Method for manufacturing chemical product and method for managing same

Abstract

Provided is a method for efficiently producing a chemical product from a waste material including waste tires, which enables long-term operation of a process by improving each step in a series of processes. A method for producing a chemical product, the method comprising: a thermal cracking step for obtaining a first gas component, a pyrolytic oil, and a residue component by thermally cracking a crushed waste material including waste tires; a low-temperature hydrogenation step in which a low-temperature hydrogenated oil is obtained by subjecting a raw oil containing at least a portion of the pyrolytic oil to low-temperature hydrogenation at 180-350 DEG C; a high-temperature hydrogenation step in which a raw oil containing at least a portion of the low-temperature hydrogenated oil is hydrotreated at a temperature higher than the low-temperature hydrotreating temperature to obtain a second gas component and a high-temperature hydrogenated oil; a separation step for separating into a naphtha fraction and another fraction by atmospheric distillation of a raw oil for atmospheric distillation containing at least a portion of the high-temperature hydrogenated oil and crude oil; and a steam cracking step for obtaining a chemical product by subjecting a steam cracking raw oil containing at least a portion of the naphtha fraction and / or other fractions to a steam cracking treatment. In the thermal cracking step, the amount of the pyrolytic oil is 40% by mass or more with respect to the total amount of the first gas component, the pyrolytic oil, and the residue component.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for producing a chemical product using waste materials. In addition, the present application relates to a management method for a chemical product, which is applied when a chemical product is produced using waste materials, and which is executed using a management device. BACKGROUND

[0002] In recent years, as a recycling method for waste materials such as waste tires, waste rubbers, waste plastics, and the like, a method for converting into a chemical product by thermal cracking or the like is being studied (for example, Patent Literature 1).

[0003] Patent Literature 1: Japanese Patent Application Laid-Open No. 2019-533041 SUMMARY

[0004] In recycling of waste materials, since the kind, quality, and the like of the waste materials are not always constant, and for the reason that a process using existing equipment is required, it is desired to develop a diversified process.

[0005] The present inventors and the like have studied a series of processes in which, in a method for producing a chemical product using waste materials, a thermal cracking step of thermally cracking the waste materials to obtain a pyrolysis oil, a separation step (atmospheric distillation step) of distilling the pyrolysis oil to obtain a naphtha fraction and other fractions (kerosene fraction, light oil fraction), and a steam cracking step of subjecting at least one of the naphtha fraction and / or the other fractions to a steam cracking treatment to obtain a chemical product. In this series of processes, it has been found that if the pyrolysis oil is directly distilled in an existing atmospheric distillation device, foulings (byproducts such as polymers of hydrocarbons) are generated in the atmospheric distillation device due to impurities such as dienes contained in the pyrolysis oil, and long-term operation of the process is not suitable.

[0006] An object of the present application is to provide a method for efficiently producing a chemical product from waste materials containing waste tires, which enables long-term operation of the process by improving each step in the series of processes. In addition, an object of the present application is to provide a management method for a chemical product, which is applied when a chemical product is produced using waste materials, and which is executed using a management device.

[0007] The present inventors and the like have studied to solve the above problem, and as a result, it has been found that, in a method for producing a chemical product using waste materials, by improving the above series of processes, and between the thermal cracking step and the separation step (atmospheric distillation step), a low-temperature hydrogenation step of subjecting the pyrolysis oil to a low-temperature hydrogenation treatment to obtain a low-temperature hydrogenated oil, and a high-temperature hydrogenation step of subjecting the low-temperature hydrogenated oil to a high-temperature hydrogenation treatment to obtain a high-temperature hydrogenated oil, generation of foulings (byproducts such as polymers of hydrocarbons) can be suppressed. The present inventors and the like have completed the present application based on this insight.

[0008] One embodiment of the present application relates to, for example, the following.

[0009] [1] A method for producing a chemical product, comprising the steps of:

[0010] a thermal cracking step of obtaining a first gas component, a pyrolysis oil, and a residue component by thermally cracking a crushed material of a waste material including a waste tire;

[0011] a low-temperature hydrogenation step of obtaining a low-temperature hydrogenated oil by subjecting a raw oil containing at least a part of the pyrolysis oil to a low-temperature hydrogenation treatment at 180°C to 350°C;

[0012] a high-temperature hydrogenation step of obtaining a second gas component and a high-temperature hydrogenated oil by subjecting a raw oil containing at least a part of the low-temperature hydrogenated oil to a hydrogenation treatment at a temperature higher than that of the low-temperature hydrogenation treatment;

[0013] a separation step of separating into a naphtha fraction and other fractions by subjecting a raw oil for atmospheric distillation containing at least a part of the high-temperature hydrogenated oil and the raw oil to atmospheric distillation; and

[0014] a steam cracking step of obtaining a chemical product by subjecting a steam cracking raw oil containing at least a part of the naphtha fraction and / or the other fractions to a steam cracking treatment;

[0015] In the thermal cracking step, the amount of the pyrolysis oil is 40% by mass or more relative to the total amount of the first gas component, the pyrolysis oil, and the residue component.

[0016] [2] The method according to [1], wherein the thermal cracking temperature in the thermal cracking step is 350°C to 750°C.

[0017] [3] The method according to [1] or [2], wherein in the thermal cracking step, the amount of the first gas component is 25% by mass or less relative to the total amount of the first gas component, the pyrolysis oil, and the residue component.

[0018] [4] The method according to any one of [1] to [3], wherein in the thermal cracking step, the amount of the pyrolysis oil is 80% by mass or less relative to the total amount of the first gas component, the pyrolysis oil, and the residue component.

[0019] [5] The method according to any one of [1] to [4], wherein the 10% distillation temperature of the pyrolysis oil is 90°C or more and the 90% distillation temperature is 350°C or more.

[0020] [6] The production method according to any one of [1] to [5], wherein the raw oil in the high-temperature hydrogenation step contains at least a part of the pyrolysis oil or a part of a fraction obtained by fractionating the pyrolysis oil.

[0021] [7] The production method according to any one of [1] to [6], wherein the pyrolysis oil is used as a part of the raw oil for the low-temperature hydrogenation step after at least a part of high-boiling oil having a boiling point exceeding 350°C is removed by distillation.

[0022] [8] The production method according to any one of [1] to [7], wherein, in the high-temperature hydrogenation step, the raw oil contains low-boiling oil having a boiling point of 350°C or lower and high-boiling oil having a boiling point exceeding 350°C, and the content of the high-boiling oil is 50% by mass or less based on the total amount of the raw oil.

[0023] [9] The production method according to any one of [1] to [8], wherein a recovered oil containing at least a part of the high-temperature hydrogenated oil obtained in the high-temperature hydrogenation step is used as a part of the raw oil for the low-temperature hydrogenation step.

[0024]

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

[0025]

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

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

[0026]

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

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

[0027]

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

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

[0028]

[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 in the raw oil for atmospheric distillation is 0.001% by mass to 9% by mass with respect to the total amount of the high-temperature hydrogenated oil and the crude oil.

[0029]

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

[14] , wherein the low-temperature hydrogenated oil has a diene value of less than 13.0 g I2 / 100 g.

[0030]

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

[15] , wherein the iodine value of the above-mentioned low-temperature hydrogenated oil is less than 160 gI2 / 100 g.

[0031]

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

[16] , wherein the total acid value of the above-mentioned low-temperature hydrogenated oil is less than 5.0 mg KOH / g.

[0032]

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

[17] , wherein, in the steam cracking process described above, at least a portion of the naphtha fraction is light naphtha.

[0033]

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

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

[0034]

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

[19] , wherein the waste further comprises at least one of waste rubber and waste plastic.

[0035]

[21] A method for manufacturing synthetic rubber includes a polymerization step of obtaining synthetic rubber by a polymerization reaction, wherein the polymerization reaction uses butadiene obtained by the manufacturing method described in

[19] as at least a portion of the raw material for synthetic rubber.

[0036]

[22] A tire comprising synthetic rubber obtained by the manufacturing method described in

[21] .

[0037]

[23] A method for manufacturing a tire includes a vulcanization step of obtaining the tire by a vulcanization reaction, wherein the vulcanization reaction uses synthetic rubber obtained by the manufacturing method described in

[21] as at least a portion of the raw material for the tire.

[0038]

[24] A method for managing chemical products, which is a method for managing chemical products using a management device when manufacturing chemical products using waste materials including waste tires.

[0039] The above-described management method utilizes the aforementioned management device to allocate the aforementioned chemical products using a mass balance method based on the proportion of renewable raw materials contained in the aforementioned waste, thereby obtaining the value of the renewable products.

[0040] The above management method includes the process (V) of confirming the acquisition of the above chemical products.

[0041] The above process (V) includes the following processes (V-1), (V-2), (V-3), (V-4), (V-5), and (V-6).

[0042] The above-mentioned process (V-1) is a process of confirming that the above-mentioned waste is used to generate the above-mentioned pyrolysis oil from the waste fed into the pyrolysis unit that produces pyrolysis oil through the pyrolysis of the above-mentioned waste.

[0043] The above-mentioned process (V-2) is a process of confirming that the above-mentioned low-temperature hydrogenated oil is generated from the above-mentioned pyrolysis oil in a low-temperature hydrogenation unit where the feedstock oil containing at least a portion of the above-mentioned pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0044] The above-mentioned process (V-3) is a process of confirming that the above-mentioned low-temperature hydrogenated oil is generated from the above-mentioned high-temperature hydrogenated oil in a high-temperature hydrogenation unit where the feed oil containing at least a portion of the above-mentioned low-temperature hydrogenated oil is hydrogenated at a temperature higher than the above-mentioned low-temperature hydrogenation treatment to obtain a second gas component and high-temperature hydrogenated oil.

[0045] The above-mentioned process (V-4) is a process that confirms the formation of the above-mentioned naphtha fraction and the above-mentioned other fractions from the above-mentioned high-temperature hydrogenated oil in an atmospheric distillation unit that separates the above-mentioned high-temperature hydrogenated oil into naphtha fraction and other fractions by atmospheric distillation of feedstock oil containing at least a portion of the above-mentioned high-temperature hydrogenated oil and crude oil.

[0046] The above-mentioned process (V-5) is a process of confirming that the above-mentioned chemical products are obtained from the steam cracking feedstock oil fed into a steam cracker that performs steam cracking treatment on the steam cracking feedstock oil containing at least a portion of the above-mentioned naphtha fraction and / or the above-mentioned other fractions.

[0047] The above-mentioned process (V-6) confirms that the above-mentioned chemical product is obtained from the above-mentioned waste by processing it in the following order: the above-mentioned pyrolysis unit, the above-mentioned low-temperature hydrogenation unit, the above-mentioned high-temperature hydrogenation unit, the above-mentioned atmospheric distillation unit, and the above-mentioned steam pyrolysis unit.

[0048] The aforementioned management method includes a process (Z) for determining the proportion of products allocated as renewable resources.

[0049] The above process (Z) includes the following processes (Z-1), (Z-2), (Z-3), and (Z-4).

[0050] The above-mentioned process (Z-1) is a process of selecting products as renewable products for distribution from the products obtained through the above-mentioned steam pyrolysis unit.

[0051] The above-mentioned process (Z-2) is a process of determining the value of the proportion (P) of the product selected in the above-mentioned process (Z-1) among the proportions of the product obtained through the above-mentioned steam pyrolysis unit, and allocating it as a renewable product.

[0052] The above-mentioned process (Z-3) is the process of determining the proportion (Q) of renewable raw materials contained in the above-mentioned waste.

[0053] The above process (Z-4) is to compare the value of the above proportion (P) with the value of the above containing proportion (Q) and confirm that the value of the above proportion (P) is below the value of the above containing proportion (Q).

[0054]

[25] A management device comprising a computer-readable storage medium storing a management program, wherein the management device executes the management method described in

[24] by executing the management program.

[0055]

[26] According to the management device described in

[25] , after executing the above management method, the result obtained by the above management method is output, which is the value of the selected product allocated as a renewable product based on the proportion of renewable raw materials contained in the waste containing waste tires.

[0056]

[27] A storage medium is a computer-readable storage medium that stores a computer program, the storage of which enables a computer to execute the management method described in

[24] .

[0057]

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

[24] .

[0058] According to the present invention, a method for efficiently manufacturing chemical products from waste materials including waste tires is provided, which enables long-term operation of the process by improving each step in a series of processes. Furthermore, the present invention provides a method for managing chemical products using a management device when manufacturing chemical products from waste materials. Attached Figure Description

[0059] Figure 1 This is a simplified diagram representing an example of a thermal pyrolysis apparatus.

[0060] Figure 2 This is a simplified diagram illustrating an example of a system for implementing a method for manufacturing a chemical product.

[0061] Figure 3 This is a simplified diagram used to illustrate the functional structure of the management device.

[0062] Figure 4 This is a block diagram illustrating an example of the hardware configuration of a management device.

[0063] Figure 5 This is a flowchart illustrating an example of the processing steps of the management procedure in the control unit of the management device.

[0064] Figure 6 This is a schematic diagram of the fouling assessment test apparatus (HLPS) used in the embodiments. Detailed Implementation

[0065] The preferred embodiments of the present invention will now be described in detail.

[0066] The method for manufacturing the chemical product according to this embodiment includes the following steps: a pyrolysis step, in which a pulverized material containing waste tires is pyrolyzed to obtain a first gaseous component, pyrolysis oil, and a residue component; a low-temperature hydrogenation step, in which a feedstock oil containing at least a portion of the pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil; a high-temperature hydrogenation step, in which a feedstock oil containing at least a portion of the low-temperature hydrogenated oil is subjected to hydrogenation treatment at a temperature higher than that of the low-temperature hydrogenation treatment to obtain a second gaseous component and high-temperature hydrogenated oil; a separation step, in which a feedstock oil for atmospheric distillation containing at least a portion of the high-temperature hydrogenated oil and crude oil is subjected to atmospheric distillation to separate naphtha fraction and other fractions; and a steam cracking step, in which a steam cracking feedstock oil containing at least a portion of the naphtha fraction and / or other fractions is subjected to steam cracking treatment to obtain the chemical product.

[0067] In the pyrolysis process of this embodiment, the amount of pyrolysis oil is 40% by mass or more relative to the total amount of the first gas component, pyrolysis oil and residue component.

[0068] In the chemical product manufacturing method of this embodiment, by using a pulverized material containing waste tires and going through the above-mentioned process, the generation of fouling in the heat exchanger in the high-temperature hydrogenation process and the atmospheric distillation process can be suppressed, enabling long-term operation of the process and efficient manufacturing of chemical products from waste tires.

[0069] The following is a detailed description of each step of the present invention.

[0070] (Thermal pyrolysis process)

[0071] The pyrolysis process involves pyrolyzing pulverized waste materials, including waste tires, to obtain a first gaseous component, pyrolysis oil, and residue components.

[0072] The waste includes at least waste tires, and may further include at least one of waste rubber and waste plastics.

[0073] Waste materials can also be referred to as polymeric waste materials containing polymers. Examples of polymeric materials include natural rubber, BR (butadiene rubber), SBR (styrene-butadiene rubber), NBR (nitrile rubber), IIR (butyl rubber), Cl-IIR (chlorinated butyl rubber), Br-IIR (brominated butyl rubber), and other rubber materials; and resin materials such as polyethylene, polypropylene, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, and polyvinyl chloride.

[0074] Waste materials can also contain metallic components. For example, waste tires sometimes contain metallic components such as steel cords and metal wires that form the tire's skeleton.

[0075] When the waste contains metallic components, the manufacturing method of this embodiment may further include a removal step to remove the metallic components from the waste or its pulverized form. The method for removing the metallic components from the waste is not particularly limited; for example, methods using magnets, sieves, etc., can be cited.

[0076] It should be noted that the metallic components in the waste do not necessarily need to be removed before the pyrolysis process. For example, when the pulverized waste contains metallic components, a mixture of the first gas component, pyrolysis oil, and residue component with the metallic components can be obtained in the pyrolysis process. The manufacturing method of this embodiment may further include a removal process to remove the metallic components from the mixture. The method for removing the metallic components from the mixture is not particularly limited; for example, methods using magnets, sieves, etc., can be cited.

[0077] There are no particular limitations on the method of crushing waste materials. For example, it can be mechanical crushing using a single-shaft crusher or a double-shaft crusher, crushing using water jet, cryogenic crushing, laser crushing, etc.

[0078] The pyrolysis of pulverized waste can be achieved, for example, by placing the pulverized waste in a pyrolysis furnace and supplying the furnace with high-temperature gas, thereby bringing the pulverized waste 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 less than 1% by volume). The high-temperature gas can be any gas other than oxygen and oxides, such as inert gases like nitrogen, argon, and helium, hydrogen, or hydrocarbons with 1 to 4 carbon atoms. The pyrolysis furnace is not particularly limited; for example, it can be a batch furnace, a fluidized bed furnace, or a rotary kiln furnace.

[0079] The pyrolysis temperature (temperature of the high-temperature gas) in the pyrolysis process can be, for example, 300°C or higher. 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. Alternatively, the pyrolysis temperature (temperature of the high-temperature gas) in the pyrolysis process can be, for example, 800°C or lower. 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. It should be noted that within such temperature ranges, there is a tendency to easily satisfy the preferred amounts of products (first gas component, pyrolysis oil, and residue component) described later, and to easily obtain feedstock oil with a high-boiling-point oil content within the preferred range.

[0080] That is, the thermal decomposition temperature (temperature of the high-temperature gas) in the thermal decomposition process can be, for example, 300-800℃, 300-750℃, 300-730℃, 300-710℃, 350-800℃, 350-750℃, 350-730℃, 350-710℃, 370-800℃, 370-750℃, 370-730℃, 370-710℃, 390-800℃, 390-750℃, 390-730℃, or 390-710℃.

[0081] Thermal pyrolysis can be carried out in the presence or without a thermal pyrolysis catalyst. As the thermal pyrolysis catalyst, catalysts commonly used in petrochemical thermal pyrolysis can be used without particular restriction. The thermal pyrolysis catalyst can be an acidic catalyst or a basic catalyst. Examples of acidic catalysts include catalysts containing aluminosilicates. Examples of aluminosilicates include zeolites, montmorillonite, and other montmorillonite groups. Examples of catalysts containing montmorillonite include clays or minerals such as activated clay, acid clay, and bentonite. Additionally, examples of basic catalysts include carbonates such as sodium carbonate.

[0082] The conditions of thermal cracking can be appropriately adjusted so that, for example, the resulting component ratio and the properties of the resulting pyrolysis oil are within the preferred range described later.

[0083] In the pyrolysis process, a first gaseous component, pyrolysis oil, and a residue component are obtained. It should be noted that, as described above, the residue component can also be obtained as a mixture with the metallic component. In the pyrolysis process, for example, pyrolysis gas is generated in a pyrolysis furnace, and by cooling this pyrolysis gas, the pyrolysis oil, as an oil component, can be recovered. Furthermore, in the pyrolysis process, for example, the first gaseous component can be recovered as a residual gas after recovering the oil component from the cooled pyrolysis gas. Additionally, in the pyrolysis process, the residue component can be recovered as a solid component remaining in the pyrolysis furnace after pyrolysis.

[0084] In this embodiment, the amount of pyrolysis oil is 40% by mass or more relative to the total amount of the first gas component, pyrolysis oil, and residue component.

[0085] It should be noted that, in the past, waste treatment methods have mainly focused on processing as much waste as possible, and have studied thermal cracking under conditions of low residue content and high gas content (e.g., Patent Document 1). In contrast, the manufacturing method of this embodiment specifically improves the yield of chemical products obtained through the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process by performing thermal cracking under conditions where the amount of pyrolysis oil is 40% by mass or more.

[0086] In the pyrolysis process, the amount of pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue component can be, for example, 45% by mass or more. 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, in the pyrolysis process, the amount of pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue component is preferably 48% by mass or more, more preferably 50% by mass or more, and may also be 51% by mass or more or 52% by mass or more. Furthermore, in the pyrolysis process, the amount of pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue component can be, for example, 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, further preferably 65% ​​by mass or less, and may also be 60% by mass or less.

[0087] That is, in the pyrolysis process, the amount of pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue component can be, for example, 40–80% by mass, 40–75% by mass, 40–70% by mass, 40–65% by mass, 40–60% by mass, 45–80% by mass, 45–75% by mass, 45–70% by mass, 45–65% by mass, 45–60% by mass, 48–80% by mass, 48–75% by 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% by mass, 51–75% by mass, 51–70% by mass, 51–65% by mass, 51–60% by mass, 52–80% by mass, 52–75% by mass, 52–70% by mass, 52–65% by mass, or 52–60% by mass.

[0088] In the pyrolysis process, the amount of the first gaseous component relative to the total amount of the first gaseous component, pyrolysis oil, and residue component is, for example, 25% 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, in the pyrolysis process, the amount of the first gaseous component relative to the total amount of the first gaseous component, pyrolysis oil, and residue component is preferably 20% by mass or less, more preferably 15% by mass or less, and may also be 13% by mass or less or 10% by mass or less. As long as the amount of the first gaseous component is 25% by mass or less in the pyrolysis conditions, the decrease in the yield of pyrolysis oil due to excessive pyrolysis of the pulverized material can be suppressed. That is, as long as the above-mentioned pyrolysis conditions are met, it is possible to prevent the pyrolysis oil generated by the pyrolysis of the pulverized material from further being pyrolyzed into gaseous components, and the yield of pyrolysis oil that becomes chemical products through the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process can be further improved, thereby further improving the yield of chemical products.

[0089] Furthermore, the amount of the first gaseous component relative to the total amount of the first gaseous component, pyrolysis oil, and residue component is, for example, 0.1% by mass or more. From the viewpoint of improving the purity of chemical products obtained through low-temperature hydrogenation, high-temperature hydrogenation, atmospheric distillation, and steam cracking processes, it can 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. When the pulverized material contains, for example, chlorine, a portion of the chlorine in the pulverized material is vaporized into chlorine gas or the like through pyrolysis. That is, a portion of the chlorine contained in the pulverized material is removed as part of the first gaseous component. Therefore, when a predetermined amount of the first gaseous component is generated in the pyrolysis process, the chlorine content in the pyrolysis oil can be reduced compared to the case where no first gaseous component is generated. Therefore, by applying thermal decomposition conditions that produce a specified amount of the first gaseous component, the purity of the chemical products obtained through low-temperature hydrogenation of the pyrolysis oil, high-temperature hydrogenation of the low-temperature hydrogenated oil, atmospheric distillation of the feedstock oil containing the high-temperature hydrogenated oil, and steam cracking of the steam cracking feedstock oil is further improved. It should be noted that the above example uses chlorine as an example, but the same principle applies when the pulverized material contains nitrogen, sulfur, or halogen elements other than chlorine.

[0090] That is, the amount of the first gaseous component relative to the total amount of the first gaseous component, pyrolysis oil, and residue components can be, for example, 0.1–25% by mass, 0.1–20% by mass, 0.1–15% by mass, 0.1–13% by mass, less than 0.1–10% by mass, 0.5–25% by mass, 0.5–20% by mass, 0.5–15% by mass, 0.5–13% by mass, less than 0.5–10% by mass, 0.7–25% by mass, 0.7–20% by mass, 0.7–15% by mass. %, 0.7–13% by mass, less than 0.7–10% by mass, 1–25% by mass, 1–20% by mass, 1–15% by mass, 1–13% by mass, less than 1–10% by mass, 1.3–25% by mass, 1.3–20% by mass, 1.3–15% by mass, 1.3–13% by mass, less than 1.3–10% by mass, 1.5–25% by mass, 1.5–20% by mass, 1.5–15% by mass, 1.5–13% by mass, or less than 1.5–10% by mass.

[0091] In the pyrolysis process, the amount of residue component relative to the total amount of the first gas component, pyrolysis oil, and residue component is, for example, 10% by mass or more. 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, in the pyrolysis process, the amount of residue component relative to the total amount of the first gas component, pyrolysis oil, and residue component is preferably 15% by mass or more, more preferably 20% by mass or more. As long as the amount of residue component is 10% by mass or more under pyrolysis conditions, the decrease in the yield of pyrolysis oil due to excessive pyrolysis of the pulverized material can be suppressed. That is, under the above-mentioned pyrolysis conditions, the further pyrolysis of the pyrolysis oil generated by the pyrolysis of the pulverized material into gaseous components can be prevented, and the yield of pyrolysis oil that becomes chemical products through the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process can be further improved, thereby further improving the yield of chemical products.

[0092] The amount of residue component relative to the total amount of the first gas component, pyrolysis oil, and residue component 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 also be 40% by mass or less. As the amount of residue component relative to the total amount of the first gas component, pyrolysis oil, and residue component increases, the amounts of the first gas component and pyrolysis oil relative to the total amount of the first gas component, pyrolysis oil, and residue component decrease. Therefore, under pyrolysis conditions where the amount of residue component is 60% by mass or less, it is possible to suppress the residue component residue from the pulverized material that escapes into pyrolysis oil, further improving the yield of pyrolysis oil that becomes chemical products through the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process, and thus further improving the yield of chemical products. That is, in the pyrolysis process, the amount of the residue component relative to the total amount of the first gas component, pyrolysis oil and residue component can be, for example, 10-60% by mass, 10-55% by mass, 10-50% by mass, 10-45% by mass, 10-40% by mass, 15-60% by mass, 15-55% by mass, 15-50% by mass, 15-45% by mass, 15-40% by mass, 20-60% by mass, 20-55% by mass, 20-50% by mass, 20-45% by mass or 20-40% by mass.

[0093] The first gaseous component may be, for example, a gaseous component in the products generated by thermal decomposition at atmospheric pressure and 20°C. The first gaseous component may include, for example, hydrogen and hydrocarbons having 1 to 4 carbon atoms.

[0094] There are no particular limitations on the method for recovering the first gas component. For example, the first gas component can be recovered as the residual gas after cooling and recovering oil (pyrolysis oil) from the pyrolysis gas generated by pyrolysis.

[0095] The first gas component can be reused, for example, as a high-temperature gas (oxygen-free gas) in pyrolysis. That is, the first gas component can be heated and supplied to the pyrolysis furnace as part (or all) of the high-temperature gas (oxygen-free gas). Alternatively, the first gas component can be used, for example, as a combustion gas for heating the pyrolysis section in the pyrolysis process, or as a combustion gas for heating furnaces in other processes.

[0096] Pyrolysis oil can be, for example, a liquid component in the products generated by pyrolysis at atmospheric pressure and 20°C. There are no particular limitations on the method for recovering pyrolysis oil. For example, pyrolysis oil can be recovered as an oil fraction distilled from a pyrolysis furnace. That is, pyrolysis oil can be recovered as an oil fraction condensed by cooling the pyrolysis gases generated by pyrolysis.

[0097] There are no particular limitations on the distillation properties of pyrolysis oil; for example, it can be used as a feedstock in both low-temperature and high-temperature hydrogenation processes.

[0098] The 10% distillation temperature (T10) of the pyrolysis oil can be, for example, 90°C or higher. From the viewpoint of being more suitable as a feedstock for low-temperature hydrogenation processes, it is preferably 140°C or higher, more preferably 150°C or higher, and even more preferably 155°C or higher. Alternatively, the 10% distillation temperature of the pyrolysis oil can be, for example, 200°C or lower, or 190°C or lower, or 180°C or lower.

[0099] That is, the 10% distillation temperature (T10) of the pyrolysis oil can be, for example, 90–200℃, 90–190℃, 90–180℃, 140–200℃, 140–190℃, 140–180℃, 150–200℃, 150–190℃, 150–180℃, 155–200℃, 155–190℃, or 155–180℃.

[0100] The 90% distillation temperature (T90) of the pyrolysis oil can 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. It can also be 410°C or higher, 420°C or higher, 430°C or higher, 440°C or higher, or 450°C or higher. In addition, the 90% distillation temperature (T90) of the pyrolysis oil can be, for example, 650°C or lower, preferably 600°C or lower, and more preferably 550°C or lower.

[0101] That is, the 90% distillation temperature (T90) of the pyrolysis oil is, for example, 350–650℃, 350–600℃, 350–550℃, 370–650℃, 370–600℃, 370–550℃, 390–650℃, 390–600℃, 390–550℃, 400–650℃, 400–600℃, 400–550℃, 410℃. ~650℃, 410~600℃, 410~550℃, 420~650℃, 420~600℃, 420~550℃, 430~650℃, 430~600℃, 430~550℃, 440~650℃, 440~600℃, 440~550℃, 450~650℃, 450~600℃ or 450~550℃.

[0102] Pyrolysis oil includes low-boiling-point oil with a boiling point below 350°C, and may further include high-boiling-point oil with a boiling point above 350°C.

[0103] The content of high-boiling-point oil in the pyrolysis oil is not particularly limited, but based on the total amount of pyrolysis oil, it is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, and even more preferably 35% by mass or less. By adjusting the content of high-boiling-point oil in the pyrolysis oil to 50% by mass or less, the diene value in the feedstock oil can be reduced, thereby reducing fouling and clogging in piping and heat exchangers during a series of processes.

[0104] In addition, the content of high-boiling-point oil in pyrolysis oil is based on the total amount of pyrolysis oil, for example, it can be more than 5% by mass, more than 8% by mass, or more than 10% by mass.

[0105] That is, the content of high-boiling-point oil in pyrolysis oil is based on the total amount of pyrolysis oil, for example, it can be 5-50% by mass, 5-45% by mass, 5-40% by mass, 5-35% by mass, 8-50% by mass, 8-45% by mass, 8-40% by mass, 8-35% by mass, 10-50% by mass, 10-45% by mass, 10-40% by mass, and 10-35% by mass.

[0106] Pyrolysis oil may also contain nitrogen, sulfur, chlorine, halogen elements, etc.

[0107] The nitrogen content of the pyrolysis oil can be, for example, 100 ppm or more by mass, or 2000 ppm or more by mass, 2500 ppm or more by mass, or 3000 ppm or more by mass. In this embodiment, even if a large amount of nitrogen is present in the pyrolysis oil, the nitrogen is easily separated from the liquid product by hydrogenation into gaseous components such as ammonia during the low-temperature hydrogenation and high-temperature hydrogenation processes. Furthermore, by supplying the liquid product with significantly reduced nitrogen content to the steam cracking process, high-purity chemical products (chemical products with low nitrogen content) can be easily obtained. The nitrogen content of the pyrolysis oil can be, for example, less than 20,000 ppm by mass, or less than 15,000 ppm by mass, or less than 10,000 ppm by mass. If the nitrogen content is less than 20,000 ppm by mass, the nitrogen content of the liquid product after the low-temperature hydrogenation and high-temperature hydrogenation processes can be reduced more significantly.

[0108] That is, the nitrogen content of the pyrolysis oil can be, for example, 100–20000 ppm by mass, 100–15000 ppm by mass, 100–10000 ppm by mass, 2000–20000 ppm by mass, 2000–15000 ppm by mass, 2000–10000 ppm by mass, 2500–20000 ppm by mass, 2500–15000 ppm by mass, 2500–10000 ppm by mass, 3000–20000 ppm by mass, 3000–15000 ppm by mass, or 3000–10000 ppm by mass.

[0109] The sulfur content of the pyrolysis oil can be, for example, 10 ppm or more by mass, or 100 ppm or more by mass, or 500 ppm or more by mass, or 1000 ppm or more by mass. In this embodiment, even if a large amount of sulfur is present in the pyrolysis oil, the sulfur is easily separated from the liquid product by hydrogenation into gaseous components such as hydrogen sulfide during the low-temperature hydrogenation and high-temperature hydrogenation processes. Furthermore, by supplying the liquid product with significantly reduced sulfur content to the steam cracking process, high-purity chemical products (chemical products with low sulfur contamination) can be easily obtained. The sulfur content of the pyrolysis oil can be, for example, less than 30,000 ppm by mass, or less than 20,000 ppm by mass, or less than 10,000 ppm by mass. If the sulfur content is less than 30,000 ppm by mass, the sulfur content of the liquid product after the low-temperature hydrogenation and high-temperature hydrogenation processes can be reduced more significantly. That is, the sulfur content of the pyrolysis oil can be, for example, 10–30,000 ppm by mass, 10–20,000 ppm by mass, 10–10,000 ppm by mass, 100–30,000 ppm by mass, 100–20,000 ppm by mass, 100–10,000 ppm by mass, 500–30,000 ppm by mass, 500–20,000 ppm by mass, 500–10,000 ppm by mass, 1,000–30,000 ppm by mass, 1,000–20,000 ppm by mass, or 1,000–10,000 ppm by mass.

[0110] The chlorine content of the pyrolysis oil can be, for example, 10 ppm by mass or more, or 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 is easily separated from the liquid product by hydrogenation into gaseous components such as hydrogen chloride during the low-temperature hydrogenation and high-temperature hydrogenation processes. Furthermore, by supplying the liquid product with significantly reduced chlorine content to the steam cracking process, high-purity chemical products (chemical products with low chlorine contamination) can be easily obtained. The chlorine content of the pyrolysis oil can be, for example, 2000 ppm by mass or less, or 1500 ppm by mass or less, or 1000 ppm by mass or less. If the chlorine content is below 1000 ppm by mass, the chlorine content of the liquid product after the low-temperature hydrogenation and high-temperature hydrogenation processes can be reduced more significantly. In addition, it is preferable that not only the chlorine content but also the other halogen element content is within the same range.

[0111] That is, the chlorine content of the pyrolysis oil can be, for example, 10–2000 ppm by mass, 10–1500 ppm by mass, 10–1000 ppm by mass, 30–2000 ppm by mass, 30–1500 ppm by mass, 30–1000 ppm by mass, 50–2000 ppm by mass, 50–1500 ppm by mass, 50–1000 ppm by mass, 100–2000 ppm by mass, 100–1500 ppm by mass, or 100–1000 ppm by mass.

[0112] The residue component may be, for example, the solid components in the products generated by pyrolysis that were not recovered as pyrolysis gases. There are no particular limitations on the method for recovering the residue component. The residue component may be recovered, for example, as the solid components remaining in the pyrolysis furnace (solid components not discharged from the reaction system as pyrolysis gases).

[0113] The residue component can be a carbide formed by the thermal decomposition of pulverized waste. In this embodiment, the residue component can be recycled as a carbide.

[0114] Carbides are predominantly carbon-based components. For example, carbides can be carbon concentrates with carbon black as the main component. Sometimes, carbides have agglomerated lumpy portions formed during thermal decomposition. In such cases, powdered carbides are obtained by crushing the agglomerated carbides using a pulverizer or similar device.

[0115] That is, the manufacturing method of this embodiment can further include a step of pulverizing the residue components to obtain powdered carbides. Such a manufacturing method can be said to be capable of producing both chemical products and carbides. Furthermore, in such a manufacturing method, by adjusting the amounts of pyrolysis oil and residue components formed in the pyrolysis process to the aforementioned preferred range, both chemical products and carbides can be obtained efficiently.

[0116] Powdered carbides can be used as additives for rubber, resins, colorants, and other applications.

[0117] It should be noted that, depending on the pyrolysis conditions, the residue composition may sometimes contain rubber components from waste materials that have not been completely pyrolyzed. In this case, because the rubber components are adhesive, the carbides are recovered in the form of a blocky mixture of carbon black and rubber components. The adhesiveness of the rubber components hinders the pulverization of such carbides, making it difficult to pulverize them using a pulverizer or similar equipment. Furthermore, the blocky carbides result in poor dispersion in the parent material, making them unsuitable for use as rubber additives, resin additives, colorants, etc. In this regard, the pyrolysis process of this embodiment, by employing the aforementioned preferred pyrolysis conditions, reduces the residual rubber components in the recovered carbides, tending to easily obtain powdered carbides suitable for use as rubber additives, resin additives, colorants, etc.

[0118] Furthermore, when it is difficult to obtain powdered carbides from the residue components due to the presence of rubber components or the like, the manufacturing method of this embodiment can further include a step of manufacturing carbides by thermal decomposition of the residue components.

[0119] The pyrolysis process can be implemented, for example, by a pyrolysis apparatus equipped with a pyrolysis furnace. The pyrolysis furnace used in the pyrolysis process only needs to be capable of pyrolyzing the pulverized material; for example, a batch pyrolysis furnace or a continuous pyrolysis furnace can be used. As a continuous pyrolysis furnace, for example, a rotary kiln or a spiral furnace can be used. It should be noted that the following description, as an example of a pyrolysis apparatus, uses a batch pyrolysis furnace, but the pyrolysis apparatus is not limited to this.

[0120] Figure 1 This is a simplified diagram representing an example of a thermal pyrolysis apparatus. Figure 1 The pyrolysis apparatus includes: a heat exchanger 1 for heating oxygen-free gas; a decomposition device 7 having a pyrolysis furnace 2 containing waste 6 internally and an external heating means 8 for heating the pyrolysis furnace 2 from the outside; an oil recovery device 5 for cooling the pyrolysis gas generated in the decomposition device 7 and recovering the condensed oil (pyrolysis oil); a circulation path 4 for supplying the residual gas after oil recovery in the oil recovery device 5 as oxygen-free gas to the heat exchanger 1; and an oxygen-free gas supply source 3 for supplying oxygen-free gas to the heat exchanger 1.

[0121] in addition, Figure 1 The pyrolysis unit includes a flow meter 9, a damper 10, and a blower 11 in the piping that connects the oxygen-free gas supply source 3 and the heat exchanger 1 to supply oxygen-free gas from the oxygen-free gas supply source 3. In the circulation path 4 that uses the residual gas recovered from the oil separation and recovery device 5 as oxygen-free gas and circulates it in the heat exchanger 1, the unit also includes a flow meter 9, a damper 10, a blower 11, and a hot blast furnace 14.

[0122] Furthermore, the oil recovery unit 5 includes multiple distillation columns 12a and 12b for separating the recovered oil based on its boiling point. Each distillation column 12 is connected to a recovery tank 13 at its lower part via piping, enabling the storage of the recovered oil. It should be noted that... Figure 1 Although the pyrolysis unit has multiple distillation columns 12a and 12b, in this embodiment, since the pyrolysis oil can be directly used as feedstock for the low-temperature hydrogenation process, there can be only one distillation column. Furthermore, in Figure 1 In the thermal cracking unit, each distillation column 12 is connected to a different recovery tank 13, but each distillation column 12 can also be connected to the same recovery tank 13.

[0123] The pyrolysis oil of the present invention preferably has at least a portion of its high-boiling-point oil (exceeding 350°C) removed by distillation or the like before the subsequent low-temperature hydrogenation process. By removing at least a portion of the high-boiling-point oil from the pyrolysis oil, the generation of fouling in heat exchangers and furnaces during the high-temperature hydrogenation and atmospheric distillation processes can be suppressed, enabling long-term operation of the process. While not limited to this, it is more preferable, for example, to remove at least a portion of the high-boiling-point oil (exceeding 450°C).

[0124] One method for removing high-boiling-point oil is to cool the pyrolysis gas generated during the pyrolysis process, separating the pyrolysis oil containing a large amount of high-boiling-point oil from a gaseous component containing a large amount of low-boiling-point oil. Then, the gaseous component containing a large amount of low-boiling-point oil is further cooled, thereby separating the first gaseous component and the pyrolysis oil containing a large amount of low-boiling-point oil. Alternatively, the pyrolysis oil can be heated and the low-boiling-point oil and high-boiling-point oil can be separated in a distillation column, but this method is not limited to those described.

[0125] The content of high-boiling-point oil in the pyrolysis oil (hereinafter also referred to as "fractionated pyrolysis oil") from which some high-boiling-point oil has been removed before the low-temperature hydrogenation process is not particularly limited, but based on the total amount of fractionated pyrolysis oil before the low-temperature hydrogenation process, it is 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and even more preferably 25% by mass or less. If the content of high-boiling-point oil in the fractionated pyrolysis oil before the low-temperature hydrogenation process is 50% by mass or less, the influence of easily weighted components such as heavy olefins and dienes can be suppressed.

[0126] In addition, the content of high-boiling-point oil in the pyrolysis oil fractionated before the low-temperature hydrogenation process is based on the total amount of pyrolysis oil fractionated before the low-temperature hydrogenation process. For example, it can be more than 1% by mass, more than 2% by mass, or more than 3% by mass.

[0127] The removed high-boiling-point oil can be recycled as a raw material for the pyrolysis process, used as a raw material for carbon black manufacturing, or used as fuel.

[0128] (Cryogenic hydrogenation process)

[0129] The low-temperature hydrogenation process is a process of hydrogenating feedstock containing at least a portion of pyrolysis oil at a low temperature of 180℃ to 350℃ to obtain low-temperature hydrogenated oil.

[0130] The feedstock oil in the low-temperature hydrogenation process can contain pyrolysis oil or fractionated pyrolysis oil. Furthermore, the feedstock oil in the low-temperature hydrogenation process can further contain components other than pyrolysis oil, or the pyrolysis oil can be used directly as the feedstock oil.

[0131] As part of the feedstock in the low-temperature hydrogenation process, recycled oil containing at least a portion of the light and heavy components obtained in the high-temperature hydrogenation process (described later) or any dilution hydrocarbon oil can be used. By using recycled oil or any dilution hydrocarbon oil, dienes and olefins that are prone to polymerization and fouling can be diluted, thus preventing fouling. Furthermore, the heating effect within the reactors in both the low-temperature and high-temperature hydrogenation processes can be reduced, improving the stability of process operation. Examples of dilution hydrocarbons include kerosene fractions, light oil fractions, and vacuum distillation fractions obtained from an atmospheric distillation unit from crude oil sources, LCO obtained from an FCC unit, and product kerosene and product light oil.

[0132] In the low-temperature hydrogenation process, the amount of recovered oil relative to the total amount of recovered oil and pyrolysis oil in the feedstock is preferably 10% to 99% by mass, more preferably 20% to 97% by mass, further preferably 30% to 95% by mass, particularly preferably 40% to 93% by mass, and most preferably 50% to 90% by mass.

[0133] Low-temperature hydrogenation can be a process of hydrogenating feedstock in the presence of a hydrogenation catalyst. Hydrogenation can be carried out, for example, by feeding the feedstock into a reactor equipped with a hydrogenation catalyst, allowing it to come into contact with the catalyst within the reactor.

[0134] As a hydrogenation catalyst, known hydrogenation catalysts used in the hydrogenation of hydrocarbon oils can be used, for example. From the viewpoint of hydrogenation capacity, hydrogenation catalysts preferably include, for example, Ni-based or Co-based catalysts. Ni-based catalysts refer to catalysts having Ni as the active metal, and Ni can exist in the form of sulfides, etc. Co-based catalysts refer to catalysts having Co as the active metal. As a hydrogenation catalyst, one hydrogenation catalyst or multiple hydrogenation catalysts can be used.

[0135] The reaction temperature in the low-temperature hydrogenation process is 180℃~350℃, preferably 190℃~340℃, more preferably 200℃~330℃, even more preferably 210℃~320℃, particularly preferably 220℃~310℃, and most preferably 240℃~305℃. By adjusting the reaction temperature in the low-temperature hydrogenation process to the above-mentioned range, especially above 200℃ or even above 240℃, a low-temperature hydrogenated oil with a reduced diene value can be obtained.

[0136] The reaction pressure in the cryogenic hydrogenation process is not particularly limited; for example, it can be 1 MPaG or more, preferably 3 MPaG or more, and more preferably 5 MPaG or more. Furthermore, the reaction pressure in the cryogenic hydrogenation process is not particularly limited; for example, it can be 20 MPaG or less, preferably 19 MPaG or less, and more preferably 18 MPaG or less.

[0137] That is, the reaction pressure in the low-temperature hydrogenation process can be, for example, 1-20 MPaG, 1-19 MPaG, 1-18 MPaG, 3-20 MPaG, 3-19 MPaG, 3-18 MPaG, 5-20 MPaG, 5-19 MPaG, or 5-18 MPaG.

[0138] When using a continuous flow reactor to implement a cryogenic hydrogenation process, the heavy hourly space velocity (WHSV) of the feedstock can be, for example, 0.1 h⁻¹. -1 The preferred value is 0.15h. -1 The above is preferred, and 0.2h is even more preferred. -1 That's all. Additionally, the heavy hourly space velocity (WHSV) of the feedstock can, for example, be 5 h⁻¹. -1 The following is preferred: 4h -1 The following is more preferably 3h -1 the following.

[0139] That is, the heavy hourly space velocity (WHSV) of the feedstock oil can be 0.1 to 5 h⁻¹. -1 0.1~4h -1 0.1 to 3 hours -1 0.15~5h -1 0.15~4h -1 0.15~3h -1 0.2-5h -1 0.2-4h -1 or 0.2 to 3 hours -1 .

[0140] The cryogenic hydrogenation process is carried out in the presence of hydrogen. When using a continuous flow reactor to carry out the cryogenic hydrogenation process, the hydrogen / oil ratio can be, for example, 100 NL / L or more, preferably 150 NL / L or more, and more preferably 200 NL / L or more. Alternatively, the hydrogen / oil ratio can be, for example, 1500 NL / L or less, preferably 1400 NL / L or less, and more preferably 1300 NL / L or less.

[0141] That is, the hydrogen / oil ratio can be, for example, 100-1500 NL / L, 100-1400 NL / L, 100-1300 NL / L, 150-1500 NL / L, 150-1400 NL / L, 150-1300 NL / L, 200-1500 NL / L, 200-1400 NL / L, or 200-1300 NL / L.

[0142] The low-temperature hydrogenated oil obtained in the low-temperature hydrogenation process preferably has the following properties.

[0143] The diene value of the low-temperature hydrogenated oil is preferably less than 14.0 gI2 / 100g, more preferably less than 13.0 gI2 / 100g, even more preferably less than 12.0 gI2 / 100g, and particularly preferably less than 11.0 gI2 / 100g.

[0144] The iodine value of the low-temperature hydrogenated oil is preferably less than 160 gI2 / 100g, more preferably less than 155 gI2 / 100g, even more preferably less than 150 gI2 / 100g, and particularly preferably less than 145 gI2 / 100g.

[0145] The total acid value of the low-temperature hydrogenated oil is less than 5.0 mg KOH / g, more preferably less than 4.8 mg KOH / g, even more preferably less than 4.7 mg KOH / g, and particularly preferably less than 4.5 mg KOH / g.

[0146] In this invention, by reducing the amount of olefins, dienes, higher fatty acids, etc., that polymerize and cause scaling in the pyrolysis oil to be processed in the low-temperature hydrogenation process in advance, the generation of scaling in the heat exchangers of the high-temperature hydrogenation process and the atmospheric distillation unit can be suppressed, thus enabling long-term operation of the process.

[0147] (High-temperature hydrogenation process)

[0148] The high-temperature hydrogenation process is a process of obtaining a second gaseous component and a high-temperature hydrogenated oil by subjecting at least a portion of a feedstock containing low-temperature hydrogenated oil to high-temperature hydrogenation treatment. It should be noted that the high-temperature hydrogenated oil contains light components with a boiling point below 350°C and heavy components with a boiling point above 350°C.

[0149] The feedstock oil in the high-temperature hydrogenation process contains low-temperature hydrogenated oil, but may also contain pyrolysis oil, fractionated pyrolysis oil, or other components.

[0150] The feedstock oil in the high-temperature hydrogenation process contains low-boiling-point oil (boiling point below 350°C) and high-boiling-point oil (boiling point above 350°C), for example, the content of high-boiling-point oil is less than 50% by mass based on the total amount of feedstock oil. By adjusting the decomposition conditions in the high-temperature hydrogenation process, the high-boiling-point oil can be made into a light component, which is supplied as a feedstock for generating chemical products in the steam cracking process described later. Therefore, the higher the content of high-boiling-point oil, the more suitable it is as a feedstock oil, and the trend is towards further increasing the yield of chemical products. However, in a series of processes, in order to reduce fouling and clogging of piping and heat exchangers, it is preferable to reduce the amount of the aforementioned high-boiling-point oil.

[0151] The content of high-boiling-point oil in the feedstock oil during the high-temperature hydrogenation process is preferably less than 50% by mass, more preferably less than 40% by mass, even more preferably less than 30% by mass, and even more preferably less than 25% by mass, based on the total amount of feedstock oil.

[0152] In addition, the content of high-boiling-point oil in the feedstock oil in the high-temperature hydrogenation process can be above 1.0% by mass, above 2.0% by mass, or above 3.0% by mass, based on the total amount of feedstock oil.

[0153] The 10% distillation temperature of the feedstock oil in the high-temperature hydrogenation process can 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. Alternatively, the 10% distillation temperature of the feedstock oil can be, for example, below 200°C, or below 190°C or below 180°C.

[0154] That is, the 10% distillation temperature of the feedstock oil in the high-temperature hydrogenation process can be, for example, 90–200℃, 90–190℃, 90–180℃, 140–200℃, 140–190℃, 140–180℃, 150–200℃, 150–190℃, 150–180℃, 155–200℃, 155–190℃, or 155–180℃.

[0155] In the high-temperature hydrogenation process, the 90% distillation temperature of the feedstock oil can 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. It can also be 410°C or higher, 420°C or higher, 430°C or higher, 440°C or higher, or 450°C or higher. Alternatively, the 90% distillation temperature of the feedstock oil can be, for example, 650°C or lower, preferably 600°C or lower, and more preferably 550°C or lower.

[0156] That is, the 90% distillation temperature of the feedstock oil in the high-temperature hydrogenation process can be, for example, 350–650℃, 350–600℃, 350–550℃, 370–650℃, 370–600℃, 370–550℃, 390–650℃, 390–600℃, 390–550℃, 400–650℃, 400–600℃, 400–550℃. 410~650℃, 410~600℃, 410~550℃, 420~650℃, 420~600℃, 420~550℃, 430~650℃, 430~600℃, 430~550℃, 440~650℃, 440~600℃, 440~550℃, 450~650℃, 450~600℃ or 450~550℃.

[0157] The feedstock oil used in the high-temperature hydrogenation process may also contain nitrogen, sulfur, chlorine and other halogen elements.

[0158] The nitrogen content of the feedstock oil in the high-temperature hydrogenation process can be, for example, 100 ppm by mass or more, or 2000 ppm by mass or more, 2500 ppm by mass or more, or 3000 ppm by mass or more. In this embodiment, chemical products are manufactured via the high-temperature hydrogenation process and the cracking process, so even if the feedstock oil contains a large amount of nitrogen, it is easy to obtain high-purity chemical products (chemical products with low nitrogen content). The nitrogen content of the feedstock oil can be, for example, less than 20000 ppm by mass, or less than 15000 ppm by mass, or less than 10000 ppm by mass.

[0159] That is, the nitrogen content of the feedstock oil in the high-temperature hydrogenation process can be, for example, 100–20000 ppm by mass, 100–15000 ppm by mass, 100–10000 ppm by mass, 2000–20000 ppm by mass, 2000–15000 ppm by mass, 2000–10000 ppm by mass, 2500–20000 ppm by mass, 2500–15000 ppm by mass, 2500–10000 ppm by mass, 3000–20000 ppm by mass, 3000–15000 ppm by mass, or 3000–10000 ppm by mass.

[0160] The sulfur content of the feedstock oil in the high-temperature hydrogenation process can be, for example, 10 ppm or more by mass, or 100 ppm or more by mass, or 500 ppm or more by mass, or 1000 ppm or more by mass. In this embodiment, chemical products are manufactured via the high-temperature hydrogenation process and the cracking process, so even if the feedstock oil contains a large amount of sulfur, it is easy to obtain high-purity chemical products (chemical products with low sulfur content). The sulfur content of the feedstock oil can be, for example, less than 30,000 ppm by mass, or less than 20,000 ppm by mass, or less than 10,000 ppm by mass.

[0161] That is, the sulfur content of the feedstock oil in the high-temperature hydrogenation process can be, for example, 10–30,000 ppm by mass, 10–20,000 ppm by mass, 10–10,000 ppm by mass, 100–30,000 ppm by mass, 100–20,000 ppm by mass, 100–10,000 ppm by mass, 500–30,000 ppm by mass, 500–20,000 ppm by mass, 500–10,000 ppm by mass, 1,000–30,000 ppm by mass, 1,000–20,000 ppm by mass, or 1,000–10,000 ppm by mass.

[0162] The chlorine content of the feedstock oil in the high-temperature hydrogenation process can be, for example, 10 ppm by mass or more, or 30 ppm by mass or more, 50 ppm by mass or more, or 100 ppm by mass or more. In this embodiment, chemical products can be manufactured through the high-temperature hydrogenation process and the cracking process, so even if there is a large amount of chlorine in the feedstock oil, it is easy to obtain high-purity chemical products (chemical products with low chlorine content). The chlorine content of the feedstock oil can be, for example, less than 2000 ppm by mass, or less than 1500 ppm by mass, or less than 1000 ppm by mass. In addition, not only chlorine content, but also other halogen element content can be within the same range.

[0163] That is, the chlorine content of the feedstock oil in the high-temperature hydrogenation process can be, for example, 10-2000 ppm by mass, 10-1500 ppm by mass, 10-1000 ppm by mass, 30-2000 ppm by mass, 30-1500 ppm by mass, 30-1000 ppm by mass, 50-2000 ppm by mass, 50-1500 ppm by mass, 50-1000 ppm by mass, 100-2000 ppm by mass, 100-1500 ppm by mass, or 100-1000 ppm by mass.

[0164] High-temperature hydrogenation can be a process of hydrogenating feedstock oil in the presence of a hydrogenation catalyst. Hydrogenation can be carried out, for example, by feeding the feedstock oil into a reactor equipped with a hydrogenation catalyst, allowing it to come into contact with the catalyst within the reactor.

[0165] As a hydrogenation catalyst, for example, a known hydrogenation catalyst used in the hydrogenation of hydrocarbon oils can be used.

[0166] In this embodiment, when the feedstock oil in the high-temperature hydrogenation process contains high-boiling-point oil, a catalyst with excellent hydrogenation capacity and the ability to effectively hydrogenate the high-boiling-point oil is preferred as the hydrogenation catalyst. From the viewpoint of hydrogenation capacity, the hydrogenation catalyst preferably comprises, for example, a Ni-based catalyst. A Ni-based catalyst refers to a catalyst having Ni as an active metal.

[0167] The high-temperature hydrogenation process can be implemented using one hydrogenation catalyst or multiple hydrogenation catalysts. For example, in the high-temperature hydrogenation process, desulfurization and denitrification catalysts, high-decomposition-capacity catalysts, and low-decomposition-capacity catalysts (described later) can be appropriately combined as hydrogenation catalysts.

[0168] For desulfurization and denitrification, any hydrogenation catalyst with excellent desulfurization and denitrification performance is suitable. Examples of desulfurization and denitrification catalysts include hydrogenolysis catalysts formed by supporting active metals on an alumina-containing support. These hydrogenation catalysts often exhibit excellent desulfurization and denitrification performance.

[0169] The support for the catalyst used for desulfurization and denitrification can be an alumina-containing support, preferably with an alumina content of 50% by mass or more. The alumina content in the support of the catalyst used for desulfurization and denitrification is based on the total amount of the support, and for example, can be 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more.

[0170] The support for the desulfurization and denitrification catalyst may also contain components other than alumina. For example, the support for the desulfurization and denitrification catalyst may contain oxides of elements from Groups 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support for the desulfurization and denitrification catalyst may contain at least one oxide selected from the following: silica, phosphorus, magnesium oxide, zirconium oxide, boron oxide, titanium oxide, calcium oxide, and zinc. Furthermore, from the viewpoints of desulfurization and denitrification performance, industrial manufacturing, and catalyst strength, the support for the desulfurization and denitrification catalyst preferably includes silica, silica-alumina, silica-alumina-phosphorus, silica-magnesium oxide, alumina-silica-magnesium oxide, and alumina-silica-zirconia. It should be noted that the support for the desulfurization and denitrification catalyst can be crystalline or amorphous. The shape of the support for the desulfurization and denitrification catalyst is not particularly limited; for example, it can be spherical, cylindrical, trilobal, or tetralobal.

[0171] Examples of active metals used in desulfurization and denitrification catalysts include Ni, Mo, Co, W, and P. A desulfurization and denitrification catalyst may contain one or more active metals. From the viewpoint of easily achieving excellent hydrogenation capacity and more effectively desulfurizing and denitrifying, a desulfurization and denitrification catalyst preferably contains at least Ni, and more preferably contains Ni and Mo or W. The active metal is activated by sulfidation treatment. Among the aforementioned metals, especially through sulfides containing Ni, desulfurization and denitrification catalysts more easily achieve excellent hydrogenation capacity.

[0172] Examples of high-decomposition-capacity catalysts include hydrogenation catalysts formed by supporting active metals on a zeolite-containing support. These hydrogenation catalysts often possess small pores and exhibit excellent hydrogenation decomposition capabilities.

[0173] The support for the high-decomposition-capacity catalyst can be a zeolite-containing support, preferably with a zeolite content of 1% by mass or more. The zeolite content in the support of the high-decomposition-capacity catalyst is based on the total amount of the support, and for example, can be 2% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more.

[0174] The support for a high-decomposition-capacity catalyst may also contain components other than zeolites. For example, the support may contain oxides of elements from Groups 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support may contain at least one oxide selected from the following: silica, alumina, phosphorus, magnesium oxide, zirconium oxide, boron oxide, titanium oxide, calcium oxide, and zinc. From the viewpoints of decomposition capacity, desulfurization and denitrification performance, industrial manufacturing, and catalyst strength, the support for a high-decomposition-capacity catalyst preferably includes alumina, silica, silica-alumina, silica-alumina-phosphorus, silica-magnesium oxide, alumina-silica-magnesium oxide, and alumina-silica-zirconia. It should be noted that the support for a high-decomposition-capacity catalyst can be crystalline or amorphous. The shape of the support for a high-decomposition-capacity catalyst is not particularly limited; for example, it can be spherical, cylindrical, trilobal, or tetralobal.

[0175] Examples of active metals that can be used as high-decomposition-capacity catalysts include Ni, Mo, Co, W, and P. A high-decomposition-capacity catalyst may contain one or more active metals. From the viewpoint of easily achieving excellent hydrogenation capacity and more effectively hydrogenating high-boiling-point oils, a high-decomposition-capacity catalyst preferably contains at least Ni, and more preferably contains Ni and Mo or W. The active metal is activated by a sulfidation treatment. Since sulfides containing Ni are particularly suitable among the aforementioned metals, desulfurization and denitrification catalysts more readily achieve excellent hydrogenation capacity.

[0176] Examples of low-decomposition-capacity catalysts include hydrogenation catalysts formed by supporting active metals on an alumina-containing support. These hydrogenation catalysts often possess a large number of pores larger than those of high-decomposition-capacity catalysts, exhibiting a milder hydrogenation-decomposition capacity compared to high-decomposition-capacity catalysts.

[0177] The support for the low-decomposition-capacity catalyst can be a support containing alumina. The alumina content in the support of the low-decomposition-capacity catalyst is based on the total amount of the support, for example, it can be 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more.

[0178] The support for a low-decomposition-capacity catalyst may also contain components other than alumina. For example, the support may contain oxides of elements from Groups 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support may include at least one oxide selected from the following: silica, phosphorus, magnesium oxide, zirconium oxide, boron oxide, titanium oxide, calcium oxide, and zinc. From the viewpoints of decomposition performance, desulfurization and denitrification performance, industrial manufacturing, and catalyst strength, the support for a low-decomposition-capacity catalyst preferably includes silica, silica-alumina, silica-alumina-phosphorus, silica-magnesium oxide, alumina-silica-magnesium oxide, and alumina-silica-zirconia. It should be noted that the support for a low-decomposition-capacity catalyst can be crystalline or amorphous. The shape of the support for a low-decomposition-capacity catalyst is not particularly limited; for example, it can be spherical, cylindrical, trilobal, or tetralobal.

[0179] Examples of active metals that can be used as low-decomposition-capacity catalysts include Ni, Mo, Co, W, and P. Low-decomposition-capacity catalysts may contain one or more active metals. From the viewpoint of efficiently hydrogenating high-boiling-point oils, low-decomposition-capacity catalysts preferably contain at least Ni, and more preferably contain Ni and Mo or W. The active metal is activated by sulfidation treatment. Among the aforementioned metals, especially through sulfides containing Ni, desulfurization and denitrification catalysts more readily achieve excellent hydrogenation capacity.

[0180] In the high-temperature hydrogenation process, desulfurization and denitrification catalysts can be used in combination with decomposition catalysts. The decomposition catalyst can be used in combination with a high-decomposition-capacity catalyst and a low-decomposition-capacity catalyst, or only a high-decomposition-capacity catalyst or only a low-decomposition-capacity catalyst. The desulfurization and denitrification catalyst can be placed at least upstream of the high-decomposition-capacity and low-decomposition-capacity catalysts, or it can be placed both upstream and downstream of the high-decomposition-capacity and low-decomposition-capacity catalysts.

[0181] In the case of feedstock containing nitrogen in the high-temperature hydrotreating process, the nitrogen in the feedstock may adhere to the active sites of both high- and low-decomposition-capacity catalysts, thereby reducing their decomposition performance. If the feedstock comes into contact with a desulfurization and denitrification catalyst, the nitrogen in the feedstock is converted into ammonia, etc., reducing the nitrogen content of the feedstock. Therefore, in the high-temperature hydrotreating process, it is preferable to place the desulfurization and denitrification catalyst upstream of the high- and low-decomposition-capacity catalysts. That is, it is preferable to place the desulfurization and denitrification catalyst upstream of the high- and low-decomposition-capacity catalysts, as described later. According to this configuration, even when the feedstock contains nitrogen, the decline in the decomposition performance of the high- and low-decomposition-capacity catalysts can be suppressed.

[0182] The high-temperature hydrogenation process can be implemented, for example, using a continuous flow reactor. In this case, it is preferable to sequentially arrange a first catalyst layer containing a desulfurization and denitrification catalyst, and a second catalyst layer containing a decomposition catalyst, from the inlet side, within the continuous flow reactor. Furthermore, a third catalyst layer containing decomposition catalysts of different decomposition capabilities, and a fourth catalyst layer containing a desulfurization and denitrification catalyst, can be further arranged downstream of the second catalyst layer.

[0183] The reaction temperature in the high-temperature hydrogenation process is not particularly limited, but can be, for example, above 300°C, preferably above 320°C, and more preferably above 340°C. Alternatively, the reaction temperature in the high-temperature hydrogenation process can be, for example, below 480°C, preferably below 460°C, and more preferably below 440°C. That is, the reaction temperature in the high-temperature hydrogenation process can be, for example, 300–480°C, 300–460°C, 300–440°C, 320–480°C, 320–460°C, 320–440°C, 340–480°C, 340–460°C, or 340–440°C.

[0184] The reaction pressure in the high-temperature hydrogenation process is not particularly limited; for example, it can be 1 MPaG or more, preferably 3 MPaG or more, and more preferably 5 MPaG or more. Furthermore, the reaction pressure in the high-temperature hydrogenation process is not particularly limited; for example, it can be 20 MPaG or less, preferably 19 MPaG or less, and more preferably 18 MPaG or less.

[0185] That is, the reaction pressure in the high-temperature hydrogenation process can be, for example, 1-20 MPaG, 1-19 MPaG, 1-18 MPaG, 3-20 MPaG, 3-19 MPaG, 3-18 MPaG, 5-20 MPaG, 5-19 MPaG, or 5-18 MPaG.

[0186] When using a continuous flow reactor to implement a high-temperature hydrogenation process, the heavy hourly space velocity (WHSV) of the feedstock can be, for example, 0.1 h⁻¹.-1 The preferred value is 0.15h. -1 The above is preferred, and 0.2h is even more preferred. -1 That's all. Additionally, the heavy hourly space velocity (WHSV) of the feedstock can, for example, be 5 h⁻¹. -1 The following is preferred: 4h -1 The following is more preferably 3h -1 the following.

[0187] That is, the heavy hourly space velocity (WHSV) of the feedstock oil can be 0.1 to 5 h⁻¹. -1 0.1~4h -1 0.1 to 3 hours -1 0.15~5h -1 0.15~4h -1 0.15~3h -1 0.2-5h -1 0.2-4h -1 or 0.2 to 3 hours -1 .

[0188] The high-temperature hydrogenation process is carried out in the presence of hydrogen. When using a continuous flow reactor to carry out the high-temperature hydrogenation process, the hydrogen / oil ratio can be, for example, 100 NL / L or more, preferably 150 NL / L or more, and more preferably 200 NL / L or more. Alternatively, the hydrogen / oil ratio can be, for example, 1500 NL / L or less, preferably 1400 NL / L or less, and more preferably 1300 NL / L or less.

[0189] That is, the hydrogen / oil ratio can be, for example, 100-1500 NL / L, 100-1400 NL / L, 100-1300 NL / L, 150-1500 NL / L, 150-1400 NL / L, 150-1300 NL / L, 200-1500 NL / L, 200-1400 NL / L, or 200-1300 NL / L.

[0190] In the high-temperature hydrogenation process, a second gas component and high-temperature hydrogenated oil can be obtained by hydrogenating the feedstock oil.

[0191] The second gaseous component can be, for example, a gaseous component in the products generated by hydrogenation at room temperature (20°C). The second gaseous component can contain, for example, hydrogen or hydrocarbons with 1 to 4 carbon atoms.

[0192] The second gas component can be used, for example, as the combustion gas for heating the pyrolysis section in a pyrolysis process, or as the combustion gas for heating furnaces in other processes.

[0193] The sulfur content in the high-temperature hydrogenated oil is, for example, less than 1500 ppm by mass. From the viewpoint of reducing the impurity content in the chemical products obtained in the cracking process, preventing catalyst poisoning in the later stages of the cracking process, and preventing equipment corrosion, it is preferably less than 1000 ppm by mass, and more preferably less than 900 ppm by mass.

[0194] The nitrogen content in the high-temperature hydrogenated oil is, for example, less than 100 ppm by mass, and from the viewpoint of reducing the impurity content in the chemical products obtained from the cracking process, it is preferably less than 25 ppm by mass, and more preferably less than 20 ppm by mass.

[0195] The chlorine content in the high-temperature hydrotreated oil is, for example, below 20 ppm by mass. From the viewpoint of reducing the impurity content in the chemical products obtained from the cracking process, preventing catalyst poisoning in the later stages of the cracking process, and preventing equipment corrosion, it is preferably below 15 ppm by mass, and more preferably below 10 ppm by mass. In addition, not only the chlorine content, but also the content of other halogen elements is preferably within the same range.

[0196] (Separation process)

[0197] The separation process involves atmospheric distillation of at least a portion of the high-temperature hydrogenated oil and the crude oil feedstock to separate the naphtha fraction into other fractions. The naphtha fraction may contain both light and heavy naphtha, but is particularly preferably composed of light naphtha. Other fractions include conventionally known fractions other than naphtha, such as low-boiling-point gas fractions, high-boiling-point kerosene fractions, light oil fractions, and residual oil fractions.

[0198] In the separation process, the amount of high-temperature hydrogenated oil in the feedstock oil for atmospheric distillation is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and preferably 9% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less.

[0199] That is, the amount of high-temperature hydrogenated oil in the feedstock oil for atmospheric distillation is preferably 0.001% to 9% by mass relative to the total amount of high-temperature hydrogenated oil and crude oil, more preferably 0.005% to 7% by mass, even more preferably 0.01% to 57% by mass, even more preferably 0.05% to 3% by mass, and most preferably 0.05% to 1% by mass.

[0200] If the amount of high-temperature hydrogenated oil is within the above-mentioned range, when it is mixed with crude oil with low nitrogen content and diene content to obtain feedstock for atmospheric distillation, the nitrogen content and diene content of the high-temperature hydrogenated oil will be diluted in the feedstock for atmospheric distillation. This will not only inhibit the generation of fouling in the heat exchanger of the atmospheric distillation unit, but also inhibit the impact of impurities such as nitrogen content on downstream units.

[0201] There are no special restrictions on the crude oil used in the separation process; any crude oil that is known in the past can be used.

[0202] The feedstock oil used in atmospheric distillation during the separation process may also contain nitrogen, sulfur, chlorine, and other halogen elements. Since the feedstock oil for atmospheric distillation is typically composed mostly of crude oil, it is preferable that the amount of nitrogen and dienes in the crude oil is lower than that in the high-temperature hydrogenated oil. For example, the crude oil preferably has the following properties.

[0203] The nitrogen content of the crude oil is preferably below 2000 ppm by mass, more preferably below 1500 ppm by mass, and even more preferably below 1000 ppm by mass.

[0204] There are no particular restrictions on the type of atmospheric distillation unit or operating conditions used in the separation process. The same units and operating conditions as before can be used, and equipment that has been installed in petroleum refineries can be directly utilized.

[0205] The nitrogen content of the naphtha fraction obtained in the separation process is preferably less than 500 ppm by mass, more preferably less than 400 ppm by mass, and even more preferably less than 300 ppm by mass. By reducing the nitrogen content of the naphtha fraction, high-purity chemical products (chemical products with low nitrogen content) can be easily obtained.

[0206] (Steam pyrolysis process)

[0207] The steam cracking process is a process of obtaining chemical products by steam cracking a steam cracking feedstock containing naphtha fractions and / or a portion of other fractions obtained from an atmospheric distillation process. In the steam cracking process, the naphtha fractions (such as light naphtha) are decomposed by heat treatment together with steam, generating components useful as chemical products.

[0208] In the steam cracking process, at least a portion, or all, of the naphtha fraction and / or other fractions obtained from the atmospheric distillation process can be supplied to the steam cracking process. Furthermore, in addition to the naphtha fraction, the steam cracking feedstock in the process may further contain ethane, naphtha, kerosene, light oil fractions, etc., derived from petroleum. In the steam cracking process, the naphtha fraction can be used directly as the steam cracking feedstock, or it can be used after additional treatments such as desulfurization.

[0209] There are no particular limitations on the conditions for steam cracking treatment; appropriate conditions can be selected from those known to be used in the steam cracking treatment of ethane, naphtha, kerosene, and light oil.

[0210] The reaction temperature for steam pyrolysis can be, for example, 650°C or higher, preferably 700°C or higher, and more preferably 750°C or higher. Alternatively, the reaction temperature for steam pyrolysis can be, for example, 1000°C or lower, preferably 950°C or lower, and more preferably 900°C or lower.

[0211] The reaction temperature for steam pyrolysis can be, for example, 650–1000℃, 650–950℃, 650–900℃, 700–1000℃, 700–950℃, 700–900℃, 750–1000℃, 750–950℃, or 750–900℃.

[0212] The reaction time (residence time) of the steam pyrolysis treatment can be, for example, 0.05 seconds or more, preferably 0.06 seconds or more, and more preferably 0.08 seconds or more. Furthermore, the reaction time of the steam pyrolysis treatment can be, for example, 2.0 seconds or less, preferably 1.9 seconds or less, and more preferably 1.8 seconds or less.

[0213] That is, the reaction time of the steam cracking treatment can be, for example, 0.05–2.0 seconds, 0.05–1.9 seconds, 0.05–1.8 seconds, 0.06–2.0 seconds, 0.06–1.9 seconds, 0.06–1.8 seconds, 0.08–2.0 seconds, 0.08–1.9 seconds, or 0.08–1.8 seconds.

[0214] The ratio (mass ratio) of steam to steam cracking feedstock in the steam cracking process can be, for example, 0.2 or more, preferably 0.25 or more, and more preferably 0.3 or more. Furthermore, the ratio (mass ratio) of steam to steam cracking feedstock can be, for example, 1.0 or less, preferably 0.9 or less, and more preferably 0.8 or less.

[0215] That is, the ratio (mass ratio) of steam to steam cracking feedstock can be, for example, 0.2–1.0, 0.2–0.9, 0.2–0.8, 0.25–1.0, 0.25–0.9, 0.25–0.8, 0.3–1.0, 0.3–0.9, or 0.3–0.8.

[0216] The outlet reaction pressure of the steam cracking treatment can be, for example, 0.1 MPaA or more, preferably 0.15 MPaA or more, and more preferably 0.2 MPaA or more. Furthermore, the reaction pressure of the steam cracking treatment can be, for example, 1.0 MPaA or less, preferably 0.8 MPaA or less, and more preferably 0.6 MPaA or less.

[0217] That is, the outlet reaction pressure of the steam cracking treatment can be, for example, 0.1–1.0 MPaA, 0.1–0.8 MPaA, 0.1–0.6 MPaA, 0.15–1.0 MPaA, 0.15–0.8 MPaA, 0.15–0.6 MPaA, 0.2–1.0 MPaA, 0.2–0.8 MPaA, or 0.2–0.6 MPaA.

[0218] Examples of chemical products obtained from the steam cracking process include ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, indene, methylstyrene, and other olefin-containing C9 aromatic hydrocarbons used in resin conversion.

[0219] In the steam cracking process, in addition to chemical products, light fractions can be further obtained. Examples of light fractions include methane, ethane, butane, pentane, propane, and hexane.

[0220] In the steam cracking process, in addition to chemical products, heavy fractions can be further obtained. These heavy fractions can be reused as feedstock for steam cracking or used as raw materials for carbide manufacturing. The heavy fractions obtained in the steam cracking process of this embodiment tend to have a higher content of aromatic components, making them suitable as feedstocks for manufacturing carbides (especially carbon black). For example, carbides (especially carbon black) can be obtained through thermal cracking or incomplete combustion of the heavy fraction.

[0221] The aforementioned heavy distillate may, for example, be a fraction with a 10% distillation temperature of 190°C or higher, or a fraction with a distillation temperature of 200°C or higher. The 10% distillation temperature of the aforementioned heavy distillate may, for example, be below 250°C or below 240°C. The 90% distillation temperature of the aforementioned heavy distillate may, for example, be above 450°C or above 500°C. The 90% distillation temperature of the aforementioned heavy distillate may, for example, be below 750°C or below 700°C.

[0222] That is, the 10% distillation temperature of the aforementioned heavy fraction can be, for example, 190–250°C, 190–240°C, 200–250°C, or 200–240°C. Furthermore, the 90% distillation temperature of the aforementioned heavy fraction can be, for example, 450–750°C, 450–700°C, 500–750°C, or 500–700°C.

[0223] The aromatic content of the aforementioned heavy distillate may be, for example, 30% by mass or more, preferably 35% by mass or more, and more preferably 40% by mass or more. Furthermore, the aromatic content of the aforementioned heavy distillate may be, for example, 90% by mass or less.

[0224] That is, the aromatic fraction of the above-mentioned heavy distillate can be, for example, 30-90% by mass, 35-90% by mass, or 40-90% by mass.

[0225] Figure 2 This is a simplified diagram illustrating an example of a system implementing the manufacturing method of this embodiment. Figure 2 The system 100 shown includes a pyrolysis unit 110, a first separation unit 111, a pulverizing unit 112, a low-temperature hydrogenation unit 115, a high-temperature hydrogenation unit 120, an atmospheric distillation unit 125, and a steam pyrolyzer 130.

[0226] In system 100, waste S1 is first fed to pyrolysis unit 110, where it is pyrolyzed. In pyrolysis unit 110, a mixture S4 of a first gaseous component S2, pyrolysis oil S3, residue component, and metallic component is produced. The first gaseous component S2 can be discharged outside the system or reused as oxygen-free gas in pyrolysis unit 110. Pyrolysis oil S3 is fed to cryogenic hydrogenation unit 115. Mixture S4 is fed to first separation unit 111, where it is separated into residue component S5 and metallic component S6. Residue component S5 is pulverized in pulverization unit 112 and recovered as powdered carbide S7.

[0227] In the low-temperature hydrogenation unit 115, low-temperature hydrogenated oil S8 is produced by low-temperature hydrogenation treatment of pyrolysis oil S3. Low-temperature hydrogenated oil S8 is then supplied to the high-temperature hydrogenation unit 120.

[0228] In the high-temperature hydrogenation unit 120, a second gaseous component S9 and a high-temperature hydrogenated oil S10 are produced through high-temperature hydrogenation of the low-temperature hydrogenated oil S8. The second gaseous component S9 can be discharged outside the system or used as combustion gas in the pyrolysis process to heat the pyrolysis section or as combustion gas in the furnaces of other processes. The high-temperature hydrogenated oil S10 is supplied to the atmospheric distillation unit 125. Alternatively, the high-temperature hydrogenated oil S10 can also be reused as recoverable oil S15 in the low-temperature hydrogenation unit 115.

[0229] In atmospheric distillation unit 125, atmospheric distillation of high-temperature hydrogenated oil S10 produces a steam cracking feedstock S11 containing at least a portion of naphtha fraction and other fractions (kerosene fraction, light oil fraction). Steam cracking feedstock S11 can be obtained as a single fraction or as a mixture. Steam cracking feedstock S11 is supplied to steam cracker 130.

[0230] In the steam cracker 130, the steam cracking feedstock oil S11 is subjected to steam cracking treatment to form product gas S12, product oil S13, and heavy fraction S14. Product gas S12 and product oil S13 contain olefin-containing C9 aromatic hydrocarbon components useful as chemical products, such as ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, indene, and methylstyrene, which are used in resin conversion. Chemical products are obtained by appropriately separating and recovering product gas S12 and product oil S13. Heavy fraction S14, for example, can be used as a feedstock for carbide manufacturing or as fuel.

[0231] (Manufacturing method of synthetic rubber)

[0232] The butadiene manufacturing method of this embodiment includes a polymerization step of obtaining synthetic rubber through a polymerization reaction, wherein the polymerization reaction uses the butadiene obtained by the above manufacturing method as at least a portion of the raw material for the synthetic rubber.

[0233] In the polymerization process, synthetic rubber can be obtained by polymerizing a polymerization composition containing at least butadiene as a monomer using conventionally known methods. 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 appropriately adjusted according to the polymerization method and the composition of the polymerization composition.

[0234] The monomer can be butadiene alone, or, depending on the composition and properties of the target synthetic rubber, other monomers known for use in synthetic rubber can be used besides butadiene. Examples of other monomers for synthetic rubber include conjugated diene compounds other than butadiene and aromatic vinyl compounds.

[0235] Examples of conjugated dienes 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, and 2-chloro-1,3-butadiene. One or more conjugated dienes other than butadiene may be used.

[0236] Examples of aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, vinyl ethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, tert-butoxystyrene, vinylbenzyl dimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, diphenylethylene, and diphenylethylene containing a tert-amino group (e.g., 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene, etc.). Aromatic vinyl compounds can be used alone or in combination with more than one other compound.

[0237] In addition to monomers, polymerization compositions may also contain conventionally known additives, solvents, etc. Examples of additives include polymerization initiators, emulsifiers, and surfactants.

[0238] Alkali metal compounds can be used as polymerization initiators, for example. Specific examples of alkali metal compounds include alkyl lithiums such as methyl lithium, ethyl lithium, n-propyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium; 1,4-dilithium butane, phenyl lithium, stilbene lithium, naphthyl lithium, 1,3-bis(1-lithium-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentanediol)dilithium, sodium naphthyl, potassium naphthyl, and potassium ethoxy.

[0239] (tire)

[0240] The tire of this embodiment comprises synthetic rubber obtained by the synthetic rubber manufacturing method described above.

[0241] (Tire manufacturing method)

[0242] The tire manufacturing method of this embodiment includes a vulcanization step of obtaining a tire through a vulcanization reaction, wherein the vulcanization reaction uses synthetic rubber obtained by the above-described synthetic rubber manufacturing method as at least a portion of the raw material for the tire.

[0243] In the vulcanization process, a vulcanizing composition containing at least synthetic rubber can be vulcanized using conventionally known methods to obtain a tire. The vulcanization conditions are not particularly limited and can be appropriately adjusted according to the composition of the vulcanizing composition, the shape and structure of the target tire, etc.

[0244] In addition to synthetic rubber, the vulcanizing composition may also contain conventionally known additives. Examples of additives include vulcanizing agents, vulcanization accelerators, vulcanization accelerator aids, anti-aging agents, softeners, antioxidants, and colorants. One or more of these additives may be used.

[0245] Examples of sulfur-based sulfur-containing agents include powdered sulfur, precipitated sulfur, highly dispersed sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, zinc oxide, magnesium oxide, lead oxide, p-quinone dioxime, p-benzoylquinone dioxime, tetrachlorop-benzoquinone, poly(p-dinitrobenzene), methylene diphenylamine, phenolic resin, brominated alkylphenolic resin, and chlorinated alkylphenolic resin.

[0246] Examples of vulcanization accelerators include thiuram-based accelerators such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM); aldehyde-amine accelerators such as hexamethylenetetramine; guanidine accelerators such as diphenylguanidine; thiazole accelerators such as 2-mercaptobenzothiazole (MBT) and dibenzothiazole disulfide (DM); sulfonamide accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and N-tert-butyl-2-benzothiazole sulfenamide (BBS); and dithiocarbamate accelerators such as zinc dimethyl dithiocarbamate (ZnPDC).

[0247] Examples of accelerators for vulcanization include fatty acids, zinc fatty acids, zinc salts of fatty acids, and zinc oxide. Examples of fatty acids include acetic acid, propionic acid, butyric acid, stearic acid, acrylic acid, and maleic acid. Examples of zinc fatty acids include zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc acrylate, and zinc maleate.

[0248] Examples of anti-aging agents include, for example, hindered amine and hindered phenolic compounds of aliphatic and aromatic types.

[0249] Examples of antioxidants include butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA).

[0250] Examples of colorants include titanium dioxide, zinc oxide, ultramarine, iron oxide red, zinc barium white, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, inorganic pigments, azo pigments, and copper phthalocyanine pigments.

[0251] There are no particular restrictions on the shape, structure, size, and material of tires; they can be selected appropriately according to the purpose. Furthermore, there are no particular restrictions on the intended use of tires; examples include passenger car tires, heavy-duty tires, motorcycle tires, and studless tires.

[0252] (Management methods for renewable products)

[0253] In recent years, in order to sell environmentally friendly products that use plant-based raw materials, recycled materials, etc. in a more attractive manner, methods such as the quality balance method (hereinafter also known as the material balance method) have gained attention in various industries such as the chemical industry, the steel industry, and the aluminum industry.

[0254] For the products generated by the manufacturing method of the present invention using waste materials including waste tires, it is also desirable to be able to allocate the value of the renewable products using a mass balance method in a simple and reliable manner.

[0255] Therefore, the present invention provides a management method that, when manufacturing chemical products using the manufacturing method of the present invention described above, can allocate the value of each product as a renewable product in a simple and reliable manner based on the proportion of renewable raw materials contained in waste materials including waste tires.

[0256] In this specification, "renewable raw materials" refers to raw materials from organic resources that can be recycled. Renewable raw materials are not limited to products derived from biological resources; they can be interpreted broadly as long as they are from organic resources that can be recycled. For example, even petroleum-derived products include products derived from recycled materials such as waste tires.

[0257] Here, the quality balancing method refers to, for example, in the circulation and processing of raw materials to products, when raw materials with specific characteristics, such as biomass raw materials, are mixed with raw materials that do not have the aforementioned characteristics, the characteristic is allocated to a portion of the product in the form of a credit based on the proportion of the raw material with that characteristic.

[0258] The mass balance method (material balance method) is a way for manufacturers to arbitrarily allocate biomass fractions in the form of quotas, and therefore usually requires certification from a third-party certification body to prove its legitimacy. Such third-party certification bodies include ISCC (International Sustainability and Carbon Certification) and RSB (Roundtable on Sustainable Biofuels).

[0259] (Management methods for chemical products implemented using management devices)

[0260] The chemical product management method of the present invention can be used when manufacturing chemical products using waste materials including waste tires.

[0261] The management method of the present invention utilizes a management device to allocate chemical products according to the proportion of renewable raw materials contained in the waste, and obtains the value of renewable products through a quality balance method.

[0262] The management method of the present invention includes, for example, a step (V), in which a chemical product is obtained by a management device described later (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 allocated as a value as a renewable product (the management device acquires information indicating the proportion of the product allocated as a value as a renewable product).

[0263] The process (V) that confirms the chemical product includes the following processes (V-1), (V-2), (V-3), (V-4), (V-5), and (V-6).

[0264] Step (V-1) is the process by which the management device confirms that the aforementioned waste is used to generate the aforementioned pyrolysis oil in the pyrolysis unit that produces pyrolysis oil through the pyrolysis of the aforementioned waste.

[0265] Step (V-2) is the process by which the management device confirms that the pyrolysis oil is generated from the pyrolysis oil in the low-temperature hydrogenation unit, which is used to perform low-temperature hydrogenation treatment on feedstock containing at least a portion of the pyrolysis oil at 180°C to 350°C.

[0266] Step (V-3) is the process by which the management device confirms that the high-temperature hydrogenated oil is generated from the low-temperature hydrogenated oil in the high-temperature hydrogenation unit, which is used to hydrogenate feedstock containing at least a portion of the low-temperature hydrogenated oil at a temperature higher than that of the low-temperature hydrogenation treatment to obtain a second gas component and high-temperature hydrogenated oil.

[0267] Step (V-4) is the process by which the management device confirms the generation of the aforementioned naphtha fraction and other fractions from the aforementioned high-temperature hydrogenated oil in an atmospheric distillation unit, which separates the aforementioned naphtha fraction and other fractions by atmospheric distillation of a feedstock oil containing at least a portion of the aforementioned high-temperature hydrogenated oil and crude oil.

[0268] Step (V-5) is the process by which the management device confirms that the chemical product is obtained from the steam cracking feedstock oil fed into a steam cracker that performs steam cracking treatment on the steam cracking feedstock oil containing at least a portion of the above-mentioned naphtha fraction and / or the above-mentioned other fractions.

[0269] Step (V-6) is the process by which the management device confirms that the chemical product is obtained from the waste by processing it in the order of the above-mentioned pyrolysis unit, the above-mentioned low-temperature hydrogenation unit, the above-mentioned high-temperature hydrogenation unit, the above-mentioned atmospheric distillation unit, and the above-mentioned steam cracker.

[0270] The process (Z) of confirming the proportion of products allocated as value as renewable products includes the following processes (Z-1), (Z-2), (Z-3), and (Z-4).

[0271] Process (Z-1) is the process by which the management device selects products from the products obtained through the steam pyrolysis unit above as renewable products for distribution.

[0272] Step (Z-2) is the step in which the management device determines the value of the proportion (P) of the product selected in step (Z-1) in the product obtained by the steam pyrolyzer, and distributes it as a renewable product.

[0273] Process (Z-3) is the process by which the management device determines the value of the proportion (Q) of renewable raw materials contained in the aforementioned waste.

[0274] Step (Z-4) is the process by which the management device compares the value of the aforementioned ratio (P) with the value containing the aforementioned ratio (Q) and confirms that the value of the aforementioned ratio (P) is below the value containing the aforementioned ratio (Q).

[0275] An example of an implementation method for a management method of chemical products performed using a management device (in particular, a method for allocating value as a renewable product) is described.

[0276] Process (Z-1): When the products obtained by the steam cracker are ethylene, propylene, butadiene and other products, butadiene is selected.

[0277] Process (Z-2): Assume that the products obtained by the steam cracker are ethylene, propylene, butadiene, and other products, and that the proportions of each product are 10% by mass for ethylene, 10% by mass for propylene, 10% by mass for butadiene, and 70% by mass for other products. Therefore, determine the proportion (P) allocated as a renewable product in the 10% by mass of butadiene product.

[0278] Process (Z-3): When the waste contains 5% renewable raw materials by mass and 95% non-renewable raw materials by mass, the proportion (Q) of renewable raw materials is controlled (obtained) to be 5% by mass.

[0279] Step (Z-4): Compare the value of the proportion (P) with the value of the content proportion (Q) to confirm that the value of the proportion (P) is below the value of the content proportion (Q). Here, if the content proportion (Q) of the renewable raw material is 5% by mass, then the proportion (P) allocated to butadiene as a renewable product is set to 5% by mass or less.

[0280] That is, if we assume that the proportion (Q) of renewable raw materials is 5% by mass, then 5% by mass of the butadiene product allocated as renewable product can be allocated as renewable butadiene.

[0281] In this way, the value of butadiene products obtained from steam cracking can be allocated as renewable products based on the proportion of renewable raw materials contained in the waste.

[0282] It should be noted that, according to a third-party certification body, in the mass balance method (material balance method), the butadiene product in 10% mass of butadiene product, excluding (P)% mass (10-(P)% mass of butadiene product), actually also contains renewable components. However, since 100% renewable butadiene is allocated to (P)% mass of butadiene, it is not treated as renewable butadiene.

[0283] It should be noted that the values ​​of 5% by mass of the above-mentioned renewable raw material content (Q) and 10% by mass of butadiene product are set for the purpose of understanding the present invention and are not limited to these values.

[0284] <Management Devices and Procedures>

[0285] As described above, the management method of the present invention can be executed using a management device. Furthermore, the processing of each step of the management method performed by the management device is executed by a computer having a control unit constituting the management device.

[0286] The following describes the management device that performs the management method of the present invention, and the management program (computer program) executed by the computer of the management device.

[0287] As a preferred embodiment of the management device of the present invention, the following management devices can be cited.

[0288] "A chemical product management device, used when manufacturing chemical products from waste materials including waste tires."

[0289] The aforementioned management device is a device that uses a mass balance method to distribute the aforementioned chemical products based on the proportion of renewable raw materials contained in the aforementioned waste, thereby obtaining the value of the renewable products.

[0290] The aforementioned management device has a confirmation unit (I) that confirms the receipt of the aforementioned chemical product.

[0291] The aforementioned confirmation unit (I) includes the following means (V-1), the following means (V-2), the following means (V-3), the following means (V-4), the following means (V-5), and the following means (V-6).

[0292] The above-mentioned means (V-1) is a means of confirming that the above-mentioned waste is used to generate the above-mentioned pyrolysis oil from the waste fed into the pyrolysis unit that produces pyrolysis oil through the pyrolysis of the above-mentioned waste.

[0293] The above-mentioned means (V-2) is a means of confirming that the above-mentioned low-temperature hydrogenated oil is generated from the above-mentioned pyrolysis oil in a low-temperature hydrogenation unit where at least a portion of the feedstock oil containing the above-mentioned pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0294] The above-mentioned means (V-3) is a means of confirming that the low-temperature hydrogenated oil is generated from the feedstock oil containing at least a portion of the low-temperature hydrogenated oil by hydrogenating it at a temperature higher than the low-temperature hydrogenation treatment to obtain a second gas component and high-temperature hydrogenated oil.

[0295] The above-mentioned means (V-4) is a means of confirming that the above-mentioned high-temperature hydrogenated oil is used to generate the above-mentioned naphtha fraction and the above-mentioned other fractions by atmospheric distillation of feedstock oil containing at least a portion of the above-mentioned high-temperature hydrogenated oil and crude oil.

[0296] The above-mentioned means (V-5) is a means of confirming that the above-mentioned chemical products are obtained from the steam cracking feedstock that is fed into a steam cracker that performs steam cracking treatment on at least a portion of the steam cracking feedstock containing the above-mentioned naphtha fraction and / or the above-mentioned other fractions.

[0297] The aforementioned method (V-6) confirms that by processing the waste in the following order—the pyrolysis unit, the cryogenic hydrogenation unit, the high-temperature hydrogenation unit, the atmospheric distillation unit, and the steam pyrolyzer—the aforementioned chemical product can be obtained.

[0298] The aforementioned management device has a confirmation unit (I) that confirms the proportion of products allocated as renewable products.

[0299] The aforementioned confirmation unit (I) includes the following means (Z-1), the following means (Z-2), the following means (Z-3), and the following means (Z-4).

[0300] The aforementioned method (Z-1) is a means of selecting products from those obtained through the aforementioned steam pyrolysis unit for distribution as renewable products.

[0301] The aforementioned method (Z-2) is a means of determining the value of the proportion (P) of the product selected in the aforementioned method (Z-1) among the proportions of the product obtained through the aforementioned steam pyrolysis unit, to be allocated as a renewable product.

[0302] The aforementioned method (Z-3) is a means of determining the proportion (Q) of renewable raw materials contained in the aforementioned waste.

[0303] The aforementioned method (Z-4) is a method of comparing the value of the aforementioned proportion (P) with the value of the aforementioned proportion (Q), and confirming that the value of the aforementioned proportion (P) is below the value of the aforementioned proportion (Q).

[0304] As a preferred embodiment of the management procedure of the present invention, the following management procedure can be cited.

[0305] "A management procedure for chemical products, which is a management procedure for chemical products implemented using a management device when manufacturing chemical products using waste materials including waste tires."

[0306] The aforementioned management procedure utilizes the aforementioned management device to allocate the aforementioned chemical products using a mass balance method, based on the proportion of renewable raw materials contained in the aforementioned waste, to obtain the value of the renewable products.

[0307] The above management procedures cause the computer to perform the following processes:

[0308] (V-1): It is confirmed that the above-mentioned waste is generated from the above-mentioned waste in the pyrolysis unit that produces pyrolysis oil through the pyrolysis of the above-mentioned waste;

[0309] (V-2): Confirm the process of generating the above-mentioned low-temperature hydrogenated oil from the above-mentioned pyrolysis oil by putting it into a low-temperature hydrogenation unit where the feedstock oil containing at least a portion of the above-mentioned pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0310] (V-3): is the process of generating the high-temperature hydrogenated oil from the low-temperature hydrogenated oil fed into a high-temperature hydrogenation unit where the feedstock containing at least a portion of the low-temperature hydrogenated oil is hydrogenated at a temperature higher than the low-temperature hydrogenation treatment to obtain a second gas component and high-temperature hydrogenated oil.

[0311] (V-4): is the process of generating the naphtha fraction and the other fractions from the high-temperature hydrogenated oil fed into an atmospheric distillation unit that separates the feedstock oil containing at least a portion of the high-temperature hydrogenated oil and crude oil into naphtha fraction and other fractions.

[0312] (V-5): Confirm the process of obtaining the above-mentioned chemical products from the steam cracking feedstock oil fed into a steam cracker that performs steam cracking treatment on at least a portion of the steam cracking feedstock oil containing the above-mentioned naphtha fraction and / or other fractions.

[0313] (V-6): This refers to the process of obtaining the aforementioned chemical product from the aforementioned waste by processing it in the following order: the aforementioned pyrolysis unit, the aforementioned low-temperature hydrogenation unit, the aforementioned high-temperature hydrogenation unit, the aforementioned atmospheric distillation unit, and the aforementioned steam pyrolysis unit.

[0314] In the above management procedures,

[0315] The aforementioned management method includes a process (Z) for determining the proportion of products allocated as renewable resources.

[0316] (Z-1): Products selected from the products obtained through the steam pyrolysis unit described above and allocated as renewable products.

[0317] (Z-2): The value of P, which is the proportion of the product selected in the above process (Z-1) that is allocated as a renewable product among the products obtained by the above steam pyrolysis unit.

[0318] (Z-3): Determine the value of the proportion (Q) of renewable raw materials contained in the above waste materials.

[0319] (Z-4): Compare the value of the above proportion (P) with the value of the above containing proportion (Q), and confirm that the value of the above proportion (P) is below the value of the above containing proportion (Q).

[0320] <<Management Device>>

[0321] As described above, the management device is an apparatus for performing the management method of the present invention.

[0322] according to Figure 3 A preferred embodiment of the management device will be described.

[0323] The management device 100 has a control unit 110 and a storage unit 120.

[0324] 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.

[0325] The hardware and functional configuration of the management device 100 will be described.

[0326] <<Hardware Composition of the Management Device>>

[0327] Figure 4 This is a block diagram illustrating an example of the hardware configuration of the management device 100.

[0328] like Figure 4 As shown, the management device 100 has the following components. Each component is connected via a bus 207.

[0329] CPU 201 is a processing device (computer) that performs various controls and calculations. CPU 201 implements various functions by executing the OS and computer programs stored in the main storage device 202, etc. That is, in this embodiment, CPU 201 functions as the control unit 110 of the management device by executing the management program and executes the management method.

[0330] In addition, the CPU 201 controls the overall operation of the management device 100. It should be noted that in this embodiment, the device that controls the overall operation of the management device 100 is the CPU 201, but it is not limited to this. For example, it can also be an FPGA (Field Programmable Gate Array).

[0331] The management program and various databases do not necessarily have to be stored in the main storage device 202, secondary storage device 203, etc. They can also be stored in other information processing devices connected to the management device 100 via the Internet, LAN (Local Area Network), WAN (Wide Area Network), etc. The management device 100 can also obtain and execute the management program and various databases from other information processing devices.

[0332] The main storage device 202 is a computer-readable storage medium that stores various programs and the data required to execute those programs.

[0333] The main storage device 202 has ROM and RAM (not shown).

[0334] ROM stores various programs such as BIOS.

[0335] RAM functions as a working area deployed when the CPU 201 executes various programs stored in ROM. There are no restrictions on the type of RAM; it can be appropriately selected depending on the purpose. Examples of RAM include DRAM and SRAM.

[0336] As an auxiliary storage device 203, there are no particular limitations as long as it can store various types of information, and it can be appropriately selected according to the purpose. For example, solid-state drives and hard disk drives can be used. In addition, the auxiliary storage device 203 can also be a removable storage device such as a CD drive, DVD drive, or BD drive.

[0337] The output device 204 can be a display, a speaker, or the like. There are no particular limitations on the display; any known display can be used, such as a liquid crystal display or an organic EL display.

[0338] The input device 205 is not particularly restricted as long as it can receive various requests to the management device 100, and can appropriately use known devices such as keyboards, mice, touch panels, etc.

[0339] The communication interface (communication I / F) 206 is not particularly restricted, and well-known communication interfaces may be used appropriately, such as wireless or wired communication devices.

[0340] The processing function of the management device 100 can be realized through the above hardware configuration.

[0341] <<Functional Composition of Management Device>>

[0342] Back Figure 3 The management device 100 has a control unit 110 and a storage unit 120. The control unit 110 controls the management device 100 as a whole.

[0343] The control unit 110 has a confirmation unit (I) 130, a comparison unit 140, and a notification unit (output unit) 150.

[0344] The confirmation unit (I) of the control unit 110 performs the confirmation operation described in the above mechanisms (V-1) to (V-6).

[0345] In addition, the confirmation unit (I) of the control unit 110 performs the following confirmation operations: in the above-mentioned mechanism (Z-1), a product is selected from the product obtained by the steam pyrolysis unit to be allocated as a renewable product; in the above-mentioned mechanism (Z-2), the proportion (P) of the product selected in the above-mentioned mechanism (Z-1) in the product obtained by the steam pyrolysis unit is determined to be allocated as a renewable product; in the above-mentioned mechanism (Z-3), the proportion (Q) of renewable raw materials contained in the waste is determined; in the above-mentioned mechanism (Z-4), the value of the proportion (P) is compared with the value of the proportion (Q), and it is confirmed that the value of the proportion (P) is below the value of the proportion (Q) (information indicating that the value of the proportion (P) is below the value of the proportion (Q) is obtained).

[0346] In the aforementioned mechanism (Z-4), the comparison unit 140 of the control unit 110 performs a comparison operation between the value of the comparison ratio (P) and the value containing the ratio (Q) in order to enable the confirmation unit (I) to perform confirmation.

[0347] When the value of the proportion (P) is less than or equal to the value containing the proportion (Q), the notification unit 150 of the control unit 110 notifies (outputs) that the selected product of the mass percentage of (P) can be allocated as a renewable product in the product. On the other hand, when the value of the proportion (P) exceeds the value containing the proportion (Q), the notification (output) notifies (outputs) that it exceeds the value containing the proportion (Q).

[0348] That is, after executing the management method, the management device 100 will output the value of the selected product as a renewable product, which is obtained by the management method and is allocated according to the proportion of renewable raw materials contained in the waste containing waste tires.

[0349] The reaction database 160 within the storage unit 120 stores information related to the apparatus used in the management method of the present invention, and information related to the reactions performed in that apparatus. Specifically, the storage unit 120 includes a computer-readable storage medium storing a management program for causing the control unit 110, which includes a computer, to execute the management method.

[0350] Although the amount and yield of products obtained from each device can be determined by measurement, yield results can be obtained not only by actual measurement, but also by calculation using the reaction database 160 or by prediction based on past accumulated data.

[0351] Next, the processing steps of the management procedure will be explained. Figure 5 This is a flowchart illustrating an example of the processing steps of the management program in the control unit 110 of the management device 100. Hereinafter, refer to... Figure 5 Please provide an explanation.

[0352] 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 moves the processing to step S102.

[0353] In step S102, the confirmation unit 130 of the control unit 110 of the management device 100 confirms, for example, that pyrolysis oil (OUT) is generated in the pyrolysis unit from waste material (IN) including waste tires, based on information output from the pyrolysis unit. If it is confirmed that the oil has been generated, the process is moved to step S103.

[0354] In step S103, the confirmation unit 130 of the control unit 110 of the management device 100 acquires information related to the cryogenic hydrogenation unit and moves the processing to step S104.

[0355] In step S104, the confirmation unit 130 of the control unit 110 of the management device 100 confirms, for example, that low-temperature hydrogenated oil (OUT) has been generated from pyrolysis oil (IN) in the low-temperature hydrogenation unit based on information output from the low-temperature hydrogenation unit, and confirms that it has been generated. Then, similarly, if it is confirmed that high-temperature hydrogenated oil has been generated from the low-temperature hydrogenated oil fed into the high-temperature hydrogenation unit, that naphtha fraction has been generated from the high-temperature hydrogenated oil fed into the atmospheric distillation unit, or that chemical products have been obtained from the naphtha fraction fed into the steam cracker, the process is moved to step S105.

[0356] In step S105, the confirmation unit 130 of the control unit 110 of the management device 100, for example, confirms, based on information output from the pyrolysis unit, the low-temperature hydrogenation unit, the high-temperature hydrogenation unit, the atmospheric distillation unit, and the steam pyrolyzer, that the processing is carried out in the order of pyrolysis unit, low-temperature hydrogenation unit, high-temperature hydrogenation unit, atmospheric distillation unit, and steam pyrolyzer, and confirms that the chemical product (OUT) is generated from waste material (IN) including waste tires, after these processes are completed. If the generation is confirmed, the processing is moved to step S106.

[0357] In step S106, the confirmation unit 130 of the control unit 110 of the management device 100 confirms the input device (within the management device 100) Figure 4 The input device 205 receives information from the operator that selects products generated by the steam pyrolyzer as renewable products for allocation, and moves the processing to step S107.

[0358] In step S107, the confirmation unit 130 of the control unit 110 of the management device 100 confirms the input device (within the management device 100) Figure 4 The input device 205 receives the value set by the operator, which allocates the proportion (P) of the selected product as a renewable product, and moves the processing to step S108.

[0359] In step S108, the confirmation unit 130 of the control unit 110 of the management device 100 obtains the value of the proportion (Q) of renewable raw materials in the waste fed into the pyrolysis unit and moves the processing to step S109.

[0360] In step S109, the comparison unit 140 of the control unit 110 of the management device 100 compares the value of the ratio (P) with the value containing the ratio (Q) and moves the processing to S110.

[0361] In step S110, the confirmation unit 130 of the control unit 110 of the management device 100 confirms whether the value of the ratio (P) is below the value of the ratio (Q) based on the comparison result of the ratio (P) and the value containing the ratio (Q) performed by the comparison unit 140 of the control unit 110 of the management device 100. When the value of the ratio (P) is confirmed to be below the value of the ratio (Q), the process ends.

[0362] After this process is completed, the value of the selected desired product as a renewable product can be allocated based on the proportion of renewable raw materials contained in the waste containing waste tires. The allocation result is notified to the user through 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 obtained by the chemical product management method, which allocates the value of the selected product as a renewable product based on the proportion of renewable raw materials contained in the waste containing waste tires.

[0363] It should be noted that if the conditions are not met during this process, the user will be notified, 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 reassess the type of product selected above, or reassess the distribution ratio (P) of the selected product, or check the content ratio (Q) of renewable raw materials, and then reassess various conditions such as reaction conditions, and try the process again.

[0364] The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.

[0365] Example

[0366] The present invention will be further described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0367] In the following embodiments, component analysis and evaluation were performed according to the following methods.

[0368] • Distillation properties: JIS K 2254 (Petroleum products - Distillation test methods - Part 7 Gas chromatography)

[0369] • Nitrogen composition: JIS K 2609 (Crude oil and petroleum products – Test method for nitrogen composition)

[0370] • Chlorine content: JPI-5S-64 (Petroleum products – Chlorine content test method – Micro-electromagnetic titration)

[0371] • Sulfur content: JIS K 2541-7 (Crude oil and petroleum products – Test methods for sulfur content – ​​Part 7: Wavelength dispersive fluorescence X-ray method (calibration curve method))

[0372] • Diene value: ASTM D1961 (Test method for maleic diene value of drying oil)

[0373] For samples that cannot be tested using the above methods, refer to the method described in Japanese Patent Application Publication No. 2011-80766. 1 HNMR measurements were performed, and the results were extrapolated using the following method.

[0374] 1. Mix approximately 20 mg of a sample with a known diene value with 500 μL of deuterated chloroform.

[0375] 2. The integral values ​​in the range of 6.0–6.8 ppm were calculated by 1H NMR analysis and corrected to the absolute area per 20 mg sample.

[0376] 3. Perform the above measurements on multiple samples and create a calibration curve of total area versus diene value.

[0377] 4. Calculate the total area of ​​the sample with unknown diene value, and infer the diene value based on the calibration curve in step 3.

[0378] • Iodine value: JIS K 0070 (Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products)

[0379] • Total acid number: JIS K 2501 (Petroleum products and lubricating oils – Neutralization test method)

[0380] • Evaluation of heat exchanger fouling for cryogenic hydrotreating oil after the cryogenic hydrotreating process: Measured in the following order Figure 6 The temperature drop (°C) caused by the fouling on the test piece 61 of the fouling evaluation test apparatus (HLPS) 60 for evaluating the fouling of the heat exchanger shown.

[0381] 1. From Figure 6 The bottom left side (inlet 62) of the fouling evaluation test apparatus (HLPS) 60 shown allows low-temperature hydrotreated oil at 25°C to flow through for a certain period of time (200 minutes).

[0382] 2. While maintaining the temperature of test piece 61 at 300℃, observe the formation and adhesion of dirt on the surface of test piece 61. If dirt adheres to test piece 61, the heat transfer between the low-temperature hydrogenated oil and test piece 61 will decrease.

[0383] 3. Measure the temperature of the low-temperature hydrotreated oil discharged from the upper right side (outlet 63) of the fouling evaluation test apparatus (HLPS) 60. The difference between the initial measured temperature at outlet 63 and the measured temperature after a certain period of time is taken as the "temperature drop caused by the decrease in heat transfer due to fouling".

[0384] (Among them, the results of Comparative Examples 1 and 3 are evaluations of pyrolysis oils that have not undergone low-temperature hydrogenation treatment.)

[0385] Here, the "Heat Exchanger Fouling Evaluation" is conducted according to the following criteria.

[0386] (Evaluation Criteria)

[0387] 〇: If the temperature drop is less than 5°C during a certain period of time (200 minutes), it is judged that the fouling of the heat exchanger has been suppressed.

[0388] ×: If the temperature drop exceeds 5°C during a certain evaluation period (200 minutes), it is judged that the heat exchanger has significant fouling.

[0389] • Evaluation of heat exchanger fouling in atmospheric distillation units: Feedstock oils for atmospheric distillation are evaluated using the same evaluation method as that used for evaluating heat exchanger fouling of cryogenic hydrogenated oils following cryogenic hydrogenation processes.

[0390] • Analysis of gaseous products from steam cracking: JIS K 2301:2011

[0391] (Fuel gases and natural gas - Analytical and experimental methods)

[0392] • Analysis of steam cracking product oil: The steam cracking product oil obtained after water-oil separation is fractionated to obtain a fraction below 250°C, and then analyzed according to JIS K 2536-2 (Petroleum products - Test methods for components - Part 2: Method for determining all components based on gas chromatography).

[0393] (Example 1)

[0394] (1) Thermal pyrolysis process

[0395] use Figure 1 The pyrolysis apparatus shown performs the pyrolysis process.

[0396] Specifically, in pyrolysis furnace 2 (capacity 0.5m³) 3 Approximately 100 kg of shredded waste truck tires (waste material 6) is introduced into the pyrolysis furnace 2. After purging with nitrogen in the furnace, the nitrogen is circulated within the pyrolysis unit while the gas temperature is raised to 500°C via heat exchanger 1 and maintained at that temperature. It should be noted that the nitrogen flow rate introduced into the pyrolysis furnace 2 is set to 0.005 m³ / h. 3 / s[ntp], and controlled at 0.0045m 3 / s[ntp]~0.0055m 3 The range of / s[ntp]. Furthermore, the oxygen concentration within the pyrolysis unit system is controlled to be below 1% of capacity. It should be noted that a zirconia oxygen sensor is used to measure the oxygen concentration within the pyrolysis unit.

[0397] Pyrolysis oil is obtained from the bottom of the distillation column 12a. Additionally, a first gaseous component is obtained from the top of the distillation column 12a.

[0398] It should be noted that the reaction continues until the distillation of the pyrolysis oil stops. After distillation stops, heat exchanger 1 is shut down and the mixture is allowed to cool for approximately 12 hours. Then, a mixture of residue and metal components is removed from the pyrolysis furnace. The metal components are removed from the mixture using a magnetic separator to obtain the residue. The residue is then pulverized into fine powder with a particle size of less than 1 mm using a hammer mill, and further classified using a wind classifier with rotating blades to remove coarse powder with a particle size of more than 50 μm, resulting in carbides with a particle size of less than 10 μm and a maximum frequency of 4 μm.

[0399] The ratios of each component and the properties of the pyrolysis oil are shown in Table 1.

[0400] (2) Low-temperature hydrogenation process

[0401] (2-1) Preparation of hydrogenation catalyst A-1

[0402] As an oxide, a cylindrical support with a diameter of approximately 1.6 mm and a length of approximately 3 mm was prepared using silica-alumina powder composed of 97% alumina and 3% silica. Nickel nitrate and ammonium molybdate were dissolved in ion-exchanged water with a water absorption capacity equivalent to the pre-determined water absorption of the support, yielding a nickel nitrate and ammonium molybdate impregnation solution. This impregnation solution was impregnated into the support using an initial wetting method, with the support supported at a Ni content of 4% by mass and a Mo content of 20% by mass (based on the oxide equivalent). The resulting impregnated material (catalyst precursor) was then dried at 120°C for 3 hours and calcined at 500°C for 1 hour under air circulation to obtain hydrogenation catalyst A-1.

[0403] (2-2) Low-temperature hydrogenation treatment

[0404] Hydrogenation catalyst A-1 was packed into the reaction tube (inner diameter 20 mm). Sulfidation was performed using oil containing 1% by mass of dimethyl disulfide dissolved in light oil, followed by a reaction pressure of 11 MPaG, a reaction temperature of 180 °C, and a WHSV of 0.3 h. -1 Low-temperature hydrogenated oil was obtained by low-temperature hydrogenation treatment using pyrolysis oil as raw material under certain conditions. The properties of the low-temperature hydrogenated oil are shown in Table 2.

[0405] (3) High-temperature hydrogenation process

[0406] (3-1) Preparation of hydrogenation catalyst B-1

[0407] Using 0.9 kg of silica-alumina powder (30% by mass of alumina and 70% by mass of silica as oxides) and 0.1 kg of USY zeolite with a SiO2 / Al2O3 ratio of 30%, a cylindrical support with a diameter of approximately 1.6 mm and a length of approximately 3 mm was prepared by addition, mixing, and calcination. Nickel nitrate and ammonium tungstate were dissolved in ion-exchanged water with a water absorption capacity equivalent to the pre-determined water absorption of the support, yielding a nickel nitrate and ammonium tungstate impregnation solution. This impregnation solution was impregnated into the support using an initial wetting method, with the support supported at a Ni content of 10% by mass and a W content of 20% by mass (based on the oxide equivalent). The resulting impregnated material (catalyst precursor) was then dried at 120°C for 3 hours and calcined at 500°C for 1 hour under air circulation to obtain hydrogenation catalyst B-1.

[0408] (3-2) High-temperature hydrogenation treatment

[0409] Hydrogenation catalyst A-1 and hydrogenation catalyst B-1 were filled into a reaction tube (20 mm inner diameter) at a weight ratio of 8:2. The filling sequence was as follows: hydrogenation catalyst A-1 was filled into the front section of the reaction tube, and hydrogenation catalyst B-1 was filled into the rear section. Sulfidation was performed using oil containing 1% by mass of dimethyl disulfide dissolved in light oil, followed by a reaction pressure of 11 MPaG, a reaction temperature of 390 °C, and a WHSV of 0.3 h. -1 Under certain conditions, high-temperature hydrogenation was carried out using low-temperature hydrogenated oil as raw material to obtain a second gaseous component and high-temperature hydrogenated oil. The results are shown in Table 3.

[0410] (4) Atmospheric distillation process

[0411] The crude oil with the properties shown in Table 2 was mixed with the high-temperature hydrogenated oil obtained from the high-temperature hydrogenation process at a mass ratio of 99:1 to obtain a feedstock for atmospheric distillation. Next, the feedstock for atmospheric distillation was fed into the atmospheric distillation unit, and distillation was carried out in the boiling point range of 60–160°C while controlling the top temperature of the column to obtain the naphtha fraction. Additionally, a light kerosene fraction with a boiling point range of 160–350°C was obtained while controlling the top temperature of the column.

[0412] (5) Steam pyrolysis process

[0413] A pyrolysis unit with a tubular reactor (reaction tube) was used to react naphtha fraction and kerosene light oil fraction obtained from the atmospheric distillation process with steam at a reactor outlet reaction temperature of 790°C, a reaction pressure of 0.15 MPa, and a residence time of 0.25 seconds. The products (product oil and product gas) were recovered and their properties were determined. The chemical yields of the products obtained from the high-temperature hydrotreating process were calculated by comparing the chemical yields of the products with those of the naphtha fraction from crude oil. The results are shown in Table 5.

[0414] (Example 2)

[0415] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 190°C. Otherwise, the chemical product was manufactured in the same manner as in Example 1.

[0416] (Example 3)

[0417] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 200°C. Otherwise, the chemical product was manufactured in the same manner as in Example 1.

[0418] (Example 4)

[0419] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 210°C. Otherwise, the chemical product was manufactured in the same manner as in Example 1.

[0420] (Example 5)

[0421] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 250°C. Otherwise, the chemical product was manufactured in the same manner as in Example 1.

[0422] (Example 6)

[0423] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 300°C. Otherwise, the chemical product was manufactured in the same manner as in Example 1.

[0424] (Example 7)

[0425] In the atmospheric distillation process, the mixing ratio of crude oil and high-temperature hydrogenated oil was changed to 99.5:0.5. Otherwise, the chemical products were manufactured in the same manner as in Example 1.

[0426] (Example 8)

[0427] In the atmospheric distillation process, the mixing ratio of crude oil and high-temperature hydrogenated oil was changed to 98:2. Otherwise, the chemical products were manufactured in the same manner as in Example 1.

[0428] (Comparative Example 1)

[0429] Without undergoing a low-temperature hydrogenation process, the pyrolysis oil obtained from the thermal cracking process is used as a raw material for the high-temperature hydrogenation process. Otherwise, the chemical products are manufactured in the same manner as in Example 1.

[0430] (Comparative Example 2)

[0431] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 150°C. Otherwise, the chemical product was manufactured in the same manner as in Example 1.

[0432] (Comparative Example 3)

[0433] Without undergoing a high-temperature hydrogenation process, the low-temperature hydrogenated oil obtained in the low-temperature hydrogenation process is used instead of the high-temperature hydrogenated oil and is used as part of the feedstock oil for atmospheric distillation. Otherwise, the chemical products are manufactured in the same manner as in Example 1.

[0434] (Comparative Example 4)

[0435] Without undergoing low-temperature hydrogenation and high-temperature hydrogenation processes, pyrolysis oil obtained from the thermal cracking process is used instead of low-temperature hydrogenated oil as part of the feedstock for atmospheric distillation. Otherwise, the chemical products are manufactured in the same manner as in Example 1.

[0436] The results of the pyrolysis, low-temperature hydrogenation, high-temperature hydrogenation, atmospheric distillation, and steam cracking processes in Examples 1-8 and Comparative Examples 1-4 are shown in Tables 1-5. It should be noted that the chemical product yield (mass%) relative to the total amount of pyrolysis products excluding metallic components refers to 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 gaseous component, pyrolysis oil, and residue components obtained in the pyrolysis process.

[0437] As shown in Table 2, compared with Examples 1-8, Comparative Examples 1-2 and 4 show that the feedstock oil (low-temperature hydrogenated oil after the low-temperature hydrogenation process) used for high-temperature hydrogenation treatment causes fouling in the heat exchanger, making it unsuitable for long-term operation. Furthermore, as shown in Table 4, compared with Examples 1-8, Comparative Example 3 shows that the feedstock oil used for atmospheric distillation in the atmospheric distillation process causes fouling in the heat exchanger, making it unsuitable for long-term operation. Moreover, as shown in Table 5, compared with Examples 1-8, Comparative Examples 3-4 have low yields of chemical products, making it impossible to efficiently manufacture chemical products.

[0438]

[0439]

[0440]

[0441]

[0442]

[0443] (Example 9)

[0444] Using a feedstock oil comprising 50% by mass of pyrolysis oil obtained in the pyrolysis process and 50% by mass of recovered oil consisting of high-temperature hydrogenated oil (light and heavy components) obtained in the high-temperature hydrogenation process, a low-temperature hydrogenation process is performed, and the chemical product is manufactured in the same manner as in Example 1.

[0445] (Example 10)

[0446] Using a feedstock oil comprising 20% ​​by mass of pyrolysis oil obtained in the pyrolysis process and 80% by mass of recovered oil consisting of high-temperature hydrogenated oil (light and heavy components) obtained in the high-temperature hydrogenation process, a low-temperature hydrogenation process is performed to produce a chemical product, otherwise the same as in Example 1.

[0447] The results of the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process in Examples 9 and 10 are shown in Tables 6 to 9.

[0448] As shown in Tables 6-9, even if the mixing ratio of pyrolysis oil and recovered oil in the low-temperature hydrogenation process is changed, the feedstock oil supplied for high-temperature hydrogenation treatment (low-temperature hydrogenated oil after the low-temperature hydrogenation process) can inhibit the fouling of the heat exchanger, and the feedstock oil supplied for atmospheric distillation in the atmospheric distillation process can also inhibit the fouling of the heat exchanger. It can efficiently manufacture chemical products, and is therefore suitable for long-term operation, which can reduce manufacturing costs.

[0449]

[0450]

[0451]

[0452]

[0453] (Example 11)

[0454] The feedstock oil (75% by mass of low-boiling-point oil and 25% by mass of high-boiling-point oil) after fractionation of pyrolysis oil to remove 18% by mass of high-boiling-point oil was used for a low-temperature hydrogenation process. Otherwise, the chemical products were manufactured in the same manner as in Example 1.

[0455] The properties of the feedstock oil used in the low-temperature hydrogenation process are shown in Table 10.

[0456] (Example 12)

[0457] The feedstock oil (67% by mass of low-boiling-point oil and 33% by mass of high-boiling-point oil) after fractionation of pyrolysis oil to remove 10% by mass of high-boiling-point oil was used for a low-temperature hydrogenation process. Otherwise, the chemical products were manufactured in the same manner as in Example 1.

[0458] The properties of the feedstock oil used in the low-temperature hydrogenation process are shown in Table 10.

[0459] (Example 13)

[0460] The pyrolysis oil was subjected to a thermal cracking process at a temperature of 400°C. Otherwise, the chemical products were manufactured in the same manner as in Example 1. The properties of the feedstock oil used in the low-temperature hydrogenation process are shown in Table 10.

[0461] (Example 14)

[0462] The pyrolysis oil was subjected to a thermal cracking process at a temperature of 700°C. Otherwise, the chemical products were manufactured in the same manner as in Example 1. The properties of the feedstock oil used in the low-temperature hydrogenation process are shown in Table 10.

[0463]

[0464] The product ratio is the ratio of products after thermal decomposition at each thermal decomposition temperature. The pyrolysis oil properties in Examples 11 and 12 represent the pyrolysis oil properties after the removal of high-boiling-point oil.

[0465] The results of the low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process in Examples 11-14 are shown in Tables 11-14.

[0466]

[0467]

[0468]

[0469]

[0470] (Example 15)

[0471] Using a feedstock comprising 50% by mass of feedstock oil after removing 18% by mass of high-boiling-point oil by distillation of pyrolysis oil and 50% by mass of recovered oil composed of high-temperature hydrogenated oil obtained from the high-temperature hydrogenation process, a low-temperature hydrogenation process is performed, and the chemical product is manufactured in the same manner as in Example 1.

[0472] (Example 16)

[0473] Using a feedstock comprising 20% ​​by mass of feedstock oil after removing 10% by mass of high-boiling-point oil by distillation of pyrolysis oil and 80% by mass of recovered oil composed of high-temperature hydrogenated oil obtained from a high-temperature hydrogenation process, a low-temperature hydrogenation process is performed, and the chemical product is manufactured in the same manner as in Example 1.

[0474] The results of the thermal cracking process, low-temperature hydrogenation process, high-temperature hydrogenation process, atmospheric distillation process, and steam cracking process in Examples 15 and 16 are shown in Tables 15-19.

[0475]

[0476] The product ratio is based on the product ratio after thermal cracking at 500°C. The pyrolysis oil properties in Examples 15 and 16 represent the pyrolysis oil properties after the removal of high-boiling-point oil.

[0477]

[0478]

[0479]

[0480]

[0481] Based on the above embodiments, it can be confirmed that the present invention enables the efficient manufacture of chemical products from waste materials including waste tires.

[0482] Symbol Explanation

[0483] 1…Heat exchanger, 2…Thermal cracking furnace, 3…Oxygen-free gas supply source, 4…Circulation path, 5…Oil recovery device, 6…Waste, 7…Decomposition device, 8…External heating means, 9…Flow meter, 10…Damper, 11…Blower, 12…Distillation tower, 13…Recovery tank, 14…Hot blast furnace, 15…Exhaust fan, 16…Exhaust treatment device, 100…System, 110…Thermal cracking unit, 111…First separation unit, 112…Micronization unit, 115…Cryogenic hydrogenation unit, 120…High-temperature hydrogenation unit, 125…Ambient distillation unit, 130… …Steam pyrolyzer, S1…waste, S2…first gas component, S3…pyrolysis oil, S4…mixture of residue and metal components, 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 pyrolysis feedstock oil, S12…product gas, S13…product oil, S14…heavy fraction, S15…recovered oil (high-temperature hydrogenated oil), 60…apparatus for evaluating heat exchanger fouling, 61…test piece, 62…inlet, 63…outlet.

Claims

1. A method for manufacturing a chemical product, comprising the following steps: The pyrolysis process involves pyrolyzing a pulverized material containing waste tires to obtain a first gaseous component, pyrolysis oil, and residue components. The low-temperature hydrogenation process involves subjecting the feedstock oil containing at least a portion of the pyrolysis oil to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil. The high-temperature hydrogenation process involves hydrogenating at least a portion of the feedstock containing the low-temperature hydrogenated oil at a temperature higher than that of the low-temperature hydrogenation treatment to obtain a second gaseous component and a high-temperature hydrogenated oil. The separation process involves atmospheric distillation of a feedstock containing at least a portion of the high-temperature hydrogenated oil and crude oil to separate it into naphtha fraction and other fractions. as well as The steam cracking process involves steam cracking a steam cracking feedstock containing at least a portion of the naphtha fraction and / or the other fractions to obtain chemical products. In the pyrolysis process, the amount of pyrolysis oil is 40% or more by mass relative to the total amount of the first gas component, the pyrolysis oil, and the residue component.

2. The manufacturing method according to claim 1, wherein, The pyrolysis temperature in the pyrolysis process is 350℃~750℃.

3. The manufacturing method according to claim 1, wherein, In the pyrolysis process, the amount of the first gas component is less than 25% by mass relative to the total amount of the first gas component, the pyrolysis oil, and the residue component.

4. The manufacturing method according to claim 1, wherein, In the pyrolysis process, the amount of pyrolysis oil is less than 80% by mass relative to the total amount of the first gas component, the pyrolysis oil, and the residue component.

5. The manufacturing 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 manufacturing method according to claim 1, wherein, The feedstock oil in the high-temperature hydrogenation process contains at least a portion of the pyrolysis oil or a portion of the fraction obtained by fractionating the pyrolysis oil.

7. The manufacturing method according to claim 1, wherein, After removing at least a portion of the high-boiling-point oil (with a boiling point exceeding 350°C) from the pyrolysis oil by distillation, it is used as part of the feedstock oil for the low-temperature hydrogenation process.

8. The manufacturing method according to claim 1, wherein, In the high-temperature hydrogenation process, the feedstock oil contains low-boiling-point oil with a boiling point below 350°C and high-boiling-point oil with a boiling point above 350°C. Based on the total amount of the feedstock oil, the content of the high-boiling-point oil is less than 50% by mass.

9. The manufacturing method according to claim 1, wherein, The recovered oil, which contains at least a portion of the high-temperature hydrogenated oil obtained in the high-temperature hydrogenation process, is used as part of the feedstock oil for the low-temperature hydrogenation process.

10. The manufacturing method according to claim 9, wherein, In the low-temperature hydrogenation process, the amount of the recovered oil in the feedstock is more than 10% by mass and less than 99% by mass relative to the total amount of the recovered oil and the pyrolysis oil.

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

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

13. The manufacturing method according to claim 1, wherein, In the high-temperature hydrogenation process, the nitrogen content in the feed oil used for atmospheric distillation is above 2000 ppm by mass, and the nitrogen content in the naphtha fraction is below 25 ppm by mass.

14. The manufacturing method according to claim 1, wherein, In the separation process, the amount of the high-temperature hydrogenated oil in the feedstock oil for atmospheric distillation is 0.001% to 9% by mass relative to the total amount of the high-temperature hydrogenated oil and the crude oil.

15. The manufacturing method according to claim 1, wherein, The diene value of the low-temperature hydrogenated oil is less than 13.0 gI2 / 100g.

16. The manufacturing method according to claim 1, wherein, The iodine value of the low-temperature hydrogenated oil is less than 160 gI2 / 100 g.

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

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

19. The manufacturing method according to claim 1, wherein, The chemical product is selected from at least one 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 further includes at least one of waste rubber and waste plastic.

21. A method for manufacturing synthetic rubber, comprising a polymerization step of obtaining synthetic rubber by a polymerization reaction, wherein the polymerization reaction uses butadiene obtained by the manufacturing method of claim 19 as at least a portion of the raw material for the synthetic rubber.

22. A tire comprising synthetic rubber obtained by the manufacturing method of claim 21.

23. A method of manufacturing a tire, comprising a vulcanization step of obtaining the tire by a vulcanization reaction, wherein the vulcanization reaction uses synthetic rubber obtained by the manufacturing method of claim 21 as at least a portion of the raw material for the tire.

24. A method for managing chemical products, which is a method for managing chemical products using a management device and applied when manufacturing chemical products from waste materials including waste tires. The management method utilizes the management device to allocate chemical products based on the proportion of renewable raw materials contained in the waste, using a mass balance approach to obtain the value of the renewable products. The management method includes a process (V) for confirming the acquisition of the chemical product. The process (V) includes the following processes (V-1), (V-2), (V-3), (V-4), (V-5), and (V-6). The process (V-1) is the process of confirming that the waste is fed into the pyrolysis unit to obtain pyrolysis oil through the pyrolysis of the waste to produce the pyrolysis oil; The process (V-2) is the process of confirming that the pyrolysis oil is generated from the pyrolysis oil fed into a low-temperature hydrogenation unit where the feedstock oil containing at least a portion of the pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil. The process (V-3) is the process of confirming that the high-temperature hydrogenated oil is generated from the low-temperature hydrogenated oil fed into a high-temperature hydrogenation unit where the feedstock containing at least a portion of the low-temperature hydrogenated oil is hydrogenated at a temperature higher than that of the low-temperature hydrogenation treatment to obtain a second gas component and high-temperature hydrogenated oil. The process (V-4) is the process of confirming that the naphtha fraction and the other fractions are generated from the high-temperature hydrogenated oil fed into an atmospheric distillation unit that separates the feedstock oil, containing at least a portion of the high-temperature hydrogenated oil and crude oil, into naphtha fractions and other fractions through atmospheric distillation. The step (V-5) is a step of confirming that the chemical product is obtained from the steam cracking feedstock that is fed into a steam cracker that performs steam cracking treatment on at least a portion of the steam cracking feedstock containing the naphtha fraction and / or the other fractions. The process (V-6) is a process that confirms that the chemical product is obtained from the waste by processing it in the order of the pyrolysis unit, the low-temperature hydrogenation unit, the high-temperature hydrogenation unit, the atmospheric distillation unit, and the steam pyrolysis unit. The management method includes a step (Z) of confirming the proportion of products allocated as value as renewable products. The process (Z) includes the following processes (Z-1), (Z-2), (Z-3), and (Z-4). The process (Z-1) is the process of selecting products from the products obtained through the steam pyrolysis unit as renewable products for distribution. The process (Z-2) is a process of determining the value of the proportion P of the product selected in the process (Z-1) in the product obtained by the steam pyrolyzer, which is then allocated as a renewable product. The process (Z-3) is the process of determining the value of Q, which represents the proportion of renewable raw materials contained in the waste. The step (Z-4) is to compare the value of the proportion P with the value containing the proportion Q and confirm that the value of the proportion P is below the value containing the proportion Q.

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

26. The management device according to claim 25, wherein, After executing the management method, the output is the result obtained by the management method, which allocates the value of the selected product as a renewable product based on the proportion of renewable raw materials contained in the waste containing waste tires.

27. A storage medium, a computer-readable storage medium storing a computer program, the storage of which enables a computer to execute the management program of claim 24.

28. A management program for causing a computer to perform the management method of claim 24.

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