered by a waste heat boiler and an economizer. If necessary, methane supplied to the combustion equipment 102 may be used as fuel for incineration of combustibles via the methane supply line L302. Water supply is preheated by an economizer, and steam is produced in a waste heat boiler. The produced steam is supplied to the oil refinery 101 via the steam supply line L201. Further, the produced steam is supplied to the power generation facility 104 via the steam supply line L204.
In addition, the incinerated ash discharged from the incinerator is sent to the ash pit and then carried out. Further, the exhaust gas generated by incineration is lowered in temperature by the above-mentioned waste heat boiler and economizer, and then released to the atmosphere after removing harmful substances by a dust collector and a denitration reaction tower.

In the power generation facility 104, power is generated by steam supplied via the steam supply line L204. The generated electric power is supplied to the oil refining facility 101 via the electric power supply line L401.

When steam is produced by burning waste and power is generated using the produced steam, it is manufactured due to partial or total shutdown due to periodic inspections and repairs, fluctuations in incinerator amount, fluctuations in waste quality, etc. There is a problem that it is difficult to use energy efficiently because the amount of steam and the power generation output are not stable. In the present embodiment, the steam produced by the incineration facility 102 and the electric power generated by the power generation facility 104 are used in the step of processing the raw material oil in the petroleum refining facility. Oil refineries use enormous amounts of energy with precise control. That is, in the oil refining facility, the energy produced by the existing boiler or power generation facility and the energy derived from the waste of the present embodiment are used in combination. Therefore, in the present embodiment, even if the amount of steam produced by the combustion equipment 102 and the power generation output of the power generation equipment 104 fluctuate, the amount of energy produced by the existing boiler or the power generation equipment is adjusted. The fluctuation can be sufficiently settled, and the electric power can be used efficiently.

The production of energy derived from waste in the microbial fermentation equipment 103 will be described by taking as an example the case where the microbial fermentation equipment 103 is the above-mentioned microbial treatment equipment provided with a sorting machine, a slurry tank, a methane fermentation tank, and a desulfurization tower.

First, a sorting machine is used to remove foreign substances such as plastic bags and plastics contained in food waste. The removed food waste is transferred to a slurry tank and water is added to make a slurry. The slurry is transferred to a methane fermentation tank, and the organic matter contained in the slurry is converted into biogas containing methane gas and carbon dioxide as main components by methane fermenting bacteria. The obtained biogas is transferred to a desulfurization tower to remove hydrogen sulfide, and biogas containing methane gas is produced. The produced biogas containing methane gas is supplied to the petroleum refining facility 101 via the methane supply line L301. Further produced biogas containing methane gas is supplied to the combustion equipment 102 via the methane supply line L302.

The steam supplied to the oil refining facility 101 via the steam supply line L201 is used as the power of the pump used in the oil refining facility 101, the reboiler of the distillation column, and the like. When the petroleum refining facility is an FCC facility, the steam is a steam for catalyst circulation, a steam for dispersing raw material oil, a steam for separating the catalyst and the decomposed oil after the reaction in the reaction tower 20, and a stripper 23. Used as the steam used. Further, when the petroleum refining equipment 101 includes a melting tank 50, the steam is used for heating the melting tank.

The methane supplied to the petroleum refining equipment 101 via the methane supply line L301 is used as a raw material for heating the heating furnace (including the preheater) of the petroleum refining equipment 101. When the generated methane is surplus, it is used as a raw material for, for example, a hydrogen production apparatus.

The electric power supplied to the petroleum refining facility 101 via the electric power supply line L401 is used for the equipment using the electric power of the petroleum refining facility 101. Further, when the petroleum refining equipment 101 includes the melting tank 50, the electric power is used to power the stirring device of the melting tank and the pump for transporting the resin dissolution liquid from the melting tank 50 to the riser 10.

When the amount of waste is small with respect to the steam and electric power required for the oil refining facility 101, steam and electric power may be supplied to the oil refining facility from a boiler and a power generation facility using ordinary fossil fuels. Further, fossil fuel may be used as an auxiliary fuel for the combustion equipment 102.

The oil refining equipment 101, the combustion equipment 102, the microbial treatment equipment 103, and the power generation equipment 104 are preferably installed in a geographically integrated manner, and the distance between each equipment is preferably 0.1 to 5 km. , 0.1 to 1 km, more preferably.
Oil refineries are usually located within refinery facilities. Since the refinery facility has a plurality of high-pressure gas facilities, it is preferable that the combustion facility 102 is installed outside the refinery facility. That is, it is preferable that one or both of the combustibles including waste and the methane obtained from the waste are burned outside the refinery equipment.

The amount of steam produced by the combustion equipment 102 is preferably 5,000 to 20,000 tons / day, and more preferably 10,000 to 15,000 tons / day.
The ratio of the amount of steam produced in the combustion equipment 102 per day to the amount of steam required in the process of processing the above-mentioned raw material oil in the petroleum refining equipment in one day is preferably 1 to 120%. More preferably, it is ~ 100%.
When the ratio is equal to or higher than the lower limit of the range, the consumption of fossil fuel can be reduced accordingly.

The amount of electric power generated by the power generation facility 104 is preferably 500,000 to 2,000,000 kWh / day, and more preferably 800,000 to 1,500,000 kWh / day.
The ratio of the amount of electric power generated per day by the electric power facility 104 to the amount of electric power required per day in the process of processing the above-mentioned raw material oil in the petroleum refining facility is preferably 1 to 120%. More preferably, it is ~ 100%.
When the ratio is equal to or higher than the lower limit of the range, the consumption of fossil fuel can be reduced accordingly.

1 ... Flowing catalytic cracking equipment, 10 ... Riser, 11 ... Flowing catalytic cracking raw material oil supply line, 12 ... Preheating device, 20 ... Reaction tower, 21 ... Cyclone, 22 ... Decomposing oil discharge line, 23 ... Stripper, 24 ... After reaction Catalytic transfer line, 30 ... Regeneration tower, 31 ... Air blower, 32 ... Air grid, 33 ... Cyclone, 34 ... Regeneration catalyst transfer line, 35 ... Exhaust line, 40 ... Purification equipment, 41 ... Distillation tower, 42 ... Line, 43 Distillation tower, 44 ... line, 45 ... distillation tower, 46 ... line, 47 ... distillation tower, 48 ... line, 50 ... resin melting tank, 51 ... resin solution supply line, 52 ... preheating device, 60 ... aromatic extraction Equipment, 61 ... line, 62 ... line, 70 ... naphtha cracker, 80 ... catalytic reforming equipment, 100 ... petroleum product manufacturing system, 101 ... petroleum refining equipment, 102 ... combustion equipment, 103 ... microbial treatment equipment, 104 ... power generation Equipment, L201 ... steam supply line, L204 ... steam supply line, L301 ... methane supply line, L302 ... methane supply line, L401 ... power supply line

Claims (5)

A petroleum product manufacturing method that manufactures petroleum products by processing raw material oil in a petroleum refining facility.
A method for producing a petroleum product, which uses energy obtained by burning either one or both of combustibles including waste and methane obtained from the waste as the energy required for the treatment. The method for producing a petroleum product according to claim 1, wherein the raw material oil contains a resin derived from waste plastic. The method for producing a petroleum product according to claim 1 or 2, wherein one or both of the combustibles including the waste and the methane obtained from the waste are burned outside the refinery equipment. The method for producing a petroleum product according to any one of claims 1 to 3, wherein the waste is general waste. Obtained by the combustion equipment between the petroleum refining facility, a combustion facility that burns one or both of combustibles including waste and methane obtained from the waste, and the combustion facility and the petroleum refining facility. A petroleum product manufacturing system that has a means of transmitting energy.

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