Method for producing chemical product and method for managing same

Abstract

[Problem] To provide a method for efficiently producing a chemical product from a waste material containing waste tires by improving each step in a series of processes to realize long-term operation of the processes. [Solution] This method for producing a chemical product involves a pyrolysis step for obtaining, through pyrolysis of a crushed product of a waste material including waste tires, a first gas component, a pyrolysis oil, and a residual component, a low-temperature hydrogenation step for subjecting a raw material oil containing at least part of the pyrolysis oil to a low-temperature hydrogenation treatment at a temperature of 180°C-350°C to obtain a low-temperature hydrogenated oil, a high-temperature hydrogenation step for subjecting a raw material oil containing at least part of the low-temperature hydrogenated oil to a hydrogenation treatment at a temperature higher than that of the low-temperature hydrogenation treatment to obtain a second gas component and a high-temperature hydrogenated oil, a separation step for separating a naphtha fraction from other fractions through atmospheric distillation of an atmospheric distillation raw material oil containing crude oil and at least part of the high-temperature hydrogenated oil, and a steam cracking step for subjecting a steam cracking raw material oil containing at least part of the naphtha fraction and / or other fractions to a steam cracking treatment to obtain a chemical product, wherein the amount of the pyrolysis oil with respect to the total amount of the first gas component, the pyrolysis oil, and the residual component in the pyrolysis step is 40% by mass or more.

Description

Chemical product manufacturing method and management method

[0001] The present invention relates to a method for manufacturing chemical products using waste materials, and also to a method for managing chemical products that is executed using a management device used when manufacturing chemical products using waste materials.

[0002] In recent years, conversion of waste materials such as waste tires, waste rubber, and waste plastics into chemical products by pyrolysis or the like has been considered as a method for recycling such waste materials (for example, Patent Document 1).

[0003] Special table 2019-533041 publication

[0004] When it comes to recycling waste materials, the development of diverse processes is desired due to the fact that the type and quality of waste materials are not necessarily constant, and processes that can utilize existing facilities are required.

[0005] The present inventors have investigated a series of processes, particularly in a method for producing chemical products using waste materials, including a thermal cracking step in which waste materials are thermally cracked to obtain thermal cracking oil, a separation step (atmospheric distillation step) in which the thermal cracking oil is distilled to obtain a naphtha fraction and other fractions (kerosene fraction, diesel fraction), and a steam cracking step in which at least one of the naphtha fraction and / or other fractions is subjected to steam cracking to obtain a chemical product. In this series of processes, the inventors have discovered a technical problem in that if the thermal cracking oil is directly distilled using an existing atmospheric distillation unit, impurities such as dienes contained in the thermal cracking oil will cause fouling in the atmospheric distillation unit (by-products such as hydrocarbon polymers), making the process unsuitable for long-term operation.

[0006] The present invention aims to provide a method for efficiently producing chemical products from waste materials including waste tires, by improving each step in the series of processes to enable long-term operation of the process. Another object of the present invention is to provide a method for managing chemical products, which is executed using a management device used when producing chemical products from waste materials.

[0007] The present inventors conducted research to solve the above problems, and as a result, found that by improving the above-mentioned series of processes in a method for producing chemical products using waste materials and performing a low-temperature hydrogenation process in which the pyrolysis oil is subjected to low-temperature hydrogenation to obtain a low-temperature hydrogenated oil, and a high-temperature hydrogenation process in which the low-temperature hydrogenated oil is subjected to high-temperature hydrogenation to obtain a high-temperature hydrogenated oil, between the pyrolysis process and the separation process (atmospheric distillation process), it is possible to suppress the generation of fouling (by-products such as hydrocarbon polymers).The present inventors completed the present invention based on this finding.

[0008] One aspect of the present invention relates to, for example: [1] A method for producing a chemical product by steam cracking a steam cracking feedstock containing at least a portion of the naphtha fraction and / or at least a portion of the other fractions, the method comprising: a thermal cracking step of obtaining a first gas fraction, a thermal cracking oil, and a residue fraction by thermal cracking a crushed waste material including waste tires; a low-temperature hydrogenation step of subjecting a feedstock containing at least a portion of the thermal cracking oil to low-temperature hydrogenation treatment at 180°C or higher and 350°C or lower to obtain a low-temperature hydrogenated oil; a high-temperature hydrogenation step of subjecting a feedstock containing at least a portion of the low-temperature hydrogenated oil to hydrogenation treatment at a temperature higher than that of the low-temperature hydrogenation treatment to obtain a second gas fraction and a high-temperature hydrogenated oil; a separation step of atmospherically distilling a feedstock containing at least a portion of the high-temperature hydrogenated oil and crude oil, thereby separating the feedstock into a naphtha fraction and other fractions; and a steam cracking step of steam cracking a steam cracking feedstock containing at least a portion of the naphtha fraction and / or other fractions to steam cracking treatment, the method comprising: a thermal cracking step of subjecting a chemical product to steam cracking treatment; A method for producing chemical products. [2] The method according to [1], wherein the thermal decomposition temperature in the thermal decomposition step is 350°C or higher and 750°C or lower. [3] The method according to [1] or [2], wherein the amount of the first gas component relative to the total amount of the first gas component, the thermal decomposition oil, and the residue component in the thermal decomposition step is 25% by mass or less. [4] The method according to any one of [1] to [3], wherein the amount of the thermal decomposition oil relative to the total amount of the first gas component, the thermal decomposition oil, and the residue component in the thermal decomposition step is 80% by mass or less. [5] The method according to any one of [1] to [4], wherein the 10% distillation temperature of the thermal decomposition oil is 90°C or higher and the 90% distillation temperature is 350°C or higher. [6] The method according to any one of [1] to [5], wherein the feedstock oil in the high-temperature hydrogenation step contains at least a portion of the thermal decomposition oil or a portion of a fraction obtained by fractional distillation of the thermal decomposition oil. [7] The thermal cracking oil is used as part of the feedstock oil for the low-temperature hydrogenation step after removing at least a portion of the high-boiling point oil having a boiling point exceeding 350 ° C. by distillation. [8] The production method according to any one of [1] to [6].[8] The production method according to any one of [1] to [7], wherein in the high-temperature hydrogenation step, the feedstock contains a low-boiling-point oil having a boiling point of 350°C or less and a high-boiling-point oil having a boiling point exceeding 350°C, and the content of the high-boiling-point oil is 50 mass% or less based on the total amount of the feedstock. [9] The production method according to any one of [1] to [8], wherein recycled oil containing at least a portion of the high-temperature hydrogenated oil obtained in the high-temperature hydrogenation step is used as part of the feedstock for the low-temperature hydrogenation step.

[10] The production method according to [9], wherein in the low-temperature hydrogenation step, the amount of the recycled oil relative to the total amount of the recycled oil and the pyrolysis oil in the feedstock is more than 10 mass% and 99 mass% or less.

[11] The production method according to any one of [1] to

[10] , wherein the high-temperature hydrogenation step is a step of hydrogenating the feedstock in the presence of a hydrogenation catalyst.

[12] The production method according to any one of [1] to

[11] , wherein the hydrogenation catalyst contains a Ni-based catalyst.

[13] The production method according to any one of [1] to

[112] , wherein in the high-temperature hydrogenation step, the nitrogen content in the atmospheric distillation feedstock is 2000 ppm by mass or more and the nitrogen content in the naphtha fraction is 25 ppm by mass or less.

[14] The production method according to any one of [1] to

[13] , wherein in the separation step, the amount of the high-temperature hydrogenated oil relative to the total amount of the high-temperature hydrogenated oil and the crude oil in the atmospheric distillation feedstock is 0.001% by mass or more and 9% by mass or less.

[15] The diene number of the low-temperature hydrogenated oil is 13.0 gI. ２

[16] The method according to any one of [1] to

[14] , wherein the iodine value of the low-temperature hydrogenated oil is less than 160 g / 100 g. ２

[17] The production method according to any one of [1] to

[16] , wherein the total acid number of the low-temperature hydrogenated oil is less than 5.0 mgKOH / g.

[18] The production method according to any one of [1] to

[17] , wherein in the steam cracking step, at least a part of the naphtha fraction is light naphtha.

[19] The production method according to any one of [1] to

[18] , wherein the chemical product is at least one selected from the group consisting of ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, indene, and methylstyrene.

[20] The production method according to any one of [1] to

[19] , wherein the waste material further comprises at least one of waste rubbers and waste plastics.

[21] A method for producing synthetic rubber, comprising a polymerization step of obtaining synthetic rubber by a polymerization reaction using butadiene obtained by the production method according to

[19] as at least a part of the raw materials for the synthetic rubber.

[22] A tire comprising the synthetic rubber obtained by the production method according to

[21] .

[23] A method for producing tire, comprising a vulcanization step of obtaining a tire by a vulcanization reaction using the synthetic rubber obtained by the production method according to

[21] as at least a part of the raw materials for the tire.

[24] A method for managing chemical products, which is carried out using a management device used when manufacturing chemical products using waste materials including waste tires, wherein the management method uses the management device to assign a value as a renewable product to the chemical product using a mass balance method in accordance with the content ratio of renewable raw materials contained in the waste material, and the management method includes a step (V) of confirming that the chemical product can be obtained, and the step (V) includes the following steps (V-1), (V-2), (V-3), (V-4), (V-5), and (V-6), and the step (V-1) is a step of confirming that pyrolysis oil is produced from the waste material input into a pyrolysis unit that obtains pyrolysis oil by pyrolysis of the waste material,The step (V-2) is a step of confirming that the low-temperature hydrogenated oil is produced from the thermal cracking oil that is input into a low-temperature hydrogenation unit in which a feedstock containing at least a portion of the thermal cracking oil is subjected to low-temperature hydrogenation treatment at 180°C or higher and 350°C or lower to obtain the low-temperature hydrogenated oil; the step (V-3) is a step of confirming that the high-temperature hydrogenated oil is produced from the low-temperature hydrogenated oil that is input into a high-temperature hydrogenation unit in which a feedstock containing at least a portion of the low-temperature hydrogenated oil is subjected to hydrogenation treatment at a temperature higher than the low-temperature hydrogenation treatment to obtain a second gas fraction and the high-temperature hydrogenated oil; and the step (V-4) is a step of confirming that the naphtha fraction and the other fractions are produced from the high-temperature hydrogenated oil that is input into an atmospheric distillation unit in which an atmospheric distillation feedstock containing at least a portion of the high-temperature hydrogenated oil and crude oil is separated into a naphtha fraction and other fractions by atmospheric distillation. The step (V-5) is a step of confirming that the chemical product can be obtained from the steam cracking feedstock fed into a steam cracker that subjects a steam cracking treatment to a steam cracking feedstock containing at least a portion of the naphtha fraction and / or the other fraction, the step (V-6) is a step of confirming that the chemical product can be obtained from the waste material by processing it in the order of the thermal cracking unit, the low-temperature hydrogenation unit, the high-temperature hydrogenation unit, the atmospheric distillation unit, and the steam cracker, the management method includes a step (Z) of confirming the proportion of products to be assigned a value as a renewable product, the step (Z) including the following steps (Z-1), (Z-2), (Z-3), and (Z-4), the step (Z-1) is a step of selecting products to be assigned as renewable products from the products obtained by the steam cracker, The step (Z-2) is a step of determining the value of the proportion (P) to be allocated as a renewable product among the proportion of the product selected in the step (Z-1) to the product obtained by the steam cracker, and the step (Z-3) is a step of determining the value of the content proportion (Q) of renewable raw materials contained in the waste material,A method for managing chemical products, wherein the step (Z-4) is a step of comparing the value of the ratio (P) with the value of the content ratio (Q) and confirming that the value of the ratio (P) is equal to or less than the value of the content ratio (Q).

[25] The management device is provided with a computer-readable storage medium storing a management program, and the management device executes the management method described in

[24] by executing the management program.

[26] The management device described in

[25] , after executing the management method, outputs a result of assigning a value as a renewable product to a selected product according to the content ratio of renewable raw materials contained in waste materials including scrap tires, obtained by the management method.

[27] A computer-readable storage medium storing a computer program, the storage medium storing the management program causing a computer to execute the management method described in

[24] .

[28] A management program causing a computer to execute the management method described in

[24] .

[0009] According to the present invention, a method for efficiently producing chemical products from waste materials including waste tires is provided, which enables long-term operation of the process by improving each step in the series of processes. The present invention also provides a method for managing chemical products, which is executed using a management device used when producing chemical products from waste materials.

[0010] FIG. 1 is a schematic diagram showing an example of a thermal decomposition device. FIG. 2 is a schematic diagram showing an example of a system for implementing a method for producing chemical products. FIG. 3 is a schematic diagram for explaining the functional configuration of a management device. FIG. 4 is a block diagram showing an example of the hardware configuration of the management device. FIG. 5 is a flowchart showing an example of the processing procedure of a management program in a control unit of the management device. FIG. 6 is a schematic diagram of a soiling evaluation test device (HLPS) used in the examples.

[0011] Preferred embodiments of the present invention will now be described in detail.

[0012] The method for producing chemical products of this embodiment includes a thermal decomposition step in which a first gas fraction, a thermal cracking oil, and a residue fraction are obtained by thermal decomposition of crushed waste materials including waste tires; a low-temperature hydrogenation step in which a feedstock containing at least a portion of the thermal cracking oil is subjected to low-temperature hydrogenation treatment at 180°C or higher and 350°C or lower to obtain low-temperature hydrogenated oil; a high-temperature hydrogenation step in which a feedstock containing at least a portion of the low-temperature hydrogenated oil is subjected to hydrogenation treatment at a temperature higher than the low-temperature hydrogenation treatment to obtain a second gas fraction and high-temperature hydrogenated oil; a separation step in which an atmospheric distillation feedstock containing at least a portion of the high-temperature hydrogenated oil and crude oil is separated into a naphtha fraction and other fractions by atmospheric distillation; and a steam cracking step in which a steam cracking feedstock containing at least a portion of the naphtha fraction and / or other fractions is subjected to steam cracking treatment to obtain chemical products.

[0013] In the thermal decomposition step of this embodiment, the amount of the thermal cracking oil relative to the total amount of the first gas component, the thermal cracking oil, and the residue component is 40 mass% or more.

[0014] In the method for producing chemical products of this embodiment, crushed waste materials including waste tires are used and subjected to the above-mentioned steps, which makes it possible to suppress the generation of fouling in the heat exchangers in the high-temperature hydrogenation step and atmospheric distillation step, thereby enabling the process to be operated for a long period of time, and chemical products can be produced efficiently from waste materials including waste tires.

[0015] Each step of the present invention will be described in detail below.

[0016] (Pyrolysis Step) The pyrolysis step is a step of obtaining a first gas component, a pyrolysis oil, and a residue component by pyrolysis of crushed waste materials including waste tires.

[0017] The waste material includes at least waste tires, and may further include at least one of waste rubbers and waste plastics.

[0018] The waste materials can also be referred to as polymer-based waste materials containing polymer materials, such as rubber materials such as natural rubber, BR (butadiene rubber), SBR (styrene-butadiene rubber), NBR (nitrile rubber), IIR (butyl rubber), Cl-IIR (chlorinated butyl rubber), and Br-IIR (brominated butyl rubber), as well as resin materials such as polyethylene, polypropylene, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, and polyvinyl chloride.

[0019] The waste material may further contain metal components. For example, waste tires may contain metal components such as steel cords and wires, which are aggregates of the tires.

[0020] When the waste material contains metals, the manufacturing method of this embodiment may further include a removal step of removing the metals from the waste material or its crushed material. The method for removing the metals from the waste material is not particularly limited, and examples thereof include methods using a magnet, a sieve, etc.

[0021] It is not necessary to remove metals from the waste material before the pyrolysis step. For example, if the crushed waste material contains metals, the pyrolysis step will produce a first gas, pyrolysis oil, and a mixture of residue and metals. The manufacturing method of this embodiment may further include a removal step of removing metals from the mixture. The method for removing metals from the mixture is not particularly limited, and examples include methods using a magnet, a sieve, etc.

[0022] The method for crushing the waste material is not particularly limited, and may be, for example, mechanical crushing using a single-axis crusher or a twin-axis crusher, crushing using a water jet, freeze crushing, laser crushing, or the like.

[0023] The pyrolysis of crushed waste material can be carried out, for example, by placing the crushed waste material in a pyrolysis furnace, supplying high-temperature gas to the pyrolysis furnace, and bringing the crushed waste material into contact with the high-temperature gas. The high-temperature gas is preferably an oxygen-free gas that is substantially free of oxygen (e.g., a gas with an oxygen content of 1% by volume or less). The high-temperature gas may be any gas other than oxygen and oxides, such as an inert gas such as nitrogen, argon, or helium, hydrogen, or a hydrocarbon having 1 to 4 carbon atoms. The pyrolysis furnace is not particularly limited, and may be, for example, a kettle-type pyrolysis furnace, a fluidized-bed pyrolysis furnace, or a kiln-type pyrolysis furnace.

[0024] The thermal decomposition temperature (temperature of the high-temperature gas) in the thermal decomposition step may be, for example, 300 ° C. or higher, and from the viewpoint of further improving the chemical product yield, it is preferably 350 ° C. or higher, more preferably 370 ° C. or higher, and even more preferably 390 ° C. or higher. The thermal decomposition temperature (temperature of the high-temperature gas) in the thermal decomposition step may be, for example, 800 ° C. or lower, and from the viewpoint of further improving the chemical product yield, it is preferably 750 ° C. or lower, more preferably 730 ° C. or lower, and even more preferably 710 ° C. or lower. In addition, such a temperature range makes it easier to satisfy the amount of the preferred products (first gas component, thermal cracking oil, and residue component) described below, and also tends to make it easier to obtain a feedstock oil having a high-boiling point oil content within a suitable range. That is, the pyrolysis temperature (temperature of the high-temperature gas) in the pyrolysis step may be, for example, 300 to 800°C, 300 to 750°C, 300 to 730°C, 300 to 710°C, 350 to 800°C, 350 to 750°C, 350 to 730°C, 350 to 710°C, 370 to 800°C, 370 to 750°C, 370 to 730°C, 370 to 710°C, 390 to 800°C, 390 to 750°C, 390 to 730°C, or 390 to 710°C.

[0025] The thermal decomposition may be carried out in the presence of a thermal decomposition catalyst or in the absence of a thermal decomposition catalyst. As the thermal decomposition catalyst, catalysts used in ordinary petrochemical thermal decomposition can be used without any particular limitation. The thermal decomposition catalyst may be an acidic catalyst or a basic catalyst. Examples of the acidic catalyst include catalysts containing aluminosilicates. Examples of the aluminosilicate include smectite groups such as zeolite and montmorillonite. Examples of catalysts containing montmorillonite include clays or minerals such as activated clay, acid clay, and bentonite. Examples of the basic catalyst include carbonates such as sodium carbonate.

[0026] The conditions for pyrolysis may be appropriately adjusted so that the resulting component ratios, the properties of the resulting pyrolysis oil, etc., fall within the preferred ranges described below.

[0027] In the thermal decomposition process, a first gas component, a pyrolysis oil, and a residue component are obtained. As described above, the residue component may be obtained as a mixture with a metal component. In the thermal decomposition process, for example, a pyrolysis gas is generated in a pyrolysis furnace, and the pyrolysis gas is cooled to recover the pyrolysis oil as an oil component. In the thermal decomposition process, for example, the first gas component can be recovered as a residual gas after cooling the pyrolysis gas to recover the oil component. In the thermal decomposition process, for example, the residue component can be recovered as a solid component remaining in the pyrolysis furnace after pyrolysis.

[0028] In this embodiment, the amount of pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue component is 40 mass% or more.

[0029] In the past, in waste material processing methods, from the viewpoint of processing as much waste material as possible, thermal decomposition has been mainly performed under conditions that result in a small amount of residue and a large amount of gas (for example, Patent Document 1). In contrast, the production method of the present embodiment deliberately performs thermal decomposition under conditions that result in an amount of pyrolysis oil of 40 mass% or more, thereby improving the yield of chemical products obtained through the low-temperature hydrogenation step, high-temperature hydrogenation step, atmospheric distillation step, and steam cracking step.

[0030] In the thermal decomposition step, the amount of pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue may be, for example, 45% by mass or more. From the viewpoint of improving the yield of chemical products obtained through the low-temperature hydrogenation step, the high-temperature hydrogenation step, the atmospheric distillation step, and the steam cracking step, in the thermal decomposition step, the amount of pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue may be preferably 48% by mass or more, more preferably 50% by mass or more, or 51% by mass or more, or 52% by mass or more. Further, in the thermal decomposition step, the amount of pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue may be, for example, 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, or may be 60% by mass or less. That is, in the thermal decomposition step, the amount of thermal cracking oil relative to the total amount of the first gas component, the thermal cracking oil, and the residue component is, for example, 40 to 80 mass%, 40 to 75 mass%, 40 to 70 mass%, 40 to 65 mass%, 40 to 60 mass%, 45 to 80 mass%, 45 to 75 mass%, 45 to 70 mass%, 45 to 65 mass%, 45 to 60 mass%, 48 to 80 mass%, 48 to 75 mass% , 48-70% by mass, 48-65% by mass, 48-60% by mass, 50-80% by mass, 50-75% by mass, 50-70% by mass, 50-65% by mass, 50-60% by mass, 51-80 quality mass%, 51-75 mass%, 51-70 mass%, 51-65 mass%, 51-60 mass%, 52-80 mass%, 52-75 mass%, 52-70 mass%, 52-65 mass% or 52-65 mass% It may be 60% by mass.

[0031] In the thermal decomposition step, the amount of the first gas component relative to the total amount of the first gas component, pyrolysis oil, and residue is, for example, 25% by mass or less. From the viewpoint of improving the yield of chemical products obtained through the low-temperature hydrogenation step, high-temperature hydrogenation step, atmospheric distillation step, and steam cracking step, in the thermal decomposition step, the amount of the first gas component relative to the total amount of the first gas component, pyrolysis oil, and residue is preferably 20% by mass or less, more preferably 15% by mass or less, and may be 13% by mass or less or 10% by mass or less. If the thermal decomposition conditions are such that the amount of the first gas component is 25% by mass or less, a decrease in the yield of pyrolysis oil due to excessive progress of pyrolysis of the crushed material can be suppressed. In other words, under the above thermal decomposition conditions, it is possible to suppress further pyrolysis of the pyrolysis oil produced by the pyrolysis of the crushed material into gas components, and the yield of pyrolysis oil that can be made into chemical products through the low-temperature hydrogenation step, high-temperature hydrogenation step, atmospheric distillation step, and steam cracking step can be further improved, and ultimately the yield of chemical products is further improved.

[0032] The amount of the first gas component relative to the total amount of the first gas component, pyrolysis oil, and residue is, for example, 0.1% by mass or more. From the viewpoint of improving the purity of the chemical product obtained through the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process, it may be 0.5% by mass or more, 0.7% by mass or more, 1% by mass or more, 1.3% by mass or more, or 1.5% by mass or more. If the crushed material contains, for example, chlorine, part of the chlorine in the crushed material is gasified as chlorine gas or the like by thermal decomposition. That is, part of the chlorine contained in the crushed material is removed as part of the first gas component. Therefore, when a predetermined amount of the first gas component is generated in the pyrolysis process, the chlorine content in the pyrolysis oil can be reduced compared to when the first gas component is not generated. Therefore, by setting the thermal cracking conditions so that a predetermined amount of the first gas component is generated, the purity of the chemical products obtained through the low-temperature hydrogenation process for the thermal cracking oil, the high-temperature hydrogenation process for the low-temperature hydrogenated oil, the atmospheric distillation process for the atmospheric distillation feed oil containing the high-temperature hydrogenated oil, and the steam cracking process for the steam cracking feed oil is further improved. Note that although the above example is given using chlorine content, the same applies when the crushed material contains nitrogen content, sulfur content, halogen element content other than chlorine content, etc. That is, the amount of the first gas component relative to the total amount of the first gas component, pyrolysis oil, and residue component is, for example, 0.1 to 25 mass%, 0.1 to 20 mass%, 0.1 to 15 mass%, 0.1 to 13 mass%, 0.1 to 10 mass% or less, 0.5 to 25 mass%, 0.5 to 20 mass%, 0.5 to 15 mass%, 0.5 to 13 mass%, 0.5 to 10 mass% or less, 0.7 to 25 mass%, 0.7 to 20 mass%, 0.7 to 15 mass% , 0.7 to 13 mass%, 0.7 to 10 mass% or less, 1 to 25 mass%, 1 to 20 mass%, 1 to 15 mass%, 1 to 13 mass%, 1 to 10 mass% or less, 1.3 to 25 mass%, 1.3 to 20 mass%, 1.3 ~15% by mass, 1.3-13% by mass, 1.3-10% by mass or less, 1.5-25% by mass, 1.5-20% by mass, 1.5-15% by mass, 1.5-13% by mass, or 1.5-10% by mass or less.

[0033] In the thermal decomposition step, the amount of the residue relative to the total amount of the first gas component, the thermal cracking oil, and the residue is, for example, 10% by mass or more. From the viewpoint of improving the yield of chemical products obtained through the low-temperature hydrogenation step, the high-temperature hydrogenation step, the atmospheric distillation step, and the steam cracking step, in the thermal decomposition step, the amount of the residue relative to the total amount of the first gas component, the thermal cracking oil, and the residue is preferably 15% by mass or more, more preferably 20% by mass or more. If the thermal decomposition conditions are such that the amount of the residue is 10% by mass or more, a decrease in the yield of the thermal cracking oil due to excessive progress of thermal decomposition of the crushed material can be suppressed. In other words, under the above thermal decomposition conditions, the thermal cracking oil produced by the thermal decomposition of the crushed material can be suppressed from being further thermally decomposed into a gas component, and the yield of the thermal cracking oil that can be made into a chemical product through the low-temperature hydrogenation step, the high-temperature hydrogenation step, the atmospheric distillation step, and the steam cracking step can be further improved, and thus the yield of the chemical product is further improved.

[0034] The amount of residue relative to the total amount of the first gas component, pyrolysis oil, and residue is, for example, 60% by mass or less. From the viewpoint of improving the yield of chemical products obtained through the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process, it is preferably 55% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, and may be 40% by mass or less. As the amount of residue relative to the total amount of the first gas component, pyrolysis oil, and residue increases, the amount of the first gas component and pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue becomes smaller. Therefore, under thermal decomposition conditions where the amount of residue is 60% by mass or less, it is possible to suppress the crushed material that should become pyrolysis oil from remaining as residue, and the yield of pyrolysis oil that can be made into chemical products through the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process can be further improved, and ultimately the yield of chemical products is further improved. That is, in the thermal decomposition step, the amount of the residue relative to the total amount of the first gas component, pyrolysis oil, and residue component is, for example, 10 to 60 mass%, 10 to 55 mass%, 10 to 50 mass%, 10 to 45 mass%, 10 to 40 mass%, 15 to 60 mass%, 15 to 55 mass%, 15 to 50 mass%, 15 to 45 mass%, 15 to 40 mass%, 20 to 60 mass%, 20 to 55 mass%, 20 to 50 mass%, 20 to 45 mass%, or 20 to 40 mass%.

[0035] The first gas component may be, for example, a component of the product produced by pyrolysis that is gaseous at atmospheric pressure and 20° C. The first gas component may contain, for example, hydrogen, hydrocarbons having 1 to 4 carbon atoms, etc.

[0036] The method for recovering the first gas component is not particularly limited. For example, the first gas component can be recovered as a residual gas after cooling a pyrolysis gas produced by pyrolysis and recovering an oil component (pyrolysis oil).

[0037] The first gas fraction can be reused, for example, as high-temperature gas (oxygen-free gas) in pyrolysis. That is, the first gas fraction may be heated and supplied to a pyrolysis furnace as part (or all) of the high-temperature gas (oxygen-free gas). The first gas fraction can also be used, for example, as combustion gas for heating the pyrolysis section in the pyrolysis step or as combustion gas for a heating furnace in other steps.

[0038] The pyrolysis oil may be, for example, a component of the product produced by pyrolysis that is liquid at atmospheric pressure and 20°C. The method for recovering the pyrolysis oil is not particularly limited. The pyrolysis oil can be recovered, for example, as an oil fraction distilled from a pyrolysis furnace. That is, the pyrolysis oil can be recovered, for example, as an oil fraction condensed by cooling the pyrolysis gas produced by pyrolysis.

[0039] The distillation properties of the pyrolysis oil are not particularly limited, and may be such that it can be used as a feedstock oil in the low-temperature hydrogenation step and the high-temperature hydrogenation step.

[0040] The 10% distillation temperature (T10) of the pyrolysis oil may be, for example, 90°C or higher. From the viewpoint of being more suitable as a feedstock oil in a low-temperature hydrogenation step, it is preferably 140°C or higher, more preferably 150°C or higher, and even more preferably 155°C or higher. The 10% distillation temperature of the pyrolysis oil may be, for example, 200°C or lower, 190°C or lower, or 180°C or lower. That is, the 10% distillation temperature (T10) of the pyrolysis oil may be, for example, 90 to 200°C, 90 to 190°C, 90 to 180°C, 140 to 200°C, 140 to 190°C, 140 to 180°C, 150 to 200°C, 150 to 190°C, 150 to 180°C, 155 to 200°C, 155 to 190°C, or 155 to 180°C.

[0041] The 90% distillation temperature (T90) of the pyrolysis oil may be, for example, 350°C or higher, preferably 370°C or higher, more preferably 390°C or higher, and even more preferably 400°C or higher, and may be 410°C or higher, 420°C or higher, 430°C or higher, 440°C or higher, or 450°C or higher. Furthermore, the 90% distillation temperature (T90) of the pyrolysis oil may be, for example, 650°C or lower, preferably 600°C or lower, and more preferably 550°C or lower. That is, the 90% distillation temperature (T90) of the pyrolysis oil is, for example, 350 to 650 ° C, 350 to 600 ° C, 350 to 550 ° C, 370 to 650 ° C, 370 to 600 ° C, 370 to 550 ° C, 390 to 650 ° C, 390 to 600 ° C, 390 to 550 ° C, 400 to 650 ° C, 400 to 600 ° C, 400 to 550 ° C, 410 to 650 ° C, 410 to 600 ° C, 410 to 550 ° C, 420 to 650 ° C, °C, 420 to 600 °C, 420 to 550 °C, 430 to 650 °C, 430 to 600 °C, 430 to 550 °C, 440 to 650 °C, 440 to 600 °C, 440 to 550 °C, 450 to 650 °C, 450 to 600 °C, or 450 to 550 °C.

[0042] The pyrolysis oil contains low-boiling oils having a boiling point of 350°C or less, and may further contain high-boiling oils having a boiling point of more than 350°C.

[0043] The content of high-boiling oil in the thermal cracking oil is not particularly limited, but is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less, based on the total amount of the thermal cracking oil. By adjusting the content of high-boiling oil in the thermal cracking oil to 50% by mass or less, the diene value in the feedstock oil can be reduced, thereby reducing the fouling and clogging of piping and heat exchangers in a series of processes. Furthermore, the content of high-boiling oil in the thermal cracking oil may be, for example, 5% by mass or more, 8% by mass or more, or 10% by mass or more, based on the total amount of the thermal cracking oil. That is, the content of high-boiling point oil in the pyrolysis oil may be, for example, 5 to 50 mass%, 5 to 45 mass%, 5 to 40 mass%, 5 to 35 mass%, 8 to 50 mass%, 8 to 45 mass%, 8 to 40 mass%, 8 to 35 mass%, 10 to 50 mass%, 10 to 45 mass%, 10 to 40 mass%, or 10 to 35 mass%, based on the total amount of the pyrolysis oil.

[0044] The pyrolysis oil may contain nitrogen, sulfur, chlorine, halogen elements, and the like.

[0045] The nitrogen content of the pyrolysis oil may be, for example, 100 ppm by mass or more, 2000 ppm by mass or more, 2500 ppm by mass or more, or 3000 ppm by mass or more. In this embodiment, even if a large amount of nitrogen is present in the pyrolysis oil, the nitrogen content is converted into gas components such as ammonia by hydrogenation in the low-temperature hydrogenation process and the high-temperature hydrogenation process, and can be easily separated from the liquid product. Then, by supplying the liquid product with a significantly reduced nitrogen content to the steam cracking process, a high-purity chemical product (a chemical product with little nitrogen contamination) can be easily obtained. The nitrogen content of the pyrolysis oil may be, for example, 20,000 ppm by mass or less, 15,000 ppm by mass or less, or 10,000 ppm by mass or less. If the nitrogen content is 20,000 ppm by mass or less, the nitrogen content of the liquid product after the low-temperature hydrogenation process and the high-temperature hydrogenation process can be more significantly reduced. That is, the nitrogen content of the pyrolysis oil may be, for example, 100 to 20,000 ppm by mass, 100 to 15,000 ppm by mass, 100 to 10,000 ppm by mass, 2,000 to 20,000 ppm by mass, 2,000 to 15,000 ppm by mass, 2,000 to 10,000 ppm by mass, 2,500 to 20,000 ppm by mass, 2,500 to 15,000 ppm by mass, 2,500 to 10,000 ppm by mass, 3,000 to 20,000 ppm by mass, 3,000 to 15,000 ppm by mass, or 3,000 to 10,000 ppm by mass.

[0046] The sulfur content of the pyrolysis oil may be, for example, 10 ppm by mass or more, 100 ppm by mass or more, 500 ppm by mass or more, or 1000 ppm by mass or more. In this embodiment, even if a large amount of sulfur is present in the pyrolysis oil, the sulfur content is converted into gas components such as hydrogen sulfide by hydrogenation in the low-temperature hydrogenation process and the high-temperature hydrogenation process, and can be easily separated from the liquid product. Then, by supplying the liquid product with a significantly reduced sulfur content to the steam cracking process, a high-purity chemical product (a chemical product with little sulfur contamination) can be easily obtained. The sulfur content of the pyrolysis oil may be, for example, 30,000 ppm by mass or less, 20,000 ppm by mass or less, or 10,000 ppm by mass or less. If the sulfur content is 30,000 ppm by mass or less, the sulfur content of the liquid product after the low-temperature hydrogenation process and the high-temperature hydrogenation process can be more significantly reduced. That is, the sulfur content of the pyrolysis oil may be, for example, 10 to 30,000 ppm by mass, 10 to 20,000 ppm by mass, 10 to 10,000 ppm by mass, 100 to 30,000 ppm by mass, 100 to 20,000 ppm by mass, 100 to 10,000 ppm by mass, 500 to 30,000 ppm by mass, 500 to 20,000 ppm by mass, 500 to 10,000 ppm by mass, 1,000 to 30,000 ppm by mass, 1,000 to 20,000 ppm by mass, or 1,000 to 10,000 ppm by mass.

[0047] The chlorine content of the pyrolysis oil may be, for example, 10 ppm by mass or more, 30 ppm by mass or more, 50 ppm by mass or more, or 100 ppm by mass or more. In this embodiment, even if a large amount of chlorine is present in the pyrolysis oil, the chlorine content is converted into gas components such as hydrogen chloride by hydrogenation in the low-temperature hydrogenation step and the high-temperature hydrogenation step, and can be easily separated from the liquid product. Then, by supplying the liquid product with a significantly reduced chlorine content to the steam cracking step, a high-purity chemical product (a chemical product with little chlorine contamination) can be easily obtained. The chlorine content of the pyrolysis oil may be, for example, 2000 ppm by mass or less, 1500 ppm by mass or less, or 1000 ppm by mass or less. If the chlorine content is 1000 ppm by mass or less, the chlorine content of the liquid product after the low-temperature hydrogenation step and the high-temperature hydrogenation step can be more significantly reduced. Furthermore, it is preferable that not only the chlorine content but also the content of other halogen elements be within a similar range. That is, the chlorine content of the pyrolysis oil may be, for example, 10 to 2000 ppm by mass, 10 to 1500 ppm by mass, 10 to 1000 ppm by mass, 30 to 2000 ppm by mass, 30 to 1500 ppm by mass, 30 to 1000 ppm by mass, 50 to 2000 ppm by mass, 50 to 1500 ppm by mass, 50 to 1000 ppm by mass, 100 to 2000 ppm by mass, 100 to 1500 ppm by mass, or 100 to 1000 ppm by mass.

[0048] The residue may be, for example, a solid component of the product produced by pyrolysis that is not recovered as pyrolysis gas. The method for recovering the residue is not particularly limited. The residue can be recovered, for example, as a solid component remaining in the pyrolysis furnace (a solid component that is not discharged to the outside of the reaction system as pyrolysis gas).

[0049] The residue may be a char formed by thermal decomposition of the crushed waste material. In an embodiment, the residue may be recovered as a char.

[0050] The carbide is a component in which carbon accounts for the majority. The carbide may be, for example, a carbon concentrate containing carbon black as the main component. The carbide may contain aggregated lumps formed during the pyrolysis process. In this case, the aggregated carbide can be crushed using a crusher or the like to obtain a powdered carbide.

[0051] That is, the manufacturing method of this embodiment may further include a step of pulverizing the residue to obtain a powdered charcoal. Such a manufacturing method can be said to be a method capable of producing both a chemical product and a charcoal. Furthermore, in such a manufacturing method, by adjusting the amounts of the pyrolysis oil and the residue formed in the pyrolysis step to fall within the above-mentioned preferred ranges, both a chemical product and a charcoal can be efficiently obtained.

[0052] The powdered carbonized material can be suitably used as, for example, an additive for rubber, an additive for resin, a colorant, and the like.

[0053] Depending on the pyrolysis conditions, the residue may contain, for example, rubber components from waste materials that were not completely pyrolyzed. In this case, because the rubber components are sticky, the carbonized material is recovered as a mass of a mixture of carbon black and the rubber components. Such carbonized material is difficult to pulverize using a grinder or the like because the stickiness of the rubber components inhibits powdering of the carbonized material. Furthermore, the mass of carbonized material leads to poor dispersion in the matrix, making it difficult to use as a rubber additive, resin additive, colorant, or other application. In this regard, by adopting the above-described preferred pyrolysis conditions in the pyrolysis process of this embodiment, the amount of remaining rubber components in the recovered carbonized material tends to be reduced, making it easier to obtain a powdered carbonized material suitable for applications such as a rubber additive, resin additive, colorant, or other application.

[0054] Furthermore, if it is difficult to obtain a powdery carbonized product from the residue due to the presence of rubber components or the like, the manufacturing method of this embodiment may further include a step of producing a carbonized product by thermal decomposition of the residue.

[0055] The pyrolysis step may be carried out, for example, by a pyrolysis apparatus equipped with a pyrolysis furnace. The pyrolysis furnace used in the pyrolysis step may be any furnace capable of pyrolyzing the crushed material, and may be, for example, a batch pyrolysis furnace, a continuous pyrolysis furnace, or the like. As a continuous pyrolysis furnace, for example, a rotary kiln, an auger furnace, or the like may be used. Note that, although a pyrolysis apparatus equipped with a batch pyrolysis furnace will be described below as an example of a pyrolysis apparatus, the pyrolysis apparatus is not limited thereto.

[0056] Fig. 1 is a schematic diagram showing an example of a thermal decomposition apparatus. The thermal decomposition apparatus of Fig. 1 includes a heat exchanger 1 for heating an oxygen-free gas, a decomposition apparatus 7 having a pyrolysis furnace 2 that accommodates waste material 6 therein and an external heating means 8 for externally heating the pyrolysis furnace 2, an oil recovery apparatus 5 for cooling the pyrolysis gas generated in the decomposition apparatus 7 and recovering the condensed oil (pyrolysis oil), a circulation path 4 for supplying the residual gas after oil recovery in the oil recovery apparatus 5 as an oxygen-free gas to the heat exchanger 1, and an oxygen-free gas supply source 3 for supplying the oxygen-free gas to the heat exchanger 1.

[0057] The thermal decomposition apparatus of FIG. 1 also includes a flow meter 9, a damper 10, and a blower 11 in the piping connecting the oxygen-free gas supply source 3 to the heat exchanger 1 in order to supply oxygen-free gas from the oxygen-free gas supply source 3, and a flow meter 9, a damper 10, a blower 11, and a hot air furnace 14 in the circulation path 4 in order to circulate the remaining gas after recovery in the oil recovery device 5 to the heat exchanger 1 as oxygen-free gas.

[0058] The oil recovery unit 5 may also include multiple dry distillation towers 12a and 12b to separate the recovered oil according to its boiling point. Each dry distillation tower 12 may be connected to a recovery tank 13 at its lower part via piping, allowing the recovered oil to be stored. While the thermal cracking unit of FIG. 1 includes multiple dry distillation towers 12a and 12b, in this embodiment, the thermal cracking oil can be used directly as feed oil for the low-temperature hydrogenation step, so only one dry distillation tower may be used. In addition, in the thermal cracking unit of FIG. 1, each dry distillation tower 12 is connected to a separate recovery tank 13, but each dry distillation tower 12 may be connected to the same recovery tank 13.

[0059] It is preferable to remove at least a portion of the high-boiling point oil exceeding 350°C from the pyrolysis oil of the present invention by distillation or the like before the subsequent low-temperature hydrogenation step. By removing at least a portion of the high-boiling point oil from the pyrolysis oil, it is possible to suppress the generation of fouling in the heat exchangers and heating furnaces in the high-temperature hydrogenation step and the atmospheric distillation step, making it possible to realize long-term operation of the process. Although not limited thereto, it is more preferable to remove at least a portion of the high-boiling point oil, for example, having a boiling point exceeding 450°C.

[0060] As a method for removing the high boiling point oil, the pyrolysis gas immediately after being produced in the pyrolysis step is cooled and separated into a pyrolysis oil rich in high boiling point oil and a gas fraction rich in low boiling point oil, and then the gas fraction rich in low boiling point oil is further cooled to separate it into a first gas fraction and a pyrolysis oil rich in low boiling point oil. As another method, the pyrolysis oil can be heated and separated into low boiling point oil and high boiling point oil in a distillation column, but this is not limited to the method described above.

[0061] The content of high-boiling-point oil in the pyrolysis oil from which a portion of the high-boiling-point oil has been removed before the low-temperature hydrogenation step (hereinafter also referred to as "fractionated pyrolysis oil") is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less, based on the total amount of pyrolysis oil fractionated before the low-temperature hydrogenation step. If the content of high-boiling-point oil in the pyrolysis oil fractionated before the low-temperature hydrogenation step is 50% by mass or less, the effects of easily heavier components such as heavy olefins and dienes can be suppressed. Furthermore, the content of high-boiling-point oil in the pyrolysis oil fractionated before the low-temperature hydrogenation step may be, for example, 1% by mass or more, 2% by mass or more, or 3% by mass or more, based on the total amount of pyrolysis oil fractionated before the low-temperature hydrogenation step. The removed high-boiling-point oil may be recycled as a raw material for the pyrolysis step, used as a raw material for producing carbon black, or used as fuel.

[0062] (Low-Temperature Hydrogenation Step) The low-temperature hydrogenation step is a step in which a feedstock oil containing at least a portion of the thermal cracking oil is subjected to low-temperature hydrogenation treatment at 180° C. or higher and 350° C. or lower to obtain a low-temperature hydrogenated oil.

[0063] The feedstock oil in the low-temperature hydrogenation step may contain a pyrolysis oil or may contain fractionated pyrolysis oil. The feedstock oil in the low-temperature hydrogenation step may further contain components other than the pyrolysis oil, or the pyrolysis oil may be used as the feedstock oil as is.

[0064] As part of the feedstock oil in the low-temperature hydrogenation step, recycled oil containing at least a portion of the light and heavy fractions obtained in the high-temperature hydrogenation step described below, or any diluent hydrocarbon oil, may be used. The use of recycled oil or any diluent hydrocarbon oil makes it possible to dilute dienes and olefins, which tend to polymerize and generate fouling, thereby preventing the occurrence of fouling. Furthermore, the heat generation effect in the reactor in the low-temperature hydrogenation step and the high-temperature hydrogenation step can be reduced, thereby improving the stability of process operation. Examples of diluent hydrocarbons include kerosene fractions, diesel fractions, and vacuum diesel fractions obtained from an atmospheric distillation unit derived from crude oil, LCO obtained from an FCC unit, and even product kerosene and product diesel.

[0065] In the low-temperature hydrogenation step, the amount of recycled oil relative to the total amount of recycled oil and pyrolysis oil in the feed oil is preferably 10% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 97% by mass or less, even more preferably 30% by mass or more and 95% by mass or less, particularly preferably 40% by mass or more and 93% by mass or less, and most preferably 50% by mass or more and 90% by mass or less.

[0066] The low-temperature hydrogenation step may be a step of hydrogenating a feedstock in the presence of a hydrogenation catalyst. Hydrogenation can be carried out, for example, by supplying the feedstock to a reactor containing a hydrogenation catalyst and bringing the feedstock into contact with the hydrogenation catalyst in the reactor.

[0067] As the hydrogenation catalyst, for example, a known hydrogenation catalyst used in the hydrogenation of hydrocarbon oils can be used. From the viewpoint of hydrogenation ability, the hydrogenation catalyst preferably contains, for example, a Ni-based or Co-based catalyst. A Ni-based catalyst is a catalyst having Ni as an active metal, and Ni may be present in the form of a sulfide or the like. A Co-based catalyst is a catalyst having Co as an active metal. As the hydrogenation catalyst, one type of hydrogenation catalyst may be used, or multiple types of hydrogenation catalysts may be used.

[0068] The reaction temperature in the low-temperature hydrogenation step is 180° C. or higher and 350° C. or lower, preferably 190° C. or higher and 340° C. or lower, more preferably 200° C. or higher and 330° C. or lower, even more preferably 210° C. or higher and 320° C. or lower, particularly preferably 220° C. or higher and 310° C. or lower, and most preferably 240° C. or higher and 305° C. By adjusting the reaction temperature in the low-temperature hydrogenation step within the above-mentioned range, particularly 200° C. or higher, further preferably 240° C. or higher, it is possible to obtain a low-temperature hydrogenated oil having a reduced diene value.

[0069] The reaction pressure in the low-temperature hydrogenation step is not particularly limited and may be, for example, 1 MPaG or more, preferably 3 MPaG or more, and more preferably 5 MPaG or more. The reaction pressure in the low-temperature hydrogenation step is also not particularly limited and may be, for example, 20 MPaG or less, preferably 19 MPaG or less, and more preferably 18 MPaG or less. That is, the reaction pressure in the low-temperature hydrogenation step may be, for example, 1 to 20 MPaG, 1 to 19 MPaG, 1 to 18 MPaG, 3 to 20 MPaG, 3 to 19 MPaG, 3 to 18 MPaG, 5 to 20 MPaG, 5 to 19 MPaG, or 5 to 18 MPaG.

[0070] When the low-temperature hydrogenation step is carried out using a flow reactor, the weight hourly space velocity (WHSV) of the feedstock is, for example, 0.1 h －１ or more, preferably 0.15 h －１ More preferably, 0.2 h －１ The weight hourly space velocity (WHSV) of the feed oil is, for example, 5 h －１ may be less than or equal to 4 h, preferably －１ Less than 3 hours, preferably －１ That is, the weight hourly space velocity (WHSV) of the feed oil is 0.1 to 5 h －１ , 0.1 to 4 h －１ , 0.1 to 3 h －１ , 0.15 to 5 h －１ , 0.15 to 4 h －１ , 0.15 to 3 h －１ , 0.2 to 5 h －１ , 0.2 to 4 h －１ Or 0.2 to 3 hours －１ may be.

[0071] The low-temperature hydrogenation step is carried out in the presence of hydrogen. When the low-temperature hydrogenation step is carried out using a flow reactor, the hydrogen / oil ratio may be, for example, 100 NL / L or more, preferably 150 NL / L or more, and more preferably 200 NL / L or more. The hydrogen / oil ratio may be, for example, 1500 NL / L or less, preferably 1400 NL / L or less, and more preferably 1300 NL / L or less. That is, the hydrogen / oil ratio may be, for example, 100 to 1500 NL / L, 100 to 1400 NL / L, 100 to 1300 NL / L, 150 to 1500 NL / L, 150 to 1400 NL / L, 150 to 1300 NL / L, 200 to 1500 NL / L, 200 to 1400 NL / L, or 200 to 1300 NL / L.

[0072] The low-temperature hydrogenated oil obtained in the low-temperature hydrogenation step preferably has the following properties: The diene value of the low-temperature hydrogenated oil is preferably 14.0 g / L ２ / 100g, more preferably less than 13.0gI ２ / 100g or less, more preferably 12.0gI ２ / 100g or less, and particularly preferably 11.0gI ２ The iodine value of the low-temperature hydrogenated oil is preferably 160 g / L or less. ２ / 100g or less, more preferably 155g / ２ / 100g or less, more preferably 150gI ２ / 100g or less, and particularly preferably 145gI ２ The total acid number of the low-temperature hydrogenated oil is less than 5.0 mgKOH / g, more preferably 4.8 mgKOH / g or less, even more preferably 4.7 mgKOH / g or less, and particularly preferably 4.5 mgKOH / g or less.

[0073] In the present invention, by reducing in advance the olefins, dienes, higher fatty acids, and the like that polymerize and cause fouling in the pyrolysis oil treated in the low-temperature hydrogenation step, it is possible to suppress the occurrence of fouling in the heat exchangers of the high-temperature hydrogenation step and the atmospheric distillation unit, thereby making it possible to operate the process for a long period of time.

[0074] (High-temperature hydrogenation step) The high-temperature hydrogenation step is a step of obtaining a second gas fraction and a high-temperature hydrogenated oil by high-temperature hydrotreating a feedstock oil containing at least a portion of the low-temperature hydrogenated oil. The high-temperature hydrogenated oil contains a light fraction having a boiling point of 350°C or less and a heavy fraction having a boiling point of more than 350°C.

[0075] The feedstock oil in the high-temperature hydrogenation step contains low-temperature hydrogenated oil, but may also contain thermal cracking oil, fractionated thermal cracking oil, or other components.

[0076] The feedstock oil in the high-temperature hydrogenation step contains low-boiling-point oils with boiling points of 350°C or less and high-boiling-point oils with boiling points above 350°C, and the content of high-boiling-point oils is, for example, 50% by mass or less based on the total amount of feedstock oil. By adjusting the cracking conditions in the high-temperature hydrogenation step, it is possible to convert the high-boiling-point oils into light fractions, and the light fractions are substances supplied as raw materials for producing chemical products in the steam cracking step described below. Therefore, the higher the content of high-boiling-point oils, the more suitable the feedstock oil becomes, and the tendency is for the yield of chemical products to be further improved. However, in order to reduce fouling and clogging of piping and heat exchangers in the series of processes, it is preferable to reduce the amount of the high-boiling-point oil.

[0077] The content of high-boiling oil in the feedstock oil in the high-temperature hydrogenation step is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less, based on the total amount of the feedstock oil. Also, the content of high-boiling oil in the feedstock oil in the high-temperature hydrogenation step may be 1.0% by mass or more, 2.0% by mass or more, or 3.0% by mass or more, based on the total amount of the feedstock oil.

[0078] The 10% distillation temperature of the feedstock oil in the high-temperature hydrogenation step may be, for example, 90°C or higher, preferably 140°C or higher, more preferably 150°C or higher, and even more preferably 155°C or higher. The 10% distillation temperature of the feedstock oil may be, for example, 200°C or lower, 190°C or lower, or 180°C or lower. That is, the 10% distillation temperature of the feedstock oil in the high-temperature hydrogenation step may be, for example, 90 to 200°C, 90 to 190°C, 90 to 180°C, 140 to 200°C, 140 to 190°C, 140 to 180°C, 150 to 200°C, 150 to 190°C, 150 to 180°C, 155 to 200°C, 155 to 190°C, or 155 to 180°C.

[0079] The 90% distillation temperature of the feedstock oil in the high-temperature hydrogenation step may be, for example, 350°C or higher, preferably 370°C or higher, more preferably 390°C or higher, and even more preferably 400°C or higher, and may be 410°C or higher, 420°C or higher, 430°C or higher, 440°C or higher, or 450°C or higher. The 90% distillation temperature of the feedstock oil may be, for example, 650°C or lower, preferably 600°C or lower, and more preferably 550°C or lower. That is, the 90% distillation temperature of the feedstock oil in the high-temperature hydrogenation step is, for example, 350 to 650°C, 350 to 600°C, 350 to 550°C, 370 to 650°C, 370 to 600°C, 370 to 550°C, 390 to 650°C, 390 to 600°C, 390 to 550°C. , 400 to 650°C, 400 to 600°C, 400 to 550°C, 410 to 650°C, 410 to 600°C, 410 to 550°C, 420 to 650°C, 420 to 600°C, 420 to 550°C, 430 to 650°C, 430 to 600°C, 430 to 550°C, 440 to 650°C, 440 to 600°C, 440 to 550°C, 450 to 650°C, 450 to 600°C, or 450 to 550°C.

[0080] The feedstock oil in the high-temperature hydrogenation step may contain nitrogen, sulfur, chlorine, other halogen elements, and the like.

[0081] The nitrogen content of the feedstock oil in the high-temperature hydrogenation step may be, for example, 100 ppm by mass or more, 2000 ppm by mass or more, 2500 ppm by mass or more, or 3000 ppm by mass or more. In this embodiment, since chemical products are produced through the high-temperature hydrogenation step and the cracking step, high-purity chemical products (chemical products with little nitrogen contamination) can be easily obtained even if a large amount of nitrogen is present in the feedstock oil. The nitrogen content of the feedstock oil may be, for example, 20,000 ppm by mass or less, 15,000 ppm by mass or less, or 10,000 ppm by mass or less. That is, the nitrogen content of the feedstock oil in the high-temperature hydrogenation step may be, for example, 100 to 20,000 ppm by mass, 100 to 15,000 ppm by mass, 100 to 10,000 ppm by mass, 2,000 to 20,000 ppm by mass, 2,000 to 15,000 ppm by mass, 2,000 to 10,000 ppm by mass, 2,500 to 20,000 ppm by mass, 2,500 to 15,000 ppm by mass, 2,500 to 10,000 ppm by mass, 3,000 to 20,000 ppm by mass, 3,000 to 15,000 ppm by mass, or 3,000 to 10,000 ppm by mass.

[0082] The sulfur content of the feedstock oil in the high-temperature hydrogenation step may be, for example, 10 ppm by mass or more, 100 ppm by mass or more, 500 ppm by mass or more, or 1000 ppm by mass or more. In this embodiment, since chemical products are produced through the high-temperature hydrogenation step and the cracking step, high-purity chemical products (chemical products with little sulfur contamination) can be easily obtained even if a large amount of sulfur is present in the feedstock oil. The sulfur content of the feedstock oil may be, for example, 30,000 ppm by mass or less, 20,000 ppm by mass or less, or 10,000 ppm by mass or less. That is, the sulfur content of the feedstock oil in the high-temperature hydrogenation step may be, for example, 10 to 30,000 ppm by mass, 10 to 20,000 ppm by mass, 10 to 10,000 ppm by mass, 100 to 30,000 ppm by mass, 100 to 20,000 ppm by mass, 100 to 10,000 ppm by mass, 500 to 30,000 ppm by mass, 500 to 20,000 ppm by mass, 500 to 10,000 ppm by mass, 1,000 to 30,000 ppm by mass, 1,000 to 20,000 ppm by mass, or 1,000 to 10,000 ppm by mass.

[0083] The chlorine content of the feedstock oil in the high-temperature hydrogenation step may be, for example, 10 ppm by mass or more, 30 ppm by mass or more, 50 ppm by mass or more, or 100 ppm by mass or more. In this embodiment, since chemical products are produced through the high-temperature hydrogenation step and the cracking step, high-purity chemical products (chemical products with little chlorine contamination) can be easily obtained even if a large amount of chlorine is present in the feedstock oil. The chlorine content of the feedstock oil may be, for example, 2000 ppm by mass or less, 1500 ppm by mass or less, or 1000 ppm by mass or less. In addition to the chlorine content, the contents of other halogen elements may also be in the same range. That is, the chlorine content of the feedstock oil in the high-temperature hydrogenation step may be, for example, 10 to 2000 ppm by mass, 10 to 1500 ppm by mass, 10 to 1000 ppm by mass, 30 to 2000 ppm by mass, 30 to 1500 ppm by mass, 30 to 1000 ppm by mass, 50 to 2000 ppm by mass, 50 to 1500 ppm by mass, 50 to 1000 ppm by mass, 100 to 2000 ppm by mass, 100 to 1500 ppm by mass, or 100 to 1000 ppm by mass.

[0084] The high-temperature hydrogenation step may be a step of hydrogenating a feedstock in the presence of a hydrogenation catalyst. The hydrogenation can be carried out, for example, by supplying the feedstock to a reactor containing a hydrogenation catalyst and bringing the feedstock into contact with the hydrogenation catalyst in the reactor.

[0085] As the hydrogenation catalyst, for example, a known hydrogenation catalyst used in the hydrogenation of hydrocarbon oils can be used.

[0086] In this embodiment, when the feedstock oil in the high-temperature hydrogenation step contains a high-boiling-point oil, the hydrogenation catalyst is preferably a catalyst that has excellent hydrogenation ability and can efficiently hydrogenate the high-boiling-point oil. From the viewpoint of hydrogenation ability, the hydrogenation catalyst preferably contains, for example, a Ni-based catalyst. The Ni-based catalyst is a catalyst that has Ni as an active metal.

[0087] The high-temperature hydrogenation step may be carried out using one type of hydrogenation catalyst or multiple types of hydrogenation catalysts. For example, in the high-temperature hydrogenation step, a desulfurization / denitrification catalyst, a high-resolution catalyst, a low-resolution catalyst, etc., which will be described later, may be used in appropriate combination as the hydrogenation catalyst.

[0088] The desulfurization / denitrification catalyst may be a hydrogenation catalyst having excellent desulfurization and denitrification performance. Examples of the desulfurization / denitrification catalyst include a hydrocracking catalyst comprising an active metal supported on an alumina-containing carrier. Such a hydrogenation catalyst tends to have excellent desulfurization and denitrification performance.

[0089] The support for the desulfurization and denitrification catalyst may be an alumina-containing support, and preferably has an alumina content of 50 mass% or more. The alumina content in the support for the desulfurization and denitrification catalyst may be, for example, 50 mass% or more, preferably 55 mass% or more, and more preferably 60 mass% or more, based on the total amount of the support.

[0090] The support for the desulfurization / denitrification catalyst may contain a component other than alumina. The support for the desulfurization / denitrification catalyst may contain, for example, an oxide of an element of Group 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support for the desulfurization / denitrification catalyst may contain, for example, at least one oxide of silica, phosphorus, magnesia, zirconia, boria, titania, calcia, zinc, or the like. Furthermore, from the viewpoints of desulfurization / denitrification performance, industrial production, and catalyst strength, the support for the desulfurization / denitrification catalyst preferably contains silica, silica-alumina, silica-alumina-phosphorus, silica-magnesia, alumina-silica-magnesia, alumina-silica-zirconia, or the like. The support for the desulfurization / denitrification catalyst may be crystalline or amorphous. The shape of the support for the desulfurization and denitrification catalyst is not particularly limited, and may be, for example, spherical, cylindrical, trilobe, or quadrilobe.

[0091] Examples of active metals contained in the desulfurization / denitrification catalyst include Ni, Mo, Co, W, and P. The desulfurization / denitrification catalyst may contain one type of active metal, or may contain two or more types. From the viewpoint of easily realizing excellent hydrogenation ability and enabling more efficient desulfurization / denitrification, the desulfurization / denitrification catalyst preferably contains at least Ni, and more preferably contains Ni and Mo or W. The active metal may be activated by sulfurization treatment. By containing a sulfide of Ni, among the above metals, in particular, the desulfurization / denitrification catalyst is more likely to realize excellent hydrogenation ability.

[0092] An example of a high-resolution catalyst is a hydrogenation catalyst comprising an active metal supported on a zeolite-containing carrier. Such a hydrogenation catalyst has small pores and tends to have excellent hydrogenation resolution.

[0093] The support of the high-resolution catalyst may be a support containing zeolite, and preferably has a zeolite content of 1 mass% or more. The zeolite content in the support of the high-resolution catalyst may be, for example, 2 mass% or more, preferably 3 mass% or more, and more preferably 5 mass% or more, based on the total amount of the support.

[0094] The support of the high-resolution catalyst may contain components other than zeolite. The support of the high-resolution catalyst may contain, for example, an oxide of an element of Group 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support of the high-resolution catalyst may contain at least one oxide of silica, alumina, phosphorus, magnesia, zirconia, boria, titania, calcia, zinc, or the like. From the viewpoints of cracking performance, desulfurization / denitrification performance, industrial production, and catalyst strength, the support of the high-resolution catalyst preferably contains alumina, silica, silica-alumina, silica-alumina-phosphorus, silica-magnesia, alumina-silica-magnesia, alumina-silica-zirconia, or the like. The support of the high-resolution catalyst may be crystalline or amorphous. The shape of the support of the high-resolution catalyst is not particularly limited and may be, for example, spherical, cylindrical, trilobe, or quadrilobe.

[0095] Examples of active metals contained in the high-resolution catalyst include Ni, Mo, Co, W, and P. The high-resolution catalyst may contain one type of active metal, or two or more types. From the viewpoint of easily realizing excellent hydrogenation ability and being able to more efficiently hydrogenate high-boiling-point oils, the high-resolution catalyst preferably contains at least Ni, and more preferably contains Ni and Mo or W. The active metal may be activated by sulfurization treatment. By containing sulfides of Ni, among the above metals, in particular, the desulfurization / denitrogenation catalyst is more likely to realize excellent hydrogenation ability.

[0096] An example of a low-resolution catalyst is a hydrogenation catalyst comprising an active metal supported on an alumina-containing carrier. Such a hydrogenation catalyst has many larger pores than a high-resolution catalyst and tends to have a milder hydrogenation resolution than a high-resolution catalyst.

[0097] The support of the low-resolution catalyst may be an alumina-containing support, and the alumina content in the support of the low-resolution catalyst may be, for example, 20 mass % or more, preferably 25 mass % or more, and more preferably 30 mass % or more, based on the total amount of the support.

[0098] The support for the low-resolution catalyst may contain a component other than alumina. The support for the low-resolution catalyst may contain, for example, an oxide of an element of Group 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support for the low-resolution catalyst may contain at least one oxide of silica, phosphorus, magnesia, zirconia, boria, titania, calcia, zinc, or the like. From the viewpoints of cracking performance, desulfurization / denitrification performance, industrial production, and catalyst strength, the support for the low-resolution catalyst preferably contains silica, silica-alumina, silica-alumina-phosphorus, silica-magnesia, alumina-silica-magnesia, alumina-silica-zirconia, or the like. The support for the low-resolution catalyst may be crystalline or amorphous. The shape of the support for the low-resolution catalyst is not particularly limited and may be, for example, spherical, cylindrical, trilobe, or quadrilobe.

[0099] Examples of active metals contained in the low-resolution catalyst include Ni, Mo, Co, W, and P. The low-resolution catalyst may contain one type of active metal, or may contain two or more types. From the viewpoint of being able to more efficiently hydrogenate high-boiling-point oils, the low-resolution catalyst preferably contains at least Ni, and more preferably contains Ni and Mo or W. The active metal may be activated by sulfurization treatment. By containing sulfides of Ni, among the above metals, in particular, the desulfurization / denitrogenation catalyst is more likely to achieve excellent hydrogenation ability.

[0100] In the high-temperature hydrogenation step, a desulfurization / denitrification catalyst and a cracking catalyst may be used in combination. The cracking catalyst may be a combination of a high-resolution catalyst and a low-resolution catalyst, or only a high-resolution catalyst or only a low-resolution catalyst. The desulfurization / denitrification catalyst may be disposed at least in the upstream stages of the high-resolution catalyst and the low-resolution catalyst, or may be disposed both in the upstream stages and the downstream stages of the high-resolution catalyst and the low-resolution catalyst.

[0101] If the feedstock oil in the high-temperature hydrogenation step contains nitrogen, the nitrogen in the feedstock oil may adhere to the active sites of the high-resolution catalyst or low-resolution catalyst, thereby reducing the cracking performance of the high-resolution catalyst or low-resolution catalyst. When the feedstock oil comes into contact with the desulfurization / denitrification catalyst, the nitrogen contained in the feedstock oil is converted to ammonia, etc., thereby reducing the nitrogen content of the feedstock oil. Therefore, in the high-temperature hydrogenation step, it is preferable to place the desulfurization / denitrification catalyst in a stage upstream of the high-resolution catalyst or low-resolution catalyst. In other words, it is preferable to place the desulfurization / denitrification catalyst in a stage upstream of the high-resolution catalyst or low-resolution catalyst, which will be described later. With this arrangement, even if the feedstock oil contains nitrogen, it is possible to prevent the cracking performance of the high-resolution catalyst or low-resolution catalyst from decreasing.

[0102] The high-temperature hydrogenation step may be carried out using, for example, a flow reactor. In this case, it is preferable to arrange, in the flow reactor from the inlet side, a first catalyst layer containing a desulfurization / denitrification catalyst and a second catalyst layer containing a decomposition catalyst in this order. Furthermore, a third catalyst layer containing a decomposition catalyst of a type different in decomposition ability and a fourth catalyst layer containing a desulfurization / denitrification catalyst may be further arranged downstream of the second catalyst layer.

[0103] The reaction temperature in the high-temperature hydrogenation step is not particularly limited and may be, for example, 300°C or higher, preferably 320°C or higher, and more preferably 340°C or higher. The reaction temperature in the high-temperature hydrogenation step may be, for example, 480°C or lower, preferably 460°C or lower, and more preferably 440°C or lower. That is, the reaction temperature in the high-temperature hydrogenation step may be, for example, 300 to 480°C, 300 to 460°C, 300 to 440°C, 320 to 480°C, 320 to 460°C, 320 to 440°C, 340 to 480°C, 340 to 460°C, or 340 to 440°C.

[0104] The reaction pressure in the high-temperature hydrogenation step is not particularly limited and may be, for example, 1 MPaG or more, preferably 3 MPaG or more, and more preferably 5 MPaG or more. The reaction pressure in the high-temperature hydrogenation step is also not particularly limited and may be, for example, 20 MPaG or less, preferably 19 MPaG or less, and more preferably 18 MPaG or less. That is, the reaction pressure in the high-temperature hydrogenation step may be, for example, 1 to 20 MPaG, 1 to 19 MPaG, 1 to 18 MPaG, 3 to 20 MPaG, 3 to 19 MPaG, 3 to 18 MPaG, 5 to 20 MPaG, 5 to 19 MPaG, or 5 to 18 MPaG.

[0105] When the high-temperature hydrogenation step is carried out using a flow reactor, the weight hourly space velocity (WHSV) of the feedstock is, for example, 0.1 h －１ or more, preferably 0.15 h －１ More preferably, 0.2 h －１ The weight hourly space velocity (WHSV) of the feed oil is, for example, 5 h －１ may be less than or equal to 4 h, preferably －１ Less than 3 hours, preferably －１ That is, the weight hourly space velocity (WHSV) of the feed oil is 0.1 to 5 h －１ , 0.1 to 4 h －１ , 0.1 to 3 h －１ , 0.15 to 5 h －１ , 0.15 to 4 h －１ , 0.15 to 3 h －１ , 0.2 to 5 h －１ , 0.2 to 4 h－１ Or 0.2 to 3 hours －１ may be.

[0106] The high-temperature hydrogenation step is carried out in the presence of hydrogen. When the high-temperature hydrogenation step is carried out using a flow reactor, the hydrogen / oil ratio may be, for example, 100 NL / L or more, preferably 150 NL / L or more, and more preferably 200 NL / L or more. The hydrogen / oil ratio may be, for example, 1500 NL / L or less, preferably 1400 NL / L or less, and more preferably 1300 NL / L or less. That is, the hydrogen / oil ratio may be, for example, 100 to 1500 NL / L, 100 to 1400 NL / L, 100 to 1300 NL / L, 150 to 1500 NL / L, 150 to 1400 NL / L, 150 to 1300 NL / L, 200 to 1500 NL / L, 200 to 1400 NL / L, or 200 to 1300 NL / L.

[0107] In the high-temperature hydrogenation step, the feedstock oil is hydrogenated to produce a second gas fraction and a high-temperature hydrogenated oil.

[0108] The second gas component may be, for example, a component of the product produced by hydrogenation that is gaseous at room temperature, 20° C. The second gas component may contain, for example, hydrogen, hydrocarbons having 1 to 4 carbon atoms, etc.

[0109] The second gas may be used, for example, as a combustion gas for heating the pyrolysis section in the pyrolysis step, or as a combustion gas for a heating furnace in other steps.

[0110] The sulfur content in the high-temperature hydrogenated oil is, for example, 1500 ppm by mass or less, and from the viewpoints of reducing the amount of impurities in the chemical products obtained in the cracking step, preventing catalyst poisoning in the subsequent stage of the cracking step, and preventing equipment corrosion, it is preferably 1000 ppm by mass or less, and more preferably 900 ppm by mass or less.

[0111] The nitrogen content in the high-temperature hydrogenated oil is, for example, 100 ppm by mass or less, and from the viewpoint of reducing the amount of impurities in the chemical products obtained in the cracking step, it is preferably 25 ppm by mass or less, more preferably 20 ppm by mass or less.

[0112] The chlorine content in the high-temperature hydrogenated oil is, for example, 20 ppm by mass or less, and from the viewpoints of reducing the amount of impurities in the chemical products obtained in the cracking step and preventing catalyst poisoning and equipment corrosion in the subsequent stages of the cracking step, it is preferably 15 ppm by mass or less, more preferably 10 ppm by mass or less. In addition to the chlorine content, it is also preferable that the contents of other halogen elements are in the same range.

[0113] (Separation step) The separation step is a step of atmospherically distilling an atmospheric distillation feedstock containing at least a portion of the high-temperature hydrogenated oil and crude oil, thereby separating the feedstock into a naphtha fraction and other fractions. The naphtha fraction may include light naphtha and heavy naphtha, but preferably includes light naphtha. The other fractions include conventionally known fractions other than the naphtha fraction, such as low-boiling gas fractions, high-boiling kerosene fractions, diesel fractions, and residual oil fractions.

[0114] The amount of high-temperature hydrogenated oil relative to the total amount of high-temperature hydrogenated oil and crude oil in the atmospheric distillation feedstock in the separation step is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and also preferably 9% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less. That is, the amount of high-temperature hydrogenated oil relative to the total amount of high-temperature hydrogenated oil and crude oil in the atmospheric distillation feedstock is, for example, preferably 0.001% by mass or more and 9% by mass or less, more preferably 0.005% by mass or more and 7% by mass or less, even more preferably 0.01% by mass or more and 57% by mass or less, even more preferably 0.05% by mass or more and 3% by mass or less, and most preferably 0.05% by mass or more and 1% by mass or less. If the amount of high-temperature hydrogenated oil is within the above-mentioned numerical range, when it is mixed with crude oil low in nitrogen and dienes to obtain atmospheric distillation feedstock, the nitrogen and dienes contained in the high-temperature hydrogenated oil are diluted in the atmospheric distillation feedstock, which can suppress the generation of fouling in the heat exchanger of the atmospheric distillation unit and also suppress the impact of impurities such as nitrogen on downstream units.

[0115] The crude oil used in the separation step is not particularly limited, and any conventionally known crude oil can be used.

[0116] The atmospheric distillation feedstock in the separation step may contain nitrogen, sulfur, chlorine, other halogen elements, etc. Since atmospheric distillation feedstock is usually mostly composed of crude oil, the amount of nitrogen and dienes in the crude oil is preferably less than the amount of nitrogen and dienes in the high-temperature hydrogenated oil. For example, the crude oil preferably has the following properties: The nitrogen content of the crude oil is preferably 2000 ppm by mass or less, more preferably 1500 ppm by mass or less, and even more preferably 1000 ppm by mass or less.

[0117] The type and operating conditions of the atmospheric distillation unit used in the separation step are not particularly limited, and conventional equipment and operating conditions may be used, and equipment that has traditionally been installed in oil refineries can be used as is.

[0118] The nitrogen content of the naphtha fraction obtained in the separation step is preferably 500 ppm by mass or less, more preferably 400 ppm by mass or less, and even more preferably 300 ppm by mass or less. By reducing the nitrogen content of the naphtha fraction, high-purity chemical products (chemical products with little nitrogen contamination) can be easily obtained.

[0119] (Steam cracking step) The steam cracking step is a step of obtaining chemical products by steam cracking a steam cracking feedstock containing the naphtha fraction and / or a portion of other fractions obtained in the atmospheric distillation step. In the steam cracking step, the steam cracking feedstock is thermally treated with steam, whereby the naphtha fraction (light naphtha, etc.) is cracked to produce components useful as chemical products.

[0120] In the steam cracking step, at least a portion of the naphtha fraction and / or other fractions obtained in the atmospheric distillation step may be subjected to the steam cracking treatment, or all of them may be subjected to the steam cracking treatment. Furthermore, the steam cracking feedstock in the steam cracking step may further contain, in addition to the naphtha fraction, ethane, naphtha, kerosene, light oil fractions, etc. derived from petroleum, etc. In the steam cracking step, the naphtha fraction may be used as the steam cracking feedstock as is, or the naphtha fraction may be used as the steam cracking feedstock after additional treatment such as desulfurization treatment.

[0121] The conditions for the steam cracking treatment are not particularly limited, and may be appropriately selected from known conditions employed in the steam cracking treatment of ethane, naphtha, kerosene, and the like.

[0122] The reaction temperature of the steam cracking treatment may be, for example, 650°C or higher, preferably 700°C or higher, and more preferably 750°C or higher. The reaction temperature of the steam cracking treatment may be, for example, 1000°C or lower, preferably 950°C or lower, and more preferably 900°C or lower. That is, the reaction temperature of the steam cracking treatment may be, for example, 650 to 1000°C, 650 to 950°C, 650 to 900°C, 700 to 1000°C, 700 to 950°C, 700 to 900°C, 750 to 1000°C, 750 to 950°C, or 750 to 900°C.

[0123] The reaction time (residence time) of the steam cracking treatment may be, for example, 0.05 seconds or more, preferably 0.06 seconds or more, and more preferably 0.08 seconds or more. The reaction time of the steam cracking treatment may be, for example, 2.0 seconds or less, preferably 1.9 seconds or less, and more preferably 1.8 seconds or less. That is, the reaction time of the steam cracking treatment may be, for example, 0.05 to 2.0 seconds, 0.05 to 1.9 seconds, 0.05 to 1.8 seconds, 0.06 to 2.0 seconds, 0.06 to 1.9 seconds, 0.06 to 1.8 seconds, 0.08 to 2.0 seconds, 0.08 to 1.9 seconds, or 0.08 to 1.8 seconds.

[0124] The steam / steam cracking feedstock ratio (mass ratio) in the steam cracking treatment may be, for example, 0.2 or more, preferably 0.25 or more, and more preferably 0.3 or more. The steam / steam cracking feedstock ratio (mass ratio) may be, for example, 1.0 or less, preferably 0.9 or less, and more preferably 0.8 or less. That is, the steam / steam cracking feedstock ratio (mass ratio) may be, for example, 0.2 to 1.0, 0.2 to 0.9, 0.2 to 0.8, 0.25 to 1.0, 0.25 to 0.9, 0.25 to 0.8, 0.3 to 1.0, 0.3 to 0.9, or 0.3 to 0.8.

[0125] The outlet reaction pressure of the steam cracking treatment may be, for example, 0.1 MPaA or more, preferably 0.15 MPaA or more, and more preferably 0.2 MPaA or more. The reaction pressure of the steam cracking treatment may be, for example, 1.0 MPaA or less, preferably 0.8 MPaA or less, and more preferably 0.6 MPaA or less. That is, the outlet reaction pressure of the steam cracking treatment may be, for example, 0.1 to 1.0 MPaA, 0.1 to 0.8 MPaA, 0.1 to 0.6 MPaA, 0.15 to 1.0 MPaA, 0.15 to 0.8 MPaA, 0.15 to 0.6 MPaA, 0.2 to 1.0 MPaA, 0.2 to 0.8 MPaA, or 0.2 to 0.6 MPaA.

[0126] Examples of chemical products obtained by the steam cracking process include ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, olefin-containing C9 aromatics for resin conversion such as indene and methylstyrene.

[0127] In the steam cracking step, in addition to chemical products, light fractions may also be obtained, such as methane, ethane, butane, pentane, propane, and hexane.

[0128] In the steam cracking step, a heavy fraction may be further obtained in addition to chemical products. The heavy fraction may be reused as a raw material for the steam cracking treatment or may be used as a raw material for producing a charcoal. The heavy fraction obtained in the steam cracking step of this embodiment tends to have a high aromatic content and can be suitably used as a raw material for producing a charcoal (particularly carbon black). For example, a charcoal (particularly carbon black) can be obtained by thermal decomposition or incomplete combustion of the heavy fraction.

[0129] The heavy fraction may be, for example, a fraction having a 10% distillation temperature of 190°C or higher, or may be a fraction having a 10% distillation temperature of 200°C or higher. The 10% distillation temperature of the heavy fraction may be, for example, 250°C or lower, or 240°C or lower. The 90% distillation temperature of the heavy fraction may be, for example, 450°C or higher, or 500°C or higher. The 90% distillation temperature of the heavy fraction may be, for example, 750°C or lower, or 700°C or lower. That is, the 10% distillation temperature of the heavy fraction may be, for example, 190 to 250°C, 190 to 240°C, 200 to 250°C, or 200 to 240°C. The 90% distillation temperature of the heavy fraction may be, for example, 450 to 750°C, 450 to 700°C, 500 to 750°C, or 500 to 700°C.

[0130] The aromatic content of the heavy fraction may be, for example, 30% by mass or more, preferably 35% by mass or more, and more preferably 40% by mass or more. The aromatic content of the heavy fraction may be, for example, 90% by mass or less. That is, the aromatic content of the heavy fraction may be, for example, 30 to 90% by mass, 35 to 90% by mass, or 40 to 90% by mass.

[0131] Fig. 2 is a schematic diagram showing an example of a system for carrying out the production method of this embodiment. The system 100 shown in Fig. 2 includes a thermal cracking unit 110, a first separation unit 111, a pulverization unit 112, a low-temperature hydrogenation unit 115, a high-temperature hydrogenation unit 120, an atmospheric distillation unit 125, and a steam cracker 130.

[0132] In the system 100, first, the waste material S1 is supplied to the thermal decomposition unit 110, where it is thermally decomposed. The thermal decomposition unit 110 produces a first gas fraction S2, a pyrolysis oil S3, and a mixture S4 of a residue and metal components. The first gas fraction S2 may be discharged to the outside of the system or may be reused as an oxygen-free gas in the thermal decomposition unit 110. The pyrolysis oil S3 is supplied to the low-temperature hydrogenation unit 115. The mixture S4 is supplied to the first separation unit 111, where it is separated into a residue fraction S5 and a metal fraction S6. The residue fraction S5 is pulverized in the pulverization unit 112 and recovered as powdered charcoal S7.

[0133] In the low-temperature hydrogenation unit 115, the pyrolysis oil S3 is subjected to low-temperature hydrogenation treatment to produce a low-temperature hydrogenated oil S8. The low-temperature hydrogenated oil S8 is supplied to the high-temperature hydrogenation unit 120.

[0134] In the high-temperature hydrogenation unit 120, high-temperature hydrotreatment of the low-temperature hydrogenated oil S8 produces a second gas fraction S9 and a high-temperature hydrogenated oil S10. The second gas fraction S9 may be discharged to the outside of the system, or may be used as combustion gas for heating the thermal cracking section in the thermal cracking step or as combustion gas for a heating furnace in another step. The high-temperature hydrogenated oil S10 is supplied to the atmospheric distillation unit 125. The high-temperature hydrogenated oil S10 may also be reused in the low-temperature hydrogenation unit 115 as recycled oil S15.

[0135] In the atmospheric distillation unit 125, the high-temperature hydrogenated oil S10 is atmospherically distilled to produce a steam cracking feedstock S11 containing at least a portion of the naphtha fraction and other fractions (kerosene fraction, light oil fraction). The steam cracking feedstock S11 may be obtained as a single fraction or as a mixture. The steam cracking feedstock S11 is supplied to a steam cracker 130.

[0136] In the steam cracker 130, the steam cracking feedstock S11 is subjected to steam cracking to produce a product gas S12, a product oil S13, and a heavy fraction S14. The product gas S12 and the product oil S13 contain ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, olefin-containing C9 aromatic compounds for resin conversion such as indene and methylstyrene, which are useful as chemical products. Chemical products can be obtained by appropriately separating and recovering the product gas S12 and the product oil S13. The heavy fraction S14 can be used, for example, as a raw material for char production or as a fuel.

[0137] (Method for Producing Synthetic Rubber) The method for producing butadiene according to this embodiment includes a polymerization step of obtaining synthetic rubber by a polymerization reaction using butadiene obtained by the above-described production method as at least a part of the raw materials for the synthetic rubber.

[0138] In the polymerization step, a polymerization composition containing at least butadiene as a monomer is polymerized by a conventionally known method to obtain a synthetic rubber. The polymerization method is not particularly limited, and conventionally known methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization can be used. The polymerization conditions are not particularly limited, and can be adjusted appropriately depending on the polymerization method, the composition of the polymerization composition, and the like.

[0139] The monomer may be butadiene alone, or in addition to butadiene, other conventionally known monomers for synthetic rubber may be used depending on the composition and properties of the target synthetic rubber. Examples of other monomers for synthetic rubber include conjugated diene compounds other than butadiene and aromatic vinyl compounds.

[0140] Examples of conjugated diene compounds other than butadiene include isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, etc. Conjugated diene compounds other than butadiene may be used alone or in combination of two or more.

[0141] Examples of aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, diphenylethylene, and tertiary amino group-containing diphenylethylene (e.g., 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene). One or more aromatic vinyl compounds may be used, or two or more may be used.

[0142] In addition to the monomer, the polymerization composition may contain conventionally known additives, solvents, etc. Examples of the additives include a polymerization initiator, an emulsifier, a surfactant, etc.

[0143] As the polymerization initiator, for example, an alkali metal compound is used. Specific examples of the alkali metal compound include alkyllithium such as methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium; 1,4-dilithiobutane, phenyllithium, stilbenelithium, naphthyllithium, 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentylidene)dilithium, naphthylsodium, naphthylpotassium, and ethoxypotassium.

[0144] (Tire) The tire of the present embodiment contains synthetic rubber obtained by the above-described method for producing synthetic rubber.

[0145] (Tire Manufacturing Method) The tire manufacturing method of this embodiment includes a vulcanization step of obtaining a tire by a vulcanization reaction using the synthetic rubber obtained by the synthetic rubber manufacturing method described above as at least a part of the raw materials for the tire.

[0146] In the vulcanization step, a tire can be obtained by vulcanizing a vulcanization composition containing at least a synthetic rubber by a conventionally known method. The vulcanization conditions are not particularly limited and can be adjusted appropriately depending on the composition of the vulcanization composition and the shape and structure of the desired tire.

[0147] The vulcanization composition may contain conventionally known additives in addition to the synthetic rubber. Examples of the additives include vulcanizing agents, vulcanization accelerators, vulcanization accelerator assistants, antioxidants, softeners, antioxidants, and colorants. These additives may be used alone or in combination of two or more.

[0148] Examples of the vulcanizing agent include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, and alkylphenol disulfide; zinc oxide, magnesium oxide, litharge, p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylenedianiline, phenol resin, brominated alkylphenol resin, and chlorinated alkylphenol resin.

[0149] Examples of the vulcanization accelerator include thiuram-based accelerators such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM); aldehyde / ammonia-based accelerators such as hexamethylenetetramine; guanidine-based accelerators such as diphenylguanidine (DPG); thiazole-based accelerators such as 2-mercaptobenzothiazole (MBT) and dibenzothiazyl disulfide (DM); sulfenamide-based accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide (CBS) and N-t-butyl-2-benzothiazylsulfenamide (BBS); and dithiocarbamate-based accelerators such as zinc dimethyldithiocarbamate (ZnPDC).

[0150] Examples of the vulcanization accelerator include fatty acids, zinc fatty acids, zinc salts of fatty acids, and zinc oxide. Examples of the fatty acids that can be used include acetic acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid. Examples of the zinc fatty acids that can be used include zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc acrylate, and zinc maleate.

[0151] Examples of antioxidants include aliphatic and aromatic hindered amine compounds, hindered phenol compounds, and the like.

[0152] Examples of antioxidants include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

[0153] Examples of colorants include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides, and sulfates, azo pigments, and copper phthalocyanine pigments.

[0154] The shape, structure, size, and material of the tire are not particularly limited and can be appropriately selected depending on the purpose. The uses of the tire are also not particularly limited and include, for example, passenger car tires, heavy-duty tires, motorcycle tires, studless tires, etc.

[0155] (Method for Managing Renewable Products) In recent years, in order to sell environmentally friendly products using plant-derived raw materials, recycled materials, etc. in a more attractive manner, a method known as the mass balance method has been attracting attention in various industries, such as the chemical, steel, and aluminum industries. It is desirable that the value of each product produced using the manufacturing method of the present invention, which uses waste materials including waste tires, be assigned a renewable product value using the mass balance method in a simple and reliable manner. Therefore, the present invention provides a management method that, when producing chemical products using the manufacturing method of the present invention, can assign a renewable product value to each product in a simple and reliable manner in accordance with the content of renewable raw materials contained in waste materials including waste tires.

[0156] In this specification, "renewable raw materials" refers to raw materials derived from renewable organic resources. Renewable raw materials are not limited to products derived from biological resources, but are broadly interpreted as any renewable organic resource. For example, even if a product is derived from petroleum, it also includes products derived from recycled petroleum-derived products, such as waste tires.

[0157] Here, the mass balance method refers to a technique in which, for example, when a raw material with a specific characteristic, such as a biomass raw material, is mixed with a raw material without that characteristic during the distribution and processing process from raw materials to a product, the characteristic is allocated as a credit to a portion of the product in accordance with the content ratio of the raw material with that characteristic. Since the mass balance method is a method in which the manufacturer arbitrarily allocates the biomass fraction as a credit, its legitimacy is generally verified by certification by a third-party certification organization. Examples of third-party certification organizations include ISCC (International Sustainability Carbon) and RSB (Roundtable on Sustainable Biofuels).

[0158] (Chemical product management method executed using a management device) The chemical product management method of the present invention can be used when producing chemical products using waste materials including waste tires. The management method of the present invention is a method of using a management device to assign a value as a renewable product to a chemical product using a mass balance method according to the content ratio of renewable raw materials contained in the waste material. The management method of the present invention includes, for example, a step (V) in which a management device described below confirms that a chemical product can be obtained (the management device acquires information indicating that a chemical product can be obtained using waste materials including waste tires), and a step (Z) in which the management device confirms the proportion of the product to which a value as a renewable product is assigned (the management device acquires information indicating the proportion of the product to which a value as a renewable product is assigned). The step (V) in which a chemical product can be obtained includes the following steps (V-1), (V-2), (V-3), (V-4), (V-5), and (V-6). Step (V-1) is a step in which the management device confirms that the pyrolysis oil is produced from the waste material input into a pyrolysis unit that obtains pyrolysis oil by pyrolysis of the waste material. Step (V-2) is a step in which the management device confirms that the low-temperature hydrogenated oil is produced from the pyrolysis oil input into a low-temperature hydrogenation unit that obtains low-temperature hydrogenated oil by subjecting a feedstock containing at least a portion of the pyrolysis oil to low-temperature hydrotreatment at a temperature of 180°C or higher and 350°C or lower. Step (V-3) is a step in which the management device confirms that the high-temperature hydrogenated oil is produced from the low-temperature hydrogenated oil input into a high-temperature hydrogenation unit that obtains a second gas fraction and high-temperature hydrogenated oil by subjecting a feedstock containing at least a portion of the low-temperature hydrogenated oil to hydrotreatment at a temperature higher than the low-temperature hydrotreatment. The step (V-4) is a step in which the management device confirms that the naphtha fraction and the other fractions are produced from the high-temperature hydrogenated oil that has been input into an atmospheric distillation unit that separates an atmospheric distillation feedstock containing at least a portion of the high-temperature hydrogenated oil and crude oil into a naphtha fraction and the other fractions by atmospheric distillation.Step (V-5) is a step in which the management device confirms that the chemical product can be obtained from the steam cracking feedstock fed into a steam cracker that subjects steam cracking treatment to a steam cracking feedstock containing at least a portion of the naphtha fraction and / or the other fraction. Step (V-6) is a step in which the management device confirms that the chemical product can be obtained from the waste material by processing it in the following order: the thermal cracking unit, the low-temperature hydrogenation unit, the high-temperature hydrogenation unit, the atmospheric distillation unit, and the steam cracker. Step (Z) of confirming the proportion of products to be assigned a value as a renewable product includes the following steps (Z-1), (Z-2), (Z-3), and (Z-4). Step (Z-1) is a step in which the management device selects products to be assigned as renewable products from the products obtained by the steam cracker. In step (Z-2), the management device determines the value of the proportion (P) to be allocated as a renewable product among the proportion of the product selected in step (Z-1) to the product obtained by the steam cracker. In step (Z-3), the management device determines the value of the content proportion (Q) of renewable raw materials contained in the waste material. In step (Z-4), the management device compares the value of the proportion (P) with the value of the content proportion (Q) and confirms that the value of the proportion (P) is equal to or less than the value of the content proportion (Q).

[0159] An example of an embodiment of a chemical product management method executed using a management device (particularly, a method of assigning a value as a renewable product) will be described below. Step (Z-1): If the products obtained by the steam cracker are ethylene, propylene, butadiene, and other products, butadiene is selected. Step (Z-2): Assume that the products obtained by the steam cracker are ethylene, propylene, butadiene, and other products, with the proportions of each product being ethylene: 10 mass%, propylene: 10 mass%, butadiene: 10 mass%, and other products: 70 mass%. Therefore, the proportion (P) of the 10 mass% butadiene product to be assigned as a renewable product is determined. Step (Z-3): If the waste material contains 5 mass% renewable raw materials and 95 mass% non-renewable raw materials, the renewable raw material content (Q) is determined (obtained) to be 5 mass%. Step (Z-4): The value of the proportion (P) is compared with the value of the content proportion (Q), and it is confirmed that the value of the proportion (P) is equal to or less than the value of the content proportion (Q). Here, if the content proportion (Q) of renewable raw materials is 5% by mass, the proportion (P) allocated to butadiene as a renewable product is 5% by mass or less. In other words, if the content proportion (Q) of renewable raw materials is 5% by mass, 5% by mass of the 10% by mass of butadiene product allocated as a renewable product can be allocated as renewable butadiene. In this way, the value of the butadiene product among the products obtained by the steam cracker can be assigned as a renewable product according to the content proportion of renewable raw materials contained in the waste material. According to a third-party certification body, in the mass balance method, the butadiene product excluding (P) mass % out of 10 mass % butadiene product (10-(P) mass % butadiene product) actually contains renewable components, but because the credits for 100% renewable butadiene have been assigned to the (P) mass % butadiene, it is not treated as renewable butadiene.The value of 5 mass% for the content ratio (Q) of the renewable raw material and the value of 10 mass% for the butadiene product are set for the sake of convenience in order to facilitate understanding of the present invention, and are not limited to these values.

[0160] <Management Device, Management Program> As described above, the management method of the present invention can be executed using a management device. Furthermore, the processing in each step of the management method performed by the management device is executed by a computer having a control unit that constitutes the management device. The management device that executes the management method of the present invention and the management program (computer program) executed by the computer of the management device are described below.

[0161] The following management device is a preferred embodiment of the management device of the present invention. "A chemical product management device used when producing chemical products using waste materials including waste tires, the management device is a device that assigns a value as a renewable product to the chemical product using a mass balance method according to the content ratio of renewable raw materials contained in the waste material, the management device has a confirmation unit (I) that confirms that the chemical product is obtained, the confirmation unit (I) including the following means (V-1), (V-2), (V-3), (V-4), (V-5), and (V-6): the means (V-1) is a means for confirming that pyrolysis oil is produced from the waste material input into a pyrolysis unit that obtains pyrolysis oil by pyrolysis of the waste material, the means (V-2) is a means for confirming that low-temperature hydrogenated oil is produced from the pyrolysis oil input into a low-temperature hydrogenation unit that obtains low-temperature hydrogenated oil by subjecting a feedstock oil containing at least a portion of the pyrolysis oil to low-temperature hydrogenation treatment at 180°C or higher and 350°C or lower, The means (V-3) is a means for confirming that the high-temperature hydrogenated oil is produced from the low-temperature hydrogenated oil that is input into a high-temperature hydrogenation unit that obtains a second gas fraction and a high-temperature hydrogenated oil by subjecting a feedstock containing at least a portion of the low-temperature hydrogenated oil to hydrotreatment at a temperature higher than that of the low-temperature hydrogenation treatment; the means (V-4) is a means for confirming that the naphtha fraction and the other fractions are produced from the high-temperature hydrogenated oil that is input into an atmospheric distillation unit that separates an atmospheric distillation feedstock containing at least a portion of the high-temperature hydrogenated oil and crude oil into a naphtha fraction and the other fractions by atmospheric distillation; and the means (V-5) is a means for confirming that the chemical product is obtained from the steam cracking feedstock that is input into a steam cracker that performs a steam cracking treatment on a steam cracking feedstock containing at least a portion of the naphtha fraction and / or the other fractions. the means (V-6) is a means for confirming that the chemical product can be obtained from the waste material by treating the waste material in the order of the thermal decomposition unit, the low-temperature hydrogenation unit, the high-temperature hydrogenation unit, the atmospheric distillation unit, and the steam cracker,The management device has a confirmation unit (I) that confirms the proportion of products to be assigned a value as a renewable product, and the confirmation unit (I) includes the following means (Z-1), (Z-2), (Z-3), and (Z-4): The means (Z-1) is a means for selecting a product to be assigned as a renewable product from among the products obtained by the steam cracker, The means (Z-2) is a means for determining the value of the proportion (P) to be assigned as a renewable product from the proportion of the product selected in the means (Z-1) to the products obtained by the steam cracker, The means (Z-3) is a means for grasping the value of the content proportion (Q) of renewable raw materials contained in the waste material, and The means (Z-4) is a means for comparing the value of the proportion (P) with the value of the content proportion (Q) and confirming that the value of the proportion (P) is equal to or less than the value of the content proportion (Q).

[0162] The following management program is a preferred embodiment of the management program of the present invention: "A management program for chemical products executed by a management device used when producing chemical products using waste materials including waste tires, the management program using the management device to assign a value as a renewable product to the chemical products using a mass balance method in accordance with the content ratio of renewable raw materials contained in the waste materials, the management program comprising: (V-1): confirming that pyrolysis oil is produced from the waste materials input into a pyrolysis unit that obtains pyrolysis oil by pyrolysis of the waste materials; (V-2): confirming that low-temperature hydrogenated oil is produced from the pyrolysis oil input into a low-temperature hydrogenation unit that obtains low-temperature hydrogenated oil by subjecting a feedstock oil containing at least a portion of the pyrolysis oil to low-temperature hydrogenation treatment at 180°C or higher and 350°C or lower; (V-3) is a step of confirming that the high-temperature hydrogenated oil is produced from the low-temperature hydrogenated oil that is input into a high-temperature hydrogenation unit, which obtains a second gas fraction and a high-temperature hydrogenated oil by subjecting a feedstock containing at least a portion of the low-temperature hydrogenated oil to a hydrotreatment at a temperature higher than that of the low-temperature hydrogenation treatment; (V-4): is a step of confirming that the naphtha fraction and the other fractions are produced from the high-temperature hydrogenated oil that is input into an atmospheric distillation unit, which separates an atmospheric distillation feedstock containing at least a portion of the high-temperature hydrogenated oil and crude oil into a naphtha fraction and other fractions by atmospheric distillation; (V-5): is a step of confirming that the chemical product is obtained from the steam cracking feedstock that is input into a steam cracker, which subjects a steam cracking treatment to a steam cracking feedstock containing at least a portion of the naphtha fraction and / or other fractions; (V-6): A step of confirming that the chemical products can be obtained from the waste materials by processing them in the order of the thermal decomposition unit, the low-temperature hydrogenation unit, the high-temperature hydrogenation unit, the atmospheric distillation unit, and the steam cracker, wherein the management program includes a step (Z) of confirming the proportion of products to which values ​​as renewable products are assigned,(Z-1): select a product to be allocated as a renewable product from among the products obtained by the steam cracker; (Z-2): determine the value of the proportion (P) to be allocated as a renewable product from the proportion of the product selected in step (Z-1) to the products obtained by the steam cracker; (Z-3): determine the value of the content proportion (Q) of renewable raw materials contained in the waste material; and (Z-4): compare the value of the proportion (P) with the value of the content proportion (Q) and confirm that the value of the proportion (P) is equal to or less than the value of the content proportion (Q).

[0163] <<Management Device>> As already described, the management device is a device that executes the management method of the present invention. A preferred embodiment of the management device will be described with reference to FIG. 3. The management device 100 has a control unit 110 and a storage unit 120. The control unit 110 has a confirmation unit (I) 130, a comparison unit 140, and a notification unit (output unit) 150, and the storage unit 120 has a reaction database 160. The hardware configuration and functional configuration of the management device 100 will be described.

[0164] <<Hardware Configuration of the Management Device>> FIG. 4 is a block diagram showing an example of the hardware configuration of the management device 100. As shown in FIG. 4, the management device 100 has the following components. The components are connected to each other via a bus 207. The CPU 201 is a processing device (computer) that performs various controls and calculations. The CPU 201 realizes various functions by executing an OS and computer programs stored in the main memory device 202, etc. That is, in this embodiment, the CPU 201 functions as the control unit 110 of the management device by executing the management program, and executes the management method. The CPU 201 also controls the overall operation of the management device 100. Note that in this embodiment, the device that controls the overall operation of the management device 100 is the CPU 201, but this is not limited thereto. For example, an FPGA (Field Programmable Gate Array) may also be used.

[0165] The management program and various databases do not necessarily have to be stored in the main memory device 202 or the auxiliary memory device 203. The management program and various databases may be stored in other information processing devices connected to the management device 100 via the Internet, a local area network (LAN), a wide area network (WAN), or the like. The management device 100 may acquire and execute the management program and various databases from these other information processing devices. The main memory device 202 is a computer-readable storage medium that stores various programs and data necessary to execute the various programs. The main memory device 202 includes a read-only memory (ROM) and a random access memory (RAM), both of which are not shown. The ROM stores various programs such as the BIOS. The RAM functions as a work area in which the various programs stored in the ROM are deployed when the CPU 201 executes them. The RAM can be selected appropriately according to the purpose without any restrictions. Examples of RAM include a dynamic random access memory (DRAM) and an static random access memory (SRAM). The auxiliary storage device 203 is not particularly limited as long as it can store various types of information and can be appropriately selected depending on the purpose, and examples include a solid state drive, a hard disk drive, etc. The auxiliary storage device 203 may also be a portable storage device such as a CD drive, a DVD drive, or a BD drive.

[0166] The output device 204 may be a display, a speaker, or the like. There are no particular limitations on the display, and any known device may be used as appropriate, such as a liquid crystal display or an organic EL display. The input device 205 is also not particularly limited, and any known device may be used as appropriate, as long as it can accept various requests to the management device 100, such as a keyboard, a mouse, or a touch panel. There are no particular limitations on the communication interface (communication I / F) 206, and any known device may be used as appropriate, such as a wireless or wired communication device. The processing functions of the management device 100 can be realized by the hardware configuration described above.

[0167] <<Functional Configuration of Management Device>> Returning to Fig. 3, the management device 100 has a control unit 110 and a storage unit 120. The control unit 110 controls the entire management device 100. The control unit 110 has a confirmation unit (I) 130, a comparison unit 140, and a notification unit (output unit) 150. The confirmation unit (I) of the control unit 110 performs the confirmation work described in the above means (V-1) to (V-6). In addition, the confirmation unit (I) of the control unit 110 selects, in the above means (Z-1), a product to be allocated as a renewable product from among the products obtained by the steam cracker, and in the above means (Z-2), determines the value of the proportion (P) to be allocated as a renewable product from the proportion of the product selected in the above means (Z-1) to the product obtained by the steam cracker, and in the above means (Z-3), determines the value of the content proportion (Q) of renewable raw materials contained in the waste material, and in the above means (Z-4), compares the value of the proportion (P) with the value of the content proportion (Q) and confirms that the value of the proportion (P) is equal to or less than the value of the content proportion (Q) (obtains information indicating that the value of the proportion (P) is equal to or less than the value of the content proportion (Q)). The comparison unit 140 of the control unit 110 performs a comparison work in the above means (Z-4), comparing the value of the proportion (P) with the value of the content proportion (Q) to have the confirmation unit (I) confirm. The notification unit 150 of the control unit 110 notifies (outputs) that (P) mass % of the selected product can be allocated as a renewable product in the product when the value of the proportion (P) is equal to or less than the content proportion (Q), and notifies (outputs) that the value of the selected product exceeds the content proportion (Q). That is, after executing the management method, the management device 100 outputs the result of allocating a value as a renewable product to the selected product according to the content proportion of renewable raw materials contained in the waste material, including scrap tires, obtained by the management method. The reaction database 160 in the memory unit 120 stores information about the apparatus used in the management method of the present invention and information about the reactions performed in the apparatus.That is, the storage unit 120 is a computer-readable storage medium storing a computer program, and includes a storage medium for storing the management program that causes the control unit 110, including a computer, to execute the management method. The amount and yield of the product obtained from each device can be determined by measurement, but by using the reaction database 160, not only can yield results be obtained by actual measurement, but also the amount and yield can be theoretically determined by calculation or predicted based on past accumulated data.

[0168] Next, the processing procedure of the management program will be described. Fig. 5 is a flowchart showing an example of the processing procedure of the management program in the control unit 110 of the management device 100. The following description will be made with reference to Fig. 5.

[0169] In step S101, the confirmation unit 130 of the control unit 110 of the management device 100 acquires information related to the pyrolysis unit, and the process proceeds to step S102. In step S102, the confirmation unit 130 of the control unit 110 of the management device 100 confirms, for example, based on information output from the pyrolysis unit, that pyrolysis oil (OUT) will be produced from waste materials (IN) including waste tires, and if it is confirmed that pyrolysis oil (OUT) has been produced, the process proceeds to step S103. In step S103, the confirmation unit 130 of the control unit 110 of the management device 100 acquires information related to the low-temperature hydrogenation unit, and the process proceeds to step S104. In step S104, the confirmation unit 130 of the control unit 110 of the management device 100 confirms, for example, based on information output from the low-temperature hydrogenation unit, that low-temperature hydrogenated oil (OUT) will be produced from the pyrolysis oil (IN), and confirms that it has been produced. Similarly, if it is confirmed that high-temperature hydrogenated oil is produced from the low-temperature hydrogenated oil fed to the high-temperature hydrogenation unit, that a naphtha fraction is produced from the high-temperature hydrogenated oil fed to the atmospheric distillation unit, and that chemical products are obtained from the naphtha fraction fed to the steam cracker, the process proceeds to step S105. In step S105, the confirmation unit 130 of the control unit 110 of the management device 100 confirms, for example, based on information output from the thermal cracking unit, low-temperature hydrogenation unit, high-temperature hydrogenation unit, atmospheric distillation unit, and steam cracker, that the processing is carried out in the order of the thermal cracking unit, low-temperature hydrogenation unit, high-temperature hydrogenation unit, atmospheric distillation unit, and steam cracker, and confirms that chemical products (OUT) are produced from the waste material (IN) including waste tires as a result of these processes. If it is confirmed that chemical products are produced, the process proceeds to step S106. In step S106, the confirmation unit 130 of the control unit 110 of the management device 100 receives information from the input device (input device 205 in Figure 4) in the management device 100 indicating that the worker has selected which products to assign as renewable products from among those produced by the steam cracker, and then proceeds to step S107.In step S107, the confirmation unit 130 of the control unit 110 of the management device 100 receives, from the input device (input device 205 in FIG. 4 ) in the management device 100, the value of the proportion (P) that the operator has set to be allocated as a renewable product, out of the proportion occupied by the selected product, and proceeds to step S108. In step S108, the confirmation unit 130 of the control unit 110 of the management device 100 obtains the value of the content proportion (Q) of renewable raw materials in the waste material input into the pyrolysis unit, and proceeds to step S109. In step S109, the comparison unit 140 of the control unit 110 of the management device 100 compares the value of the proportion (P) with the value of the content proportion (Q), and proceeds to step S110. In step S110, the confirmation unit 130 of the control unit 110 of the management device 100 checks whether the value of the percentage (P) is equal to or less than the value of the content percentage (Q) based on the comparison result between the value of the percentage (P) and the value of the content percentage (Q) performed by the comparison unit 140 of the control unit 110 of the management device 100, and if it is confirmed that the value is equal to or less than the value of the content percentage (Q), the process ends. Upon completion of the process, a value as a renewable product can be assigned to the selected desired product in accordance with the content percentage of renewable raw materials contained in the waste material, including waste tires. The assignment result is notified to the user via the notification unit 150 of the control unit 110 of the chemical product management device 100. That is, as described above, after executing the chemical product management method, the chemical product management device 100 outputs the result of assigning a value as a renewable product to the selected product in accordance with the content percentage of renewable raw materials contained in the waste material, including waste tires, obtained by the chemical product management method. If the conditions are not met during this process, the user is notified of this fact, for example, through the notification unit 150 of the control unit 110 of the chemical product management device 100. In this case, the operator can review the type of product to be selected, the value of the allocation ratio (P) of the selected product, the value of the renewable raw material content ratio (Q), and further review various conditions such as reaction conditions, and then attempt the process again.

[0170] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0171] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0172] In the following examples, component analysis and evaluation are performed by the following methods. Distillation properties: JIS K 2254 (Petroleum products - Distillation test methods - Part 7 Gas chromatography) Nitrogen content: JIS K 2609 (Crude oil and petroleum products - Nitrogen content test methods) Chlorine content: JPI-5S-64 (Petroleum products - Chlorine content test methods - Microcoulometric titration) Sulfur content: JIS K 2541-7 (Crude oil and petroleum products - Sulfur content test methods Part 7: Wavelength dispersive X-ray fluorescence spectroscopy (calibration curve method)) Diene number: ASTM D1961 (Method of Test for Maleic Diene Value of Drying Oils) For samples to which the above test methods cannot be applied, the method described in JP 2011-80766 A was used as a reference. １ It is estimated by HNMR measurement as follows: 1. About 20 mg of a sample with a known diene number is mixed with 500 μL of deuterated chloroform. １1. Calculate the integrated value in the range of 6.0 to 6.8 ppm by HNMR analysis and correct to the absolute area per 20 mg of sample. 3. Perform the above measurement on several samples to create a calibration curve of total area - diene number. 4. Calculate the total area of ​​the sample with an unknown diene number and estimate the diene number from the calibration curve in 3. Iodine number: JIS K 0070 (Test methods for acid value, saponification number, ester number, iodine number, hydroxyl number, and unsaponifiable matter of chemical products) Total acid number: JIS K 2501 (Petroleum products and lubricating oils -- Test method for neutralization) Heat exchanger fouling evaluation for low-temperature hydrogenated oil after low-temperature hydrogenation process: Measure the temperature drop (°C) due to fouling adhering to test piece 61 of heat exchanger fouling evaluation test device (HLPS) 60 shown in Figure 6 in the following order. 1. 1. Low-temperature hydrogenated oil at 25°C is passed through the left bottom (inlet 62) of the fouling evaluation test device (HLPS) 60 shown in Figure 6 for a fixed time (200 minutes). 2. While maintaining the temperature of the test piece 61 at a constant 300°C, the generation and adhesion of fouling to the surface of the test piece 61 is observed. Adhesion of fouling to the test piece 61 reduces heat transfer between the low-temperature hydrogenated oil and the test piece 61. 3. The temperature of the low-temperature hydrogenated oil discharged from the upper right (outlet 63) of the fouling evaluation test device (HLPS) 60 is measured. The difference between the initial measured temperature at the outlet 63 and the measured temperature after a fixed time has elapsed is defined as the "temperature decrease caused by the decrease in heat transfer due to fouling." (Note that the results of Comparative Examples 1 and 3 are evaluations of pyrolysis oil that has not undergone low-temperature hydrogenation treatment.) Here, "heat exchanger fouling evaluation" is performed according to the following criteria. (Evaluation criteria) ◯: The temperature drop during evaluation for a certain period of time (200 minutes) is 5°C or less, and it is judged that fouling of the heat exchanger is suppressed. ×: The temperature drop during evaluation for a certain period of time (200 minutes) is more than 5°C, and it is judged that fouling of the heat exchanger is significant. - Evaluation of heat exchanger fouling in atmospheric distillation unit: The atmospheric distillation feedstock oil is evaluated using the same evaluation method as the evaluation of heat exchanger fouling for low-temperature hydrogenated oil after the low-temperature hydrogenation step.・Analysis of steam cracking product gas: JIS K 2301:2011 (Fuel gas and natural gas -- Analysis and testing methods) ・Analysis of steam cracking product oil: The steam cracking product oil obtained after oil-water separation is fractionated to obtain a fraction of 250°C or less, and then analyzed according to JIS K 2536-2 (Petroleum products -- Testing methods for components, Part 2: Determination of all components by gas chromatography).

[0173] (Example 1) (1) Pyrolysis step The pyrolysis step is carried out using the pyrolysis apparatus shown in Figure 1. Specifically, a pyrolysis furnace 2 (capacity 0.5 m ３ Approximately 100 kg of scrap truck tire cut-ups (waste material 6) are placed in the pyrolysis furnace 2, and the atmosphere inside the pyrolysis furnace 2 is replaced with nitrogen gas. After that, the nitrogen gas is circulated in the pyrolysis device, and the gas temperature is raised to 500°C by the heat exchanger 1, and this temperature is maintained. The flow rate of the nitrogen gas introduced into the pyrolysis furnace 2 is 0.005 m ３ / s [ntp], set to 0.0045m ３ / s [ntp] ~ 0.0055 m ３ / s [ntp] range. The oxygen concentration in the pyrolysis system is controlled to a range of 1% by volume or less. A zirconia oxygen sensor is used to measure the oxygen concentration in the pyrolysis system. Pyrolysis oil is obtained from the bottom of the pyrolysis tower 12a. A first gas fraction is obtained from the top of the pyrolysis tower 12a. The reaction is continued until the distillation of the pyrolysis oil stops. After the distillation stops, the heat exchanger 1 is turned off and the mixture is left to cool for approximately 12 hours. The mixture of residue and metals is then removed from the pyrolysis furnace. The metals are removed from the mixture using a magnetic separator to obtain the residue. The residue is pulverized into fine powder with a particle size of 1 mm or less using a hammer-type pulverizer, and then classified using a wind classifier with rotating blades to remove coarse powder with a particle size of 50 μm or more, thereby obtaining a charcoal product with a particle size of 10 μm or less and a most frequent value of 4 μm. The ratios of each component and the properties of the pyrolysis oil are as shown in Table 1.

[0174] (2) Low-Temperature Hydrogenation Step (2-1) Production of Hydrogenation Catalyst A-1 A cylindrical support having a diameter of approximately 1.6 mm and a length of approximately 3 mm is prepared using silica-alumina powder having a composition of 97% by mass of alumina and 3% by mass of silica as oxides. Nickel nitrate and ammonium molybdate are dissolved in ion-exchanged water in an amount corresponding to the previously measured water absorption of the support to obtain a nickel nitrate and ammonium molybdate impregnation solution. The support is impregnated with this impregnation solution by incipient wetness to load the support so that the Ni content, calculated as oxide, is 4% by mass and the Mo content, calculated as oxide, is 20% by mass, based on the mass of the support. Next, the obtained impregnated product (catalyst precursor) is dried at 120°C for 3 hours and then calcined at 500°C for 1 hour in an air stream to obtain hydrogenation catalyst A-1.

[0175] (2-2) Low-temperature hydrogenation treatment The hydrogenation catalyst A-1 was packed into a reaction tube (inner diameter 20 mm). After sulfurization treatment with a diesel oil in which 1% by mass of dimethyl disulfide was dissolved, the reaction pressure was 11 MPaG, the reaction temperature was 180°C, and the WHSV was 0.3 h. －１ The pyrolysis oil is subjected to low-temperature hydrogenation under the conditions described above to obtain low-temperature hydrogenated oil. The properties of the low-temperature hydrogenated oil are shown in Table 2.

[0176] (3) High-Temperature Hydrogenation Step (3-1) Production of Hydrogenation Catalyst B-1 0.9 kg of silica-alumina powder containing 30% by mass of alumina and 70% by mass of silica as oxides and SiO ２ / Al ２ O ３ Using 0.1 kg of USY zeolite (SEQ ID NO: 30), a cylindrical support having a diameter of approximately 1.6 mm and a length of approximately 3 mm was prepared by adding, kneading, and calcining. Nickel nitrate and ammonium tungstate were dissolved in ion-exchanged water in an amount corresponding to the previously measured water absorption of the support, to obtain a nickel nitrate and ammonium tungstate impregnation solution. The support was impregnated with this impregnation solution by incipient wetness, and the Ni content, calculated as oxide, was 10 mass% and the W content, calculated as oxide, was 20 mass%, based on the mass of the support. Next, the obtained impregnated product (catalyst precursor) was dried at 120°C for 3 hours and then calcined at 500°C for 1 hour in an air stream, to obtain hydrogenation catalyst B-1.

[0177] (3-2) High-Temperature Hydrogenation Treatment Hydrogenation catalyst A-1 and hydrogenation catalyst B-1 are packed into a reaction tube (inner diameter 20 mm) in a weight ratio of 8:2. The packing order is hydrogenation catalyst A-1 in the front stage of the reaction tube and hydrogenation catalyst B-1 in the rear stage of the reaction tube. After sulfurization treatment with oil in which 1% by mass of dimethyl disulfide is dissolved in diesel fuel, the reaction pressure is 11 MPaG, the reaction temperature is 390°C, and the WHSV is 0.3 h. －１ The low-temperature hydrogenated oil was subjected to high-temperature hydrotreatment under the conditions of (a) to (c) to obtain a second gas fraction and a high-temperature hydrogenated oil. The results are shown in Table 3.

[0178] (4) Atmospheric Distillation Step: Crude oil having the properties shown in Table 2 and the high-temperature hydrogenated oil obtained in the high-temperature hydrogenation step are mixed in a mass ratio of 99:1 to obtain an atmospheric distillation feedstock. The atmospheric distillation feedstock is then fed into an atmospheric distillation unit, and distilled over a boiling point range of 60 to 160°C while controlling the column top temperature to obtain a naphtha fraction. Furthermore, a kerosene fraction with a boiling point range of 160 to 350°C is obtained while controlling the column top temperature.

[0179] (5) Steam Cracking Process Using a thermal cracking apparatus having a tubular reactor (reaction tube), the naphtha fraction and kerosene fraction obtained in the atmospheric distillation process are reacted with steam under the following conditions: reactor outlet reaction temperature 790 ° C, reaction pressure 0.15 MPa, and reaction tube residence time 0.25 seconds. The products (product oil and product gas) after the reaction are recovered and their properties are determined. The difference between the chemical product yield of the obtained product and the chemical product yield from the naphtha fraction derived from crude oil is calculated, and the results of the chemical product yield derived from the high-temperature hydrogenated oil obtained in the high-temperature hydrogenation process are shown in Table 5.

[0180] Example 2 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 190°C.

[0181] Example 3 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 200°C.

[0182] Example 4 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 210°C.

[0183] Example 5 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 250°C.

[0184] Example 6 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 300°C.

[0185] Example 7 Chemical products are produced in the same manner as in Example 1, except that the mixing ratio of crude oil to high-temperature hydrogenated oil in the atmospheric distillation step is changed to 99.5:0.5.

[0186] Example 8 Chemical products were produced in the same manner as in Example 1, except that the mixing ratio of crude oil to high-temperature hydrogenated oil in the atmospheric distillation step was changed to 98:2.

[0187] Comparative Example 1 A chemical product is produced in the same manner as in Example 1, except that the pyrolysis oil obtained in the pyrolysis step is used as the raw material for the high-temperature hydrogenation step without being subjected to the low-temperature hydrogenation step.

[0188] Comparative Example 2 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 150°C.

[0189] Comparative Example 3 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenated oil obtained in the low-temperature hydrogenation step without going through the high-temperature hydrogenation step is used as part of the atmospheric distillation feedstock instead of the high-temperature hydrogenated oil.

[0190] Comparative Example 4 Chemical products are produced in the same manner as in Example 1, except that the pyrolysis oil obtained in the pyrolysis step, without going through the low-temperature hydrogenation step and the high-temperature hydrogenation step, is used as part of the feedstock oil for atmospheric distillation instead of the low-temperature hydrogenated oil.

[0191] The results of the thermal decomposition process, low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process in Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Tables 1 to 5. The chemical product yield (mass%) relative to the total amount of thermal decomposition products excluding metals is the ratio of the total amount of chemical products (ethylene, propylene, butadiene, butenes, isoprene, cyclopentadiene, benzene, toluene, xylene, ethylbenzene, styrene, indene, methylstyrene) to the total amount of the first gas component, thermal decomposition oil, and residue obtained in the thermal decomposition process. As shown in Table 2, in Comparative Examples 1 to 2 and 4, compared to Examples 1 to 8, the feedstock oil (low-temperature hydrogenated oil after the low-temperature hydrogenation process) subjected to high-temperature hydrogenation treatment causes heat exchanger fouling, and therefore is not suitable for long-term operation. Also, as shown in Table 4, in Comparative Example 3, the feedstock oil for atmospheric distillation supplied to the atmospheric distillation step causes fouling of the heat exchanger, and therefore, it is not suitable for long-term operation, compared to Examples 1 to 8. Furthermore, as shown in Table 5, in Comparative Examples 3 and 4, the yield of chemical products is lower than in Examples 1 to 8, and chemical products cannot be produced efficiently.

[0192]

[0193]

[0194]

[0195]

[0196]

[0197] (Example 9) Chemical products are produced in the same manner as in Example 1, except that a feedstock oil containing 50 mass% of the pyrolysis oil obtained in the pyrolysis step and 50 mass% of the recycled oil consisting of the high-temperature hydrogenated oil (light and heavy fractions) obtained in the high-temperature hydrogenation step is used and low-temperature hydrogenation treatment is carried out in the low-temperature hydrogenation step.

[0198] (Example 10) Chemical products are produced in the same manner as in Example 1, except that a feedstock oil containing 20 mass% of pyrolysis oil obtained in the pyrolysis step and 80 mass% of recycled oil consisting of high-temperature hydrogenated oil (light and heavy fractions) obtained in the high-temperature hydrogenation step is used and low-temperature hydrogenation treatment is carried out in the low-temperature hydrogenation step.

[0199] The results for the low-temperature hydrogenation step, high-temperature hydrogenation step, atmospheric distillation step, and steam cracking step in Examples 9 and 10 are shown in Tables 6 to 9. As shown in Tables 6 to 9, even if the mixing ratio of the pyrolysis oil and recycled oil in the low-temperature hydrogenation step is changed, the feed oil subjected to the high-temperature hydrogenation treatment (low-temperature hydrogenated oil after the low-temperature hydrogenation step) suppresses heat exchanger fouling, and the feed oil for atmospheric distillation subjected to the atmospheric distillation step suppresses heat exchanger fouling, and chemical products can be produced efficiently. Therefore, it is suitable for long-term operation and can reduce production costs.

[0200]

[0201]

[0202]

[0203]

[0204] (Example 11) Chemical products are produced in the same manner as in Example 1, except that the low-temperature hydrogenation step is carried out using a feedstock oil (75% by mass of low-boiling oil, 25% by mass of high-boiling oil) obtained by fractionating the thermal cracking oil to remove 18% by mass of high-boiling oil. The properties of the feedstock oil used in the low-temperature hydrogenation step are shown in Table 10.

[0205] (Example 12) Chemical products are produced in the same manner as in Example 1, except that the low-temperature hydrogenation step is carried out using a feedstock oil (67% by mass of low-boiling oil, 33% by mass of high-boiling oil) obtained by fractionating the thermal cracking oil to remove 10% by mass of high-boiling oil. The properties of the feedstock oil used in the low-temperature hydrogenation step are shown in Table 10.

[0206] Example 13 Chemical products are produced in the same manner as in Example 1, except that the pyrolysis step is carried out at a pyrolysis oil temperature of 400° C. Table 10 shows the properties of the feedstock oil used in the low-temperature hydrogenation step.

[0207] Example 14 Chemical products are produced in the same manner as in Example 1, except that the pyrolysis step is carried out at a pyrolysis oil temperature of 700° C. Table 10 shows the properties of the feedstock oil used in the low-temperature hydrogenation step.

[0208] The product ratios are the product ratios after pyrolysis at each pyrolysis temperature, and the pyrolysis oil properties of Examples 11 and 12 indicate the pyrolysis oil properties after removal of high boiling oil.

[0209] The results of the low-temperature hydrogenation step, high-temperature hydrogenation step, atmospheric distillation step, and steam cracking step in Examples 11 to 14 are shown in Tables 11 to 14.

[0210]

[0211]

[0212]

[0213]

[0214] (Example 15) Chemical products are produced in the same manner as in Example 1, except that a low-temperature hydrogenation treatment is carried out in the low-temperature hydrogenation step using a feedstock oil containing 50 mass% of a feedstock oil obtained by distilling a pyrolysis oil to remove 18 mass% of high-boiling-point oil and 50 mass% of a recycled oil composed of high-temperature hydrogenated oil obtained in the high-temperature hydrogenation step.

[0215] (Example 16) Chemical products are produced in the same manner as in Example 1, except that a low-temperature hydrogenation treatment is carried out in the low-temperature hydrogenation step using a feedstock oil containing 20 mass% of a feedstock oil obtained by distilling a thermal cracking oil to remove 10 mass% of high-boiling-point oil and 80 mass% of a recycled oil consisting of high-temperature hydrogenated oil obtained in the high-temperature hydrogenation step.

[0216] The results of the thermal decomposition step, low-temperature hydrogenation step, high-temperature hydrogenation step, atmospheric distillation step, and steam cracking step in Examples 15 and 16 are shown in Tables 15 to 19.

[0217] The product ratios are the product ratios after pyrolysis at 500°C, and the pyrolysis oil properties of Examples 15 and 16 indicate the pyrolysis oil properties after removal of high boiling oil.

[0218]

[0219]

[0220]

[0221]

[0222] From the above examples, it is confirmed that the present invention makes it possible to efficiently produce chemical products from waste materials including waste tires.

[0223] 1...heat exchanger, 2...pyrolysis furnace, 3...oxygen-free gas supply source, 4...circulation path, 5...oil recovery device, 6...waste material, 7...cracking device, 8...external heating means, 9...flow meter, 10...damper, 11...blower, 12...drying tower, 13...recovery tank, 14...hot air furnace, 15...exhaust fan, 16...exhaust gas treatment device, 100...system, 110...pyrolysis unit, 111...first separation unit, 112...pulverization unit, 115...low-temperature hydrogenation unit, 120...high-temperature hydrogenation unit, 125...atmospheric distillation unit, 130...Steam cracker, S1...Waste material, S2...First gas component, S3...Pyrolysis oil, S4...Mixture of residue and metal component, S5...Residue component, S6...Metal component, S7...Powdered carbide, S8...Low-temperature hydrogenated oil, S9...Second gas component, S10...High-temperature hydrogenated oil, S11...Steam cracking feedstock oil, S12...Produced gas, S13...Produced oil, S14...Heavy fraction, S15...Recycled oil (high-temperature hydrogenated oil), 60...Measuring device for evaluating heat exchanger fouling, 61...Test piece, 62...Inlet, 63...Outlet

Claims

1. A method for producing a chemical product comprising: a thermal decomposition step of obtaining a first gas fraction, a thermal decomposition oil, and a residual fraction by thermal decomposition of crushed waste materials including waste tires; a low-temperature hydrogenation step of subjecting a feedstock oil containing at least a portion of the thermal decomposition oil to low-temperature hydrogenation treatment at 180°C or higher and 350°C or lower to obtain low-temperature hydrogenated oil; a high-temperature hydrogenation step of subjecting a feedstock oil containing at least a portion of the low-temperature hydrogenated oil to hydrogenation treatment at a temperature higher than the low-temperature hydrogenation treatment to obtain a second gas fraction and a high-temperature hydrogenated oil; a separation step of separating a feedstock oil for atmospheric distillation containing at least a portion of the high-temperature hydrogenated oil and crude oil into a naphtha fraction and other fractions by atmospheric distillation; and a steam cracking step of steam cracking a steam cracking feedstock oil containing at least a portion of the naphtha fraction and / or the other fractions to steam cracking treatment to obtain a chemical product, wherein in the thermal decomposition step, the amount of the thermal decomposition oil is 40 mass% or more relative to the total amount of the first gas fraction, the thermal decomposition oil, and the residual fraction. Manufacturing methods for chemical products.

2. The method according to claim 1, wherein the pyrolysis temperature in the pyrolysis step is 350°C or higher and 750°C or lower.

3. The manufacturing method described in claim 1, wherein in the pyrolysis step, the amount of the first gas component relative to the total amount of the first gas component, the pyrolysis oil and the residue component is 25 mass% or less.

4. The manufacturing method described in claim 1, wherein in the pyrolysis step, the amount of the pyrolysis oil relative to the total amount of the first gas fraction, the pyrolysis oil and the residue fraction is 80 mass% or less.

5. The method according to claim 1, wherein the pyrolysis oil has a 10% distillation temperature of 90°C or higher and a 90% distillation temperature of 350°C or higher.

6. The method according to claim 1, wherein the feedstock oil in the high-temperature hydrogenation step contains at least a portion of the pyrolysis oil or a portion of a fraction obtained by fractional distillation of the pyrolysis oil.

7. The method according to claim 1, wherein the pyrolysis oil is used as part of the feedstock oil for the low-temperature hydrogenation step after removing at least a portion of the high-boiling oil having a boiling point of more than 350°C by distillation.

8. The manufacturing method described in claim 1, wherein in the high-temperature hydrogenation process, the feed oil contains a low-boiling point oil having a boiling point of 350°C or less and a high-boiling point oil having a boiling point of more than 350°C, and the content of the high-boiling point oil is 50 mass% or less based on the total amount of the feed oil.

9. The method according to claim 1, wherein recycled oil containing at least a portion of the high-temperature hydrogenated oil obtained in the high-temperature hydrogenation step is used as a part of the feedstock oil in the low-temperature hydrogenation step.

10. The manufacturing method described in claim 9, wherein in the low-temperature hydrogenation step, the amount of the recycled oil relative to the total amount of the recycled oil and the pyrolysis oil in the feed oil is more than 10 mass% and not more than 99 mass%.

11. The process according to claim 1, wherein the high-temperature hydrogenation step is a step of hydrogenating the feedstock in the presence of a hydrogenation catalyst.

12. The method according to claim 11, wherein the hydrogenation catalyst comprises a Ni-based catalyst.

13. The production method according to claim 1, wherein in the high-temperature hydrogenation step, the nitrogen content in the atmospheric distillation feedstock oil is 2000 ppm by mass or more, and the nitrogen content in the naphtha fraction is 25 ppm by mass or less.

14. The manufacturing method described in claim 1, wherein in the separation step, the amount of the high-temperature hydrogenated oil relative to the total amount of the high-temperature hydrogenated oil and the crude oil in the atmospheric distillation feedstock oil is 0.001 mass% or more and 9 mass% or less.

15. The diene value of the low-temperature hydrogenated oil is 13.0 gI ２ The method of claim 1, wherein the weight ratio is less than 1 / 100 g.

16. The iodine value of the low-temperature hydrogenated oil is 160 gI ２ The method of claim 1, wherein the weight ratio is less than 1 / 100 g.

17. The method according to claim 1, wherein the low-temperature hydrogenated oil has a total acid value of less than 5.0 mg KOH / g.

18. The process according to claim 1, wherein in the steam cracking step, at least a portion of the naphtha fraction is a light naphtha.

19. The method of claim 1, wherein the chemical product is at least one selected from the group consisting of ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, indene, and methylstyrene.

20. The manufacturing method according to any one of claims 1 to 19, wherein the waste material further includes at least one of waste rubber and waste plastic.

21. A method for producing synthetic rubber, comprising a polymerization step of obtaining synthetic rubber by a polymerization reaction using the butadiene obtained by the production method according to claim 19 as at least a part of the raw material of the synthetic rubber.

22. A tire comprising a synthetic rubber obtained by the process of claim 21.

23. A method for producing a tire, comprising a vulcanization step of obtaining a tire by a vulcanization reaction using the synthetic rubber obtained by the production method according to claim 21 as at least a part of the raw materials for the tire.

24. A method for managing chemical products, which is carried out using a management device and is used when manufacturing chemical products using waste materials including waste tires, the management method is a method for using the management device to assign a value as a renewable product to the chemical product using a mass balance method according to the content ratio of renewable raw materials contained in the waste material, the management method includes a step (V) of confirming that the chemical product is obtained, the step (V) including the following steps (V-1), (V-2), (V-3), (V-4), (V-5), and (V-6), the step (V-1) being a step of confirming that the pyrolysis oil is produced from the waste material input into a pyrolysis unit that obtains the pyrolysis oil by pyrolysis of the waste material, The step (V-2) is a step of confirming that the low-temperature hydrogenated oil is produced from the pyrolysis oil input into a low-temperature hydrogenation unit in which a feedstock oil containing at least a part of the pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180° C. or higher and 350° C. or lower to obtain low-temperature hydrogenated oil; the step (V-3) is a step of confirming that the high-temperature hydrogenated oil is produced from the low-temperature hydrogenated oil input into a high-temperature hydrogenation unit in which a feedstock oil containing at least a part of the low-temperature hydrogenated oil is subjected to hydrogenation treatment at a temperature higher than the low-temperature hydrogenation treatment to obtain a second gas fraction and high-temperature hydrogenated oil; and the step (V-4) is a step of confirming that the naphtha fraction and the other fractions are produced from the high-temperature hydrogenated oil input into an atmospheric distillation unit in which an atmospheric distillation feedstock oil containing at least a part of the high-temperature hydrogenated oil and crude oil is subjected to atmospheric distillation to separate the naphtha fraction and the other fractions, The step (V-5) is a step of confirming that the chemical product can be obtained from the steam cracking feedstock oil that is fed into a steam cracker that subjects a steam cracking treatment to a steam cracking feedstock oil containing at least a portion of the naphtha fraction and / or the other fraction, and the step (V-6) is a step of confirming that the chemical product can be obtained from the waste material by treating it in the order of the thermal cracking unit, the low-temperature hydrogenation unit, the high-temperature hydrogenation unit, the atmospheric distillation unit, and the steam cracker,The management method includes a step (Z) of confirming a proportion of a product to be assigned a value as a renewable product, and the step (Z) includes the following steps (Z-1), (Z-2), (Z-3), and (Z-4): The step (Z-1) is a step of selecting a product to be assigned as a renewable product from among products obtained by the steam cracker; The step (Z-2) is a step of determining a value of a proportion (P) to be assigned as a renewable product from the proportion of the product selected in the step (Z-1) to the product obtained by the steam cracker; The step (Z-3) is a step of determining a value of a content proportion (Q) of renewable raw materials contained in the waste material; and The step (Z-4) is a step of comparing the value of the proportion (P) with the value of the content proportion (Q) and confirming that the value of the proportion (P) is equal to or less than the value of the content proportion (Q).

25. A management device comprising a computer-readable storage medium storing a management program, the management device executing the management method according to claim 24 by executing the management program.

26. The management device according to claim 25, which outputs a result of assigning a value as a renewable product to a product selected according to the content ratio of renewable raw materials contained in waste materials including scrap tires, obtained by the management method, after executing the management method.

27. A computer-readable storage medium storing a computer program, the storage medium storing a management program that causes a computer to execute the management method according to claim 24.

28. A management program for causing a computer to execute the management method according to claim 24.

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