Method for producing chemical product and carbide, and method for managing chemical product

Abstract

Provided is a method for efficiently producing a chemical product from a waste tire by improving each step in a series of processes, and also efficiently obtaining a carbide. A method for producing a chemical product and a carbide, the method comprising: a pyrolysis step for obtaining a first gas component, a pyrolysis oil, and a residue component by pyrolysis of a crushed waste tire; a carbide recovery step for recovering carbide from the residue component; a low-temperature hydrogenation step in which a low-temperature hydrogenated oil is obtained by subjecting a starting material oil containing at least a portion of the pyrolysis oil to a low-temperature hydrogenation treatment at 180-350 DEG C; a hydrocracking step in which a raw oil containing at least a portion of the low-temperature hydrogenated oil is hydrocracked at a temperature higher than the low-temperature hydrotreating temperature to obtain a second gas component, a light component having a boiling point of 350 DEG C or less, and a heavy component having a boiling point of more than 350 DEG C; and a steam cracking step for obtaining a raw material for producing a carbide, which comprises a chemical product and a heavy fraction having a 10% distillation temperature of 190 DEG C or higher, by steam cracking of a steam cracking raw material oil containing at least a portion of the light component. The thermal cracking temperature of the thermal cracking is 350-750 DEG C.

Description

Technical Field

[0001] This invention relates to methods for manufacturing chemical products and carbides. Furthermore, this invention relates to a method for managing chemical products using a management device when manufacturing chemical products from waste tires. Background Technology

[0002] In recent years, as a method for recycling waste materials such as waste tires, waste rubber, and waste plastics, research has been conducted on the conversion into chemical products through methods such as pyrolysis (e.g., Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Publication No. 2019-533041 Summary of the Invention

[0006] In the recycling of waste materials, since the types and qualities of waste materials are not fixed, and there is a need to effectively utilize existing equipment and processes, there is a desire to develop various processes.

[0007] The inventors have studied a series of processes, particularly in methods for manufacturing chemical products using waste tires, including a pyrolysis process to obtain pyrolysis oil through the pyrolysis of waste tires, a hydrogenation pyrolysis process to obtain at least light components by hydrogenation of the pyrolysis oil, and a steam pyrolysis process to obtain chemical products by steam pyrolysis of the light components. In this series of processes, the following technical problem was discovered: if the pyrolysis oil is directly hydrogenated, impurities such as dienes contained in the pyrolysis oil cause fouling (byproducts such as hydrocarbon polymers) during the hydrogenation pyrolysis process.

[0008] The purpose of this invention is to provide an improved method for efficiently manufacturing chemical products from waste tires and also efficiently obtaining carbides. Furthermore, the purpose of this invention is to provide a method for managing chemical products using a management device when manufacturing chemical products from waste tires.

[0009] In order to solve the above-mentioned problems, the inventors conducted research and discovered that, in the method of manufacturing chemical products using waste tires, by improving the above-mentioned series of processes, a low-temperature hydrogenation process is performed between the thermal cracking process and the hydrogenation cracking process to obtain low-temperature hydrogenated oil through low-temperature hydrogenation treatment, thereby suppressing the generation of fouling (byproducts such as hydrocarbon polymers). Based on this insight, the inventors completed the present invention.

[0010] One aspect of the present invention relates to, for example, the following.

[0011] [1] A method for manufacturing a chemical product and a carbide, comprising:

[0012] The pyrolysis process involves the pyrolysis of waste tire fragments to obtain the first gaseous component, pyrolysis oil, and residue components.

[0013] The carbide recovery process recovers carbides from the above-mentioned residue components;

[0014] The low-temperature hydrogenation process involves subjecting the feedstock containing at least a portion of the aforementioned thermally cracked oil to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0015] The hydrogenation cracking process involves subjecting the feedstock containing at least a portion of the aforementioned low-temperature hydrogenated oil to hydrogenation cracking at a temperature higher than that of the aforementioned low-temperature hydrogenation treatment, to obtain a second gaseous component, a light component with a boiling point below 350°C, and a heavy component with a boiling point above 350°C; and

[0016] The steam cracking process obtains chemical products and a raw material for manufacturing carbides containing at least 10% of a heavy fraction with a distillation temperature of 190°C or higher by steam cracking a steam cracking feedstock oil containing at least a portion of the light components mentioned above.

[0017] The thermal pyrolysis temperature of the above-mentioned thermal pyrolysis is 350℃~750℃.

[0018] [2] According to the manufacturing method described in [1], in the above-mentioned thermal cracking process, the amount of the first gas component is 25% by mass or less relative to the total amount of the first gas component, the thermal cracking oil and the residue component.

[0019] [3] According to the manufacturing method described in [1] or [2], in the above-mentioned thermal cracking process, the amount of the thermal cracking oil is 40% by mass or more relative to the total amount of the first gas component, the thermal cracking oil and the residue component.

[0020] [4] The manufacturing method according to any one of [1] to [3], wherein the 10% distillation temperature of the above-mentioned thermal cracked oil is 90°C or higher, and the 90% distillation temperature is 350°C or higher.

[0021] [5] The manufacturing method according to any one of [1] to [4], wherein the feedstock oil in the above-mentioned hydrogenation cracking process further contains at least a portion of the above-mentioned thermal cracking oil or a portion of the thermal cracking oil (fractionated thermal cracking oil) obtained by fractionating the above-mentioned thermal cracking oil.

[0022] [6] The manufacturing method according to any one of [1] to [5], wherein the above-mentioned thermal cracking oil is used as part of the feed oil for the above-mentioned low-temperature hydrogenation process after at least a portion of the high-boiling-point oil with a boiling point exceeding 350°C is removed by distillation.

[0023] [7] The manufacturing method according to any one of [1] to [6], wherein in the above-mentioned hydrogenation cracking process, the above-mentioned feed oil contains low-boiling-point oil with a boiling point of less than 350°C and high-boiling-point oil with a boiling point of more than 350°C, and the content of the high-boiling-point oil is less than 50% by mass based on the total amount of the above-mentioned feed oil.

[0024] [8] The manufacturing method according to any one of [1] to [7], wherein a recycled oil containing at least a portion of the light and heavy components obtained in the above-mentioned hydrocracking process is used as part of the feedstock oil for the above-mentioned low-temperature hydrotreating process.

[0025] [9] According to the manufacturing method described in [8], in the above-mentioned low-temperature hydrogenation process, the amount of the recycle oil is 10% to 99% by mass relative to the total amount of the recycle oil and the thermal cracking oil in the above-mentioned feedstock oil.

[0026]

[10] The manufacturing method according to any one of [1] to [9], wherein the above-mentioned hydrogenation cracking step is a step of hydrogenating and cracking the above-mentioned feedstock oil in the presence of a hydrogenation cracking catalyst.

[0027]

[11] According to the manufacturing method described in

[10] , the above-mentioned hydrogenation cracking catalyst contains a Ni-based catalyst.

[0028]

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

[11] , wherein, in the above-mentioned hydrogenation cracking process, the nitrogen content in the above-mentioned feed oil is 2000 ppm by mass or more, and the nitrogen content in the above-mentioned light components is 25 ppm by mass or less.

[0029]

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

[12] , wherein the diene value of the above-mentioned low-temperature hydrogenated oil is less than 13.0 gI2 / 100g.

[0030]

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

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

[0031]

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

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

[0032]

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

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

[0033]

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

[16] further includes a carbide manufacturing step of obtaining carbides by thermal decomposition or incomplete combustion of the raw materials for carbide manufacturing described above.

[0034]

[18] A method for manufacturing synthetic rubber includes a polymerization step, wherein the polymerization step obtains synthetic rubber by using at least a portion of butadiene obtained by the manufacturing method described in

[16] as a raw material for synthetic rubber through a polymerization reaction.

[0035]

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

[18] .

[0036]

[20] A method for manufacturing a tire includes a vulcanization step, wherein the vulcanization step yields a tire by vulcanizing at least a portion of a synthetic rubber obtained by the manufacturing method described in

[18] as a raw material for the tire.

[0037]

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

[0038] The above-described management method uses the aforementioned management device to allocate the value of the aforementioned chemical products as renewable products based on the proportion of renewable raw materials contained in the aforementioned waste tires using a mass balance method.

[0039] The above management methods include confirming the process (V) for obtaining the above chemical products.

[0040] The above process (V) includes the following processes (V-1), (V-2), (V-3), (V-4), and (V-5).

[0041] The above-mentioned process (V-1) is a process that confirms the generation of the above-mentioned pyrolysis oil from the waste tires fed into the pyrolysis unit that performs pyrolysis treatment on the waste tires at 350°C to 750°C to obtain pyrolysis oil.

[0042] 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 thermal cracking oil in a low-temperature hydrogenation unit where the feedstock oil containing at least a portion of the above-mentioned thermal cracking oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0043] The above-mentioned process (V-3) is a process that confirms the generation of the light components from the low-temperature hydrogenated oil in a hydrogenation cracking unit where at least a portion of the feedstock oil containing the above-mentioned low-temperature hydrogenated oil is subjected to hydrogenation cracking treatment at a temperature higher than the above-mentioned low-temperature hydrogenation treatment to obtain light components with a boiling point of less than 350°C.

[0044] The above-described process (V-4) is a process of confirming that the above-described chemical product is obtained from the light components fed into a steam pyrolysis reactor that performs steam pyrolysis treatment on at least a portion of the steam pyrolysis feedstock containing the above-described light components.

[0045] The above-described process (V-5) confirms that the above-described chemical product is obtained from the above-described waste tires by sequentially processing them using the above-described pyrolysis unit, the above-described low-temperature hydrogenation unit, the above-described hydrogenation pyrolysis unit, and the above-described steam pyrolysis unit.

[0046] The aforementioned management method includes a process (Z) for determining the proportion of products allocated as renewable resources.

[0047] The above process (Z) includes the following processes (Z-1), (Z-2), (Z-3), and (Z-4).

[0048] The above-mentioned process (Z-1) is a process of selecting products from the products obtained from the above-mentioned steam pyrolysis unit for distribution as renewable products.

[0049] The above-mentioned step (Z-2) is a step in which the proportion (P) of the product selected in the above-mentioned step (Z-1) relative to the proportion of the product obtained from the above-mentioned steam pyrolysis unit is determined as a renewable product.

[0050] The above-mentioned process (Z-3) is the process of determining the value of the proportion (Q) of renewable raw materials contained in the above-mentioned waste tires.

[0051] 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 less than or equal to the value of the above containing proportion (Q).

[0052]

[22] A management device comprising a computer-readable storage medium storing a management program,

[0053] The aforementioned management device executes the management method described in

[21] by executing the aforementioned management procedure.

[0054]

[23] According to the management device described in

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

[0055]

[24] A storage medium is a computer-readable storage medium that stores a computer program.

[0056] The storage enables the computer to execute the management program of the management method described in

[21] .

[0057]

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

[21] .

[0058] According to the present invention, an improved series of processes is provided for the efficient manufacture of chemical products from waste tires, and also for the efficient production of carbides. Furthermore, the present invention provides a method for managing chemical products using a management device when manufacturing chemical products from waste tires. Attached Figure Description

[0059] Figure 1 This is a schematic diagram showing an example of a pyrolysis device.

[0060] Figure 2 This is a schematic diagram illustrating an example of a system for implementing a method for manufacturing chemical products and carbides.

[0061] Figure 3 It is a schematic diagram used to illustrate the functional configuration 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 sequence of the management procedure in the control section of a 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 chemical products and carbides according to this embodiment includes: a pyrolysis step, in which a first gaseous component, pyrolysis oil, and residue component are obtained by pyrolysis of waste tire fragments; a carbide recovery step, in which carbides are recovered from the 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 hydrogenation cracking step, in which a feedstock oil containing at least a portion of the low-temperature hydrogenated oil is subjected to hydrogenation cracking treatment at a temperature higher than that of the low-temperature hydrogenation treatment to obtain a second gaseous component, a light component with a boiling point of less than 350°C, and a heavy component with a boiling point of more than 350°C; and a steam cracking step, in which a chemical product and a raw material for carbide manufacturing containing 10% heavy fraction with a distillation temperature of 190°C or higher are obtained by steam cracking of the steam cracking feedstock oil containing at least a portion of the light component.

[0067] In the pyrolysis process of this embodiment, the pyrolysis temperature is 350°C to 750°C.

[0068] In the method for manufacturing chemical products and carbides according to this embodiment, by using waste tires through the above-described process, chemical products can be manufactured efficiently, and powdered carbides that can be used as rubber additives, resin additives, colorants, etc. can also be manufactured efficiently.

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

[0070] (Thermal pyrolysis process)

[0071] The pyrolysis process is a process of obtaining the first gas component, pyrolysis oil and residue component by pyrolyzing waste tires and other crushed materials (hereinafter referred to as waste).

[0072] Waste tires sometimes contain metallic components. For example, waste tires may also contain metallic components such as steel cords and wires used as tire aggregates.

[0073] When waste tires contain metallic components, the manufacturing method of this embodiment may further include a removal step to remove the metallic components from the waste tires or their shredded form. The method for removing the metallic components from the waste tires or their shredded form is not particularly limited; for example, methods using magnets, sieves, etc., can be cited.

[0074] It should be noted that the metallic components in waste tires do not necessarily need to be removed before the pyrolysis process. For example, when waste tires contain metallic components, the pyrolysis process yields a mixture of a first gas component, pyrolysis oil, residue components, and metallic components. The manufacturing method of this embodiment may further include a removal process to remove the metallic components from this 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.

[0075] There are no particular limitations on the crushing methods for waste tires. For example, it can be mechanical crushing using a single-shaft crusher or a double-shaft crusher, crushing using water spray, cryogenic crushing, laser crushing, etc.

[0076] The pyrolysis of waste tire fragments can be carried out, for example, by placing the waste tire fragments in a pyrolysis furnace and supplying the furnace with high-temperature gas, thereby bringing the waste tire fragments into contact with the high-temperature gas. The high-temperature gas is preferably an oxygen-free gas (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 and can be, for example, a batch furnace, a fluidized bed furnace, or a kiln furnace.

[0077] The pyrolysis temperature (temperature of the high-temperature gas) in the pyrolysis process is 350°C or higher. From the viewpoints of further improving the chemical product yield, making it easier to obtain powdered carbides from the residue components, further improving the dispersibility of the obtained powdered carbides when added to resins, elastomers, etc., and making the heavy fraction obtained in the steam pyrolysis process more suitable as a raw material for carbide manufacturing (especially for carbon black manufacturing), it is preferably 370°C or higher, and more preferably 390°C or higher. Alternatively, the pyrolysis temperature (temperature of the high-temperature gas) in the pyrolysis process can be, for example, 750°C or lower. From the viewpoints of further improving the chemical product yield, making it easier to obtain powdered carbides from the residue components, and making the heavy fraction obtained in the steam pyrolysis process more suitable as a raw material for carbide manufacturing (especially for carbon black manufacturing), it is preferably 730°C or lower, and more preferably 710°C or lower. It should be noted that if such a temperature range is available, there is a tendency to easily meet the appropriate amounts of the products (first gas components, thermally cracked oil, and residue components) described later, and to easily obtain feedstock oil with a high-boiling-point oil content within an appropriate range.

[0078] That is, the thermal decomposition temperature (temperature of high-temperature gas) in the thermal decomposition process can be, for example, 350~750℃, 350~730℃, 350~710℃, 370~750℃, 370~730℃, 370~710℃, 390~750℃, 390~730℃ or 390~710℃.

[0079] Thermal pyrolysis can be carried out in the presence or absence of a thermal pyrolysis catalyst. The thermal pyrolysis catalyst can be any catalyst commonly used in petrochemical thermal pyrolysis without particular limitations. The thermal pyrolysis catalyst can be either an acidic or basic catalyst. Examples of acidic catalysts include catalysts containing aluminosilicates. Examples of aluminosilicates include zeolites, montmorillonite, and other saponites. 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.

[0080] The conditions for thermal cracking, such as the resulting component ratio and the properties of the resulting thermally cracked oil, can be appropriately adjusted within the appropriate ranges described later.

[0081] 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 be obtained in the form of a mixture with the metallic component. In the pyrolysis process, the pyrolysis oil can be recovered as an oil fraction, for example, by generating pyrolysis gas in the pyrolysis furnace and cooling the pyrolysis gas. Additionally, in the pyrolysis process, the first gaseous component can be recovered, for example, as the residual gas after cooling the pyrolysis gas and recovering the oil fraction. Furthermore, in the pyrolysis process, the residue component can be recovered, for example, as the solid component remaining in the pyrolysis furnace after pyrolysis.

[0082] 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% by mass or more. From the viewpoint of improving the yield of chemical products obtained through the low-temperature hydrogenation process, the hydrogenation pyrolysis process, and the steam pyrolysis 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 45% by mass or more, more preferably 48% by mass or more, further 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.

[0083] That is, in the pyrolysis process, relative to the total amount of the first gas component, the pyrolysis oil, and the residue component, the amount of pyrolysis oil 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 ... 0% 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.

[0084] It should be noted that in previous waste treatment methods, from the viewpoint of processing as much waste as possible, the main focus was on thermal cracking under conditions of low residue content and high gas content (e.g., Patent Document 1). In contrast, in the manufacturing method of this embodiment, by performing thermal cracking under conditions where the amount of thermally cracked oil is within the aforementioned range, the yield of chemical products obtained through the low-temperature hydrogenation process, the hydrogenation cracking process, and the steam cracking process is further improved, it is easier to obtain powdered carbides from the residue content, and the heavy fraction obtained in the steam cracking process is more suitable as a raw material for carbide manufacturing.

[0085] In the pyrolysis process, the amount of the first gas component is, for example, 25% by mass or less relative to the total amount of the first gas component, the pyrolysis oil, and the residue component. From the viewpoint of improving the yield of chemical products obtained through the cryogenic hydrogenation process, the hydrogenation cracking process, and the steam cracking process, in the pyrolysis process, the amount of the first gas component is preferably 20% by mass or less relative to the total amount of the first gas component, the pyrolysis oil, and the residue component, more preferably 15% by mass or less, and may also be 13% by mass or less or 10% by mass or less. If the pyrolysis condition is such that the amount of the first gas component is 25% by mass or less, the decrease in the yield of the pyrolysis oil due to excessive pyrolysis of the broken material can be suppressed. That is, if the above-mentioned pyrolysis condition is met, the situation where the pyrolysis oil generated by the pyrolysis of the broken material further undergoes pyrolysis and becomes a gas component can be suppressed, and the yield of the pyrolysis oil that can become a chemical product through the cryogenic hydrogenation process, the hydrogenation cracking process, and the steam cracking process can be further improved, and the yield of the chemical product is further improved.

[0086] Furthermore, relative to the total amount of the first gas component, the thermal cracking oil, and the residue component, the amount of the first gas component can be, for example, 0.1% by mass or more, or 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. In the case where the crushed material contains, for example, chlorine, a portion of the chlorine in the crushed material is vaporized as chlorine gas or the like due to thermal cracking. That is, a portion of the chlorine in the crushed material is removed as part of the first gas component. Therefore, when a predetermined amount of the first gas component is generated in the thermal cracking process, the chlorine content in the thermal cracking oil can be reduced compared to the case where no first gas component is generated in the thermal cracking process. Therefore, by setting thermal cracking conditions that generate a predetermined amount of the first gas component, the purity of the chemical products obtained through the low-temperature hydrogenation process of the thermal cracking oil, the hydrogenation cracking process of the low-temperature hydrogenated oil, and the steam cracking process of the steam cracking feedstock oil is further improved. Furthermore, when a catalyst is used in the hydrogenation cracking process, catalyst poisoning caused by chlorine can be suppressed, and catalyst deterioration can be prevented. It should be noted that although chlorine was mentioned above, the same applies when the crushed material contains nitrogen, sulfur, or halogens other than chlorine.

[0087] That is, relative to the total amount of the first gas component, the thermal cracking oil, and the residue component, the amount of the first gas component can be, for example, 0.1–25% by mass, 0.1–20% by mass, 0.1–15% by mass, 0.1–13% by mass, 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, 0.5–10% by mass, 0.7–25% by mass, 0.7–20% by mass, 0.7–1 5% by mass, 0.7–13% by mass, 0.7–10% by mass, 1–25% by mass, 1–20% by mass, 1–15% by mass, 1–13% by mass, 1–10% by mass, 1.3–25% by mass, 1.3–20% by mass, 1.3–15% by mass, 1.3–13% by mass, 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 1.5–10% by mass.

[0088] In the pyrolysis process, relative to the total amount of the first gas component, pyrolysis oil, and residue component, the amount of residue component can be, for example, 10% by mass or more. From the viewpoint of improving the yield of chemical products obtained through the cryogenic hydrogenation process, the hydrogenation cracking process, and the steam cracking process, and from the viewpoint of improving the yield of carbides recovered in the form of residue component, it is preferable to be 15% by mass or more, and more preferably 20% by mass or more. If the pyrolysis condition with a residue component amount of 10% by mass or more is met, the decrease in the yield of pyrolysis oil due to excessive pyrolysis of the crushed material can be suppressed. That is, if the above-mentioned pyrolysis condition is met, the situation where the pyrolysis oil generated by the pyrolysis of the crushed material further undergoes pyrolysis and becomes a gas component can be suppressed, and the yield of pyrolysis oil that can become a chemical product through the cryogenic hydrogenation process, the hydrogenation cracking process, and the steam cracking process can be further improved, thereby further improving the yield of chemical products. In addition, from the viewpoint of recovering more carbides, the above range is also preferred.

[0089] Furthermore, relative to the total amount of the first gas component, the thermal cracking oil, and the residue component, the amount of the residue component can be, for example, 60% by mass or less. From the viewpoint of improving the yield of chemical products obtained through the low-temperature hydrogenation process, the hydrogenation cracking process, and the steam cracking process, and from the viewpoint of more easily obtaining powdered carbides from the residue component, 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 increases relative to the total amount of the first gas component, the thermal cracking oil, and the residue component, the amounts of the first gas component and the thermal cracking oil decrease relative to the total amount of the first gas component, the thermal cracking oil, and the residue component. Therefore, if the thermal cracking conditions have a residue component amount of 60% by mass or less, it is possible to suppress the residue of broken material that should become thermal cracking oil as residue component, thereby improving the yield of thermal cracking oil that can become chemical products through the low-temperature hydrogenation process, the hydrogenation cracking process, and the steam cracking process, and further improving the yield of chemical products.

[0090] That is, relative to the total amount of the first gas component, the thermal cracking oil, and the residue component, the amount of the 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.

[0091] The first gaseous component may be, for example, a gaseous component in the products generated by thermal decomposition at normal pressure and 20°C. The first gaseous component may include, for example, hydrogen and hydrocarbons having 1 to 4 carbon atoms.

[0092] There are no particular limitations on the method for recovering the first gaseous component. For example, the first gaseous component can be recovered in the form of the residual gas after cooling and recovering the oil (pyrolysis oil) from the thermally cracked gas generated by thermal cracking.

[0093] 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.

[0094] Thermal cracking oil can be, for example, a liquid component in the products generated by thermal cracking at atmospheric pressure and 20°C. There are no particular limitations on the method for recovering thermal cracking oil. For example, thermal cracking oil can be recovered as oil fraction distilled from the thermal cracking furnace. That is, thermal cracking oil can be recovered, for example, as oil fraction condensed by cooling the thermal cracking gases generated by thermal cracking.

[0095] There are no particular limitations on the distillation properties of thermal cracking oil. For example, it can be used as a feedstock in low-temperature hydrogenation or hydrogenation cracking processes.

[0096] The 10% distillation temperature (T10) of the thermally cracked oil 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 thermally cracked oil can be, for example, below 200°C, or below 190°C or below 180°C.

[0097] That is, the 10% distillation temperature (T10) of the thermal cracking 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℃.

[0098] The 90% distillation temperature (T90) of the thermally cracked 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 thermally cracked oil can be, for example, 650°C or lower, preferably 600°C or lower, and more preferably 550°C or lower.

[0099] That is, the 90% distillation temperature (T90) of the thermal cracking oil 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℃, 4 10~650℃, 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℃.

[0100] Thermolytic cracking oil may contain low-boiling-point oil with a boiling point below 350°C, and further contain high-boiling-point oil with a boiling point above 350°C.

[0101] The content of high-boiling-point oil in the thermal cracking oil is not particularly limited, but it is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less, based on the total amount of thermal cracking oil. By adjusting the content of high-boiling-point oil in the thermal cracking 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 in a series of processes.

[0102] In addition, the content of high-boiling-point oil in the thermal cracking oil, based on the total amount of thermal cracking oil, can be, for example, 5% or more by mass, 8% or more by mass, or 10% or more by mass.

[0103] That is, the content of high-boiling-point oil in thermal cracking oil, based on the total amount of thermal cracking oil, can be, for example, 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, or 10-35% by mass.

[0104] Thermal cracking oil may contain nitrogen, sulfur, chlorine, halogens, etc.

[0105] The nitrogen content of the thermal cracking 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 there is a high nitrogen content in the thermal cracking oil, the nitrogen content is converted into gaseous components such as ammonia during the hydrogenation cracking process, and can be easily separated from the liquid product. Moreover, by feeding the liquid product with a significantly reduced nitrogen content to the steam cracking process, high-purity chemical products (chemical products mixed with less nitrogen content) can be easily obtained. The nitrogen content of the thermal cracking 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. If the nitrogen content is less than 20000 ppm by mass, the nitrogen content of the liquid product after the hydrogenation cracking process can be reduced more significantly.

[0106] That is, the nitrogen content of the thermal cracking 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.

[0107] The sulfur content of the thermal cracking 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 there is a high sulfur content in the thermal cracking oil, the sulfur is converted into gaseous components such as hydrogen sulfide during the hydrogenation cracking process, and can be easily separated from the liquid product. Moreover, by feeding the liquid product with a significantly reduced sulfur content to the steam cracking process, high-purity chemical products (chemical products mixed with less sulfur content) can be easily obtained. The sulfur content of the thermal cracking oil can be, for example, 30,000 ppm or less by mass, or 20,000 ppm or less by mass, or 10,000 ppm or less by mass. Thus, the sulfur content of the liquid product after the hydrogenation cracking process can be reduced more significantly.

[0108] That is, the sulfur content of the thermal cracking 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.

[0109] The chlorine content of the thermal cracking 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 there is a high chlorine content in the thermal cracking oil, the chlorine is converted into gaseous components such as hydrogen chloride during the hydrogenation cracking process, and can be easily separated from the liquid product. Moreover, by feeding the liquid product with a significantly reduced chlorine content to the steam cracking process, high-purity chemical products (chemical products mixed with less chlorine) can be easily obtained. The chlorine content of the thermal cracking 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 1000 ppm by mass or less, the chlorine content of the liquid product after the hydrogenation cracking process can be reduced more significantly. In addition, not only the chlorine content, but also other halogen elements can be within the same range.

[0110] That is, the chlorine content of the thermal cracking 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.

[0111] The residue components may be, for example, 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 components. The residue components may be recovered, for example, as solid components remaining in the pyrolysis furnace (solid components not discharged to the outside of the reaction system as pyrolysis gases).

[0112] The residue may be carbides formed by the thermal decomposition of waste tires or similar shredded materials. In this embodiment, the residue may be recovered in the form of carbides (carbide recovery process).

[0113] Carbides are predominantly carbon-based components. For example, carbides can be carbon concentrates primarily composed of carbon black. Carbides sometimes have agglomerated lumpy portions formed during pyrolysis. In such cases, powdered carbides are obtained by pulverizing the agglomerated carbides using a pulverizer or similar device.

[0114] That is, the carbide recovery step in the manufacturing method of this embodiment can be a step of pulverizing the residue components to obtain powdered carbides.

[0115] Powdered carbides are suitable for applications such as rubber additives, resin additives, and colorants.

[0116] It should be noted that, depending on the pyrolysis conditions, the residue sometimes contains rubber components, such as those from incompletely pyrolyzed waste. 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. For such carbides, the adhesiveness of the rubber components hinders pulverization, making pulverization using a pulverizer or similar equipment difficult. Furthermore, the blocky carbides are associated with poor dispersion in the parent material, making them unsuitable for use as rubber additives, resin additives, colorants, etc. In contrast, in the pyrolysis process of this embodiment, by employing the aforementioned pyrolysis conditions, the residual rubber components in the recovered carbides are reduced, enabling the efficient production of powdered carbides suitable for use as rubber additives, resin additives, colorants, etc.

[0117] The thermal pyrolysis process can be carried out, for example, by a thermal pyrolysis unit equipped with a thermal pyrolysis furnace. Figure 1 This is a schematic diagram showing an example of a thermoelectric pyrolysis device.

[0118] Figure 1 The pyrolysis apparatus includes: a heat exchanger 1 for heating oxygen-free gas; a pyrolysis unit 7 having a pyrolysis furnace 2 that internally houses waste 6 and an external heating mechanism 8 for heating the pyrolysis furnace 2 from the outside; an oil recovery unit 5 for cooling the pyrolysis gas generated in the pyrolysis unit 7 to recover the condensed oil (pyrolysis oil); a circulation path 4 for supplying the remaining gas after the oil recovery unit 5 has recovered the oil 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.

[0119] 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 to the heat exchanger 1 to supply oxygen-free gas from the oxygen-free gas supply source 3. In the circulation path 4 for circulating the residual gas recovered by the oil separation and recovery device 5 as oxygen-free gas back to the heat exchanger 1, the flow meter 9, the damper 10, the blower 11, and the hot blast furnace 14 are included.

[0120] Furthermore, in order to separate the recovered oil fractions according to their boiling points, the oil recovery unit 5 can be equipped with multiple distillation towers 12a and 12b. Each distillation tower 12 can be connected to a recovery tank 13 via piping at its lower part, where the recovered oil fractions can be stored. It should be noted that... Figure 1 The thermal cracking unit has multiple distillation columns 12a and 12b, but in this embodiment, the thermally cracked oil can be directly used as feedstock for the hydrogenation cracking process, so there can only be one distillation column. Additionally, 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.

[0121] The thermal cracking 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 cryogenic hydrogenation process. By removing at least a portion of the high-boiling-point oil from the thermal cracking oil, the formation of fouling in the heat exchangers and furnaces during the cryogenic hydrogenation and hydrogenation cracking processes can be suppressed, enabling long-term operation of the process. While not limiting, it is more preferable to remove, for example, at least a portion of the high-boiling-point oil with a boiling point exceeding 450°C.

[0122] One method for removing high-boiling-point oil is to cool the thermally cracked gas immediately generated during the thermal cracking process, separating it into thermally cracked oil containing a higher proportion of high-boiling-point oil and a gaseous component containing a higher proportion of low-boiling-point oil. The gaseous component containing a higher proportion of low-boiling-point oil is then further cooled, thereby separating it into a first gaseous component and thermally cracked oil containing a higher proportion of low-boiling-point oil. Alternatively, the thermally cracked oil can be heated and separated into low-boiling-point oil and high-boiling-point oil in a distillation column, but the method described is not limited to this.

[0123] The content of high-boiling-point oil in the thermal cracking oil obtained by removing a portion of the high-boiling-point oil before the low-temperature hydrogenation process (hereinafter also referred to as "fractionated thermal cracking oil") is not particularly limited, but is 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less, based on the total amount of fractionated thermal cracking oil before the low-temperature hydrogenation process. If the content of high-boiling-point oil in the fractionated thermal cracking oil before the low-temperature hydrogenation process is 40% by mass or less, the influence of easily weighted components such as heavy olefins and dienes can be suppressed.

[0124] In addition, the content of high-boiling-point oil in the thermally cracked oil after fractionation before the low-temperature hydrogenation process can be, for example, more than 1% by mass, more than 3% by mass, or more than 5% by mass, based on the total amount of thermally cracked oil after fractionation before the low-temperature hydrogenation process.

[0125] 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.

[0126] (Cryogenic hydrogenation process)

[0127] The low-temperature hydrogenation process is a process of hydrogenating feedstock containing at least a portion of thermally cracked oil at a low temperature of 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0128] The feedstock in the low-temperature hydrotreating process can contain thermally cracked oil or a fraction obtained by fractionating thermally cracked oil. Furthermore, the feedstock in the low-temperature hydrotreating process can contain components other than thermally cracked oil, or the thermally cracked oil can be used directly as the feedstock.

[0129] As part of the feedstock in the cryogenic hydrotreating process, recycled oil containing at least a portion of the light and heavy components obtained in the hydrocracking 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 the cryogenic hydrotreating and hydrocracking processes can be reduced, improving the stability of process operation. Examples of dilution hydrocarbons include kerosene fractions, light oil fractions, vacuum distillation light oil fractions from crude oil obtained from an atmospheric distillation unit, LCO from an FCC unit, and subsequently, product kerosene and product light oil.

[0130] In the low-temperature hydrogenation process, the amount of recycle oil 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, relative to the total amount of recycle oil and thermal cracked oil in the feedstock.

[0131] The cryogenic hydrogenation process 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 and bringing it into contact with the catalyst within the reactor.

[0132] 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, the hydrogenation catalyst preferably includes, for example, Ni-based or Co-based catalysts. Ni-based catalysts refer to catalysts having Ni as the active metal. Co-based catalysts refer to catalysts having Co as the active metal. As a hydrogenation catalyst, one type of hydrogenation catalyst or multiple types of hydrogenation catalysts can be used.

[0133] 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℃, and even more preferably above 240℃, a low-temperature hydrogenated oil with a reduced diene value can be obtained.

[0134] 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.

[0135] 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.

[0136] When using a flow-through reactor for cryogenic hydrogenation, the weight 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 weight space velocity (WHSV) of the feedstock oil can, for example, be 5 hours. －1 The following is preferred: 4h －1 The following is more preferably 3h －1 the following.

[0137] That is, the weight space velocity (WHSV) of the feedstock oil can be 0.1 to 5 h. －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 .

[0138] The cryogenic hydrogenation process is carried out in the presence of hydrogen. When using a flow-through 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.

[0139] 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.

[0140] The low-temperature hydrogenated oil obtained in the low-temperature hydrogenation process preferably has the following properties.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] In this invention, by reducing the amount of olefins, dienes, higher fatty acids, etc., which are the main factors of fouling due to polymerization in the thermal cracking oil processed in the low-temperature hydrogenation process in advance, the generation of fouling in the heat exchanger and heating furnace can be suppressed even when heated to the required high temperature zone in the later stage of the hydrogenation cracking process, thus enabling long-term operation of the process.

[0145] (Hydrogenation cracking process)

[0146] The hydrocracking process is a process of obtaining a second gaseous component, a light component with a boiling point below 350°C, and a heavy component with a boiling point above 350°C by hydrocracking a feedstock containing at least a portion of a low-temperature hydrogenated oil.

[0147] The feedstock oil in the hydrocracking process contains low-temperature hydrogenated oil, may contain a portion of thermally cracked oil, may contain a portion of the fraction obtained by fractionating thermally cracked oil, and may further contain other components.

[0148] The feedstock oil in the hydrocracking process contains low-boiling-point oil (boiling point below 350°C) and high-boiling-point oil (boiling point above 350°C), with the high-boiling-point oil content, for example, being less than 50% by mass based on the total amount of feedstock oil. By adjusting the cracking conditions in the hydrocracking 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, a higher content of high-boiling-point oil tends to make it more suitable as a feedstock and further improve the yield of chemical products. However, to reduce fouling and clogging in piping and heat exchangers throughout the process, it is preferable to reduce the amount of high-boiling-point oil mentioned above.

[0149] The content of high-boiling-point oil in the feedstock oil during the hydrogenation cracking process is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, and most preferably 5% by mass or less, based on the total amount of feedstock oil.

[0150] In addition, the content of high-boiling-point oil in the feedstock oil in the hydrogenation cracking process can be 1.0% by mass or more, 2.0% by mass or more, or 3.0% by mass or more, based on the total amount of feedstock oil.

[0151] The 10% distillation temperature of the feedstock oil in the hydrocracking 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 in the hydrocracking process can be, for example, below 200°C, below 190°C, or below 180°C.

[0152] That is, the 10% distillation temperature of the feedstock oil in the hydrogenation cracking 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℃.

[0153] The 90% distillation temperature of the feedstock oil in the hydrocracking process 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 in the hydrocracking process can be, for example, 650°C or lower, preferably 600°C or lower, and more preferably 550°C or lower.

[0154] That is, the 90% distillation temperature of the feedstock oil in the hydrocracking 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℃.

[0155] The feedstock oil used in the hydrocracking process may contain nitrogen, sulfur, chlorine, and other halogens.

[0156] The nitrogen content of the feedstock oil in the hydrocracking 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, since chemical products are manufactured through the hydrocracking and cracking processes, high-purity chemical products (chemical products with less nitrogen content) can be easily obtained even if the feedstock oil contains a high 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.

[0157] That is, the nitrogen content of the feedstock oil in the hydrocracking 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.

[0158] The sulfur content of the feedstock oil in the hydrocracking 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, since chemical products are manufactured through the hydrocracking and cracking processes, even if the feedstock oil contains a high sulfur content, high-purity chemical products (chemical products mixed with a low sulfur content) can be easily obtained. The sulfur content of the feedstock oil can be, for example, 30,000 ppm or less by mass, or 20,000 ppm or less by mass, or 10,000 ppm or less by mass.

[0159] That is, the sulfur content of the feedstock oil in the hydrocracking 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.

[0160] The chlorine content of the feedstock oil in the hydrocracking 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, since chemical products are manufactured through the hydrocracking and cracking processes, high-purity chemical products (chemical products mixed with less chlorine content) can be easily obtained even if the feedstock oil contains a high chlorine content. The chlorine content of the feedstock 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. Furthermore, not only the chlorine content, but also the other halogen element content can be within the same range.

[0161] That is, the chlorine content of the feedstock oil in the hydrocracking 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.

[0162] Hydrocracking can be a process of hydrocracking feedstock oil in the presence of a hydrocracking catalyst. Hydrocracking can be carried out, for example, by feeding feedstock oil into a reactor containing a hydrocracking catalyst and bringing it into contact with the catalyst within the reactor.

[0163] As a hydrogenation cracking catalyst, for example, a known hydrogenation cracking catalyst used in the hydrogenation cracking of hydrocarbon oils can be used.

[0164] In this embodiment, when the feedstock oil in the hydrocracking process contains high-boiling-point oil, the preferred hydrocracking catalyst is one with excellent hydrogenation capacity and the ability to efficiently hydrogenate and crack high-boiling-point oil. From the viewpoint of hydrogenation capacity, the hydrocracking catalyst preferably comprises, for example, a Ni-based catalyst. A Ni-based catalyst refers to a catalyst having Ni as an active metal.

[0165] The hydrogenation cracking process can be implemented using one type of hydrogenation cracking catalyst or multiple types of hydrogenation cracking catalysts. For example, in the hydrogenation cracking process, desulfurization / denitrification catalysts, high-cracking-capacity catalysts, and low-cracking-capacity catalysts, as described later, can be appropriately combined as hydrogenation cracking catalysts.

[0166] Desulfurization / denitrification catalysts can be hydrogenation cracking catalysts with excellent desulfurization and denitrification performance. Examples of desulfurization / denitrification catalysts include hydrogenation cracking catalysts formed by supporting active metals on an alumina-containing support. Such hydrogenation cracking catalysts tend to exhibit excellent desulfurization and denitrification performance.

[0167] The support for the catalyst used for desulfurization / 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 / denitrification, based on the total amount of the support, can be, for example, 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more.

[0168] The support for the desulfurization / denitrification catalyst may 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 contain at least one oxide selected from the following: silica, phosphorus, magnesium oxide, zirconium oxide, boron oxide, titanium oxide, calcium oxide, zinc, etc. From the viewpoints of desulfurization / denitrification performance, industrial manufacturing, and catalytic strength, the support for the desulfurization / denitrification catalyst preferably comprises silica, silica-alumina, silica-alumina-phosphorus, silica-magnesium oxide, alumina-silica-magnesium oxide, alumina-silica-zirconia, etc. It should be noted that the support for the desulfurization / denitrification catalyst can be crystalline or amorphous. The shape of the support for the desulfurization / denitrification catalyst is not particularly limited; for example, it can be spherical, cylindrical, trilobal, tetralobal, etc.

[0169] Examples of active metals used in desulfurization / denitrification catalysts include Ni, Mo, Co, W, and P. A desulfurization / denitrification catalyst may contain one or more active metals. From the viewpoint of easily achieving excellent hydrogenation capacity and enabling more efficient desulfurization / denitrification, a desulfurization / denitrification catalyst preferably contains at least Ni, and more preferably contains Ni and also Mo or W. The active metals can be activated by sulfidation treatment. By including sulfides of the aforementioned metals, particularly Ni, the desulfurization / denitrification catalyst more easily achieves excellent hydrogenation capacity.

[0170] Examples of high-cracking-capacity catalysts include hydrogenation cracking catalysts formed by supporting active metals on a zeolite-containing support. Such hydrogenation cracking catalysts tend to have smaller pores and excellent hydrogenation cracking capacity.

[0171] The support for the high-cracking-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-cracking-capacity catalyst, based on the total amount of the support, can be, for example, 2% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more.

[0172] The support for a high-cracking-capacity catalyst may 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, zinc, etc. From the viewpoints of cracking performance, desulfurization / denitrification performance, industrial manufacturing, and catalytic intensity, the support for a high-cracking-capacity catalyst preferably contains alumina, silica, silica-alumina, silica-alumina-phosphorus, silica-magnesium oxide, alumina-silica-magnesium oxide, alumina-silica-zirconia, etc. It should be noted that the support for a high-cracking-capacity catalyst can be crystalline or amorphous. The shape of the support for a high-cracking-capacity catalyst is not particularly limited; for example, it can be spherical, cylindrical, trilobal, tetralobal, etc.

[0173] Examples of active metals that can be used as high-cracking-capacity catalysts include Ni, Mo, Co, W, and P. A high-cracking-capacity catalyst may contain one or more active metals. From the viewpoint of easily achieving excellent hydrogenation capacity and more efficiently hydrogenating and cracking high-boiling-point oils, a high-cracking-capacity catalyst preferably contains at least Ni, and more preferably contains Ni and also Mo or W. The active metals can be activated by sulfidation treatment. By including sulfides of the aforementioned metals, particularly Ni, desulfurization / denitrification catalysts can more easily achieve excellent hydrogenation capacity.

[0174] Examples of low-cracking-capacity catalysts include hydrogenation cracking catalysts formed by supporting active metals on an alumina-containing support. Such hydrogenation cracking catalysts tend to have more pores than high-cracking-capacity catalysts and exhibit a milder hydrogenation cracking capacity than high-cracking-capacity catalysts.

[0175] The support for the low-cracking-capacity catalyst can be an alumina-containing support. The alumina content in the support of the low-cracking-capacity catalyst, based on the total amount of the support, can be, for example, 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more.

[0176] The support for a low-cracking-capacity catalyst may 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 contain at least one oxide selected from the following: silica, phosphorus, magnesium oxide, zirconium oxide, boron oxide, titanium oxide, calcium oxide, zinc, etc. From the viewpoints of cracking performance, desulfurization / denitrification performance, industrial manufacturing, and catalytic intensity, the support for a low-cracking-capacity catalyst preferably comprises silica, silica-alumina, silica-alumina-phosphorus, silica-magnesium oxide, alumina-silica-magnesium oxide, alumina-silica-zirconia, etc. It should be noted that the support for a low-cracking-capacity catalyst can be crystalline or amorphous. The shape of the support for a low-cracking-capacity catalyst is not particularly limited; for example, it may be spherical, cylindrical, trilobal, tetralobal, etc.

[0177] Examples of active metals suitable for low-cracking-capacity catalysts include Ni, Mo, Co, W, and P. A low-cracking-capacity catalyst may contain one or more active metals. From the viewpoint of more efficiently hydrogenating and cracking high-boiling-point oils, a low-cracking-capacity catalyst preferably contains at least Ni, and more preferably contains Ni and also Mo or W. The active metals can be activated by sulfidation treatment. Sulfides containing Ni, in particular, of the aforementioned metals, make it easier for desulfurization / denitrification catalysts to achieve excellent hydrogenation capacity.

[0178] In the hydrogenation cracking process, desulfurization / denitrification catalysts can be used in combination with cracking catalysts. The cracking catalyst can be a combination of high-cracking-capacity and low-cracking-capacity catalysts, or it can use only the high-cracking-capacity catalyst or only the low-cracking-capacity catalyst. Furthermore, the desulfurization / denitrification catalyst can be placed at least upstream of the high-cracking-capacity and low-cracking-capacity catalysts, or it can be placed both upstream and downstream of the high-cracking-capacity and low-cracking-capacity catalysts.

[0179] When the feedstock in the hydrocracking process contains nitrogen, the nitrogen in the feedstock may adhere to the active sites of high-cracking-capacity catalysts and low-cracking-capacity catalysts, thus reducing their cracking performance. If the feedstock comes into contact with a desulfurization / denitrification catalyst, the nitrogen in the feedstock is converted into ammonia, reducing the nitrogen content in the feedstock. Therefore, in the hydrocracking process, it is preferable to place the desulfurization / denitrification catalyst upstream of the high-cracking-capacity catalysts and low-cracking-capacity catalysts. That is, it is preferable to place the desulfurization / denitrification catalyst upstream of the hydrocracking unit described later. According to this configuration, even when the feedstock contains nitrogen, the reduction in the cracking performance of the high-cracking-capacity catalysts and low-cracking-capacity catalysts can be suppressed.

[0180] The hydrogenation cracking process can be implemented, for example, using a flow-through reactor. In this case, it is preferable to sequentially arrange a first catalyst layer containing a desulfurization / denitrification catalyst and a second catalyst layer containing a cracking catalyst from the inlet side within the flow-through reactor. Furthermore, a third catalyst layer containing different types of cracking catalysts with varying cracking capabilities and a fourth catalyst layer containing a desulfurization / denitrification catalyst can be further arranged downstream of the second catalyst layer.

[0181] The reaction temperature in the hydrogenation cracking 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 hydrogenation cracking 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 hydrogenation cracking 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.

[0182] The reaction pressure in the hydrogenation cracking process is not particularly limited, but can be, for example, 1 MPaG or more, preferably 3 MPaG or more, and more preferably 5 MPaG or more. Furthermore, the reaction pressure in the hydrogenation cracking process is not particularly limited, but can be, for example, 20 MPaG or less, preferably 19 MPaG or less, and more preferably 18 MPaG or less.

[0183] That is, the reaction pressure in the hydrogenation cracking 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.

[0184] When using a flow-through reactor to implement the hydrocracking process, the weight 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 weight space velocity (WHSV) of the feedstock oil can, for example, be 5 hours. －1 The following is preferred: 4h －1 The following is more preferably 3h －1 the following.

[0185] That is, the weight space velocity (WHSV) of the feedstock oil can be 0.1 to 5 h. －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 .

[0186] The hydrogenation cracking process is carried out in the presence of hydrogen. When using a flow-through reactor to carry out the hydrogenation cracking 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. In addition, 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.

[0187] 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.

[0188] In the hydrogenation cracking process, the feedstock oil is hydrogenated to obtain a second gaseous component, a light component with a boiling point below 350°C, and a heavy component with a boiling point above 350°C.

[0189] The second gaseous component can be, for example, a gaseous component in the products generated by hydrogenation cracking at room temperature (20°C). The second gaseous component can include, for example, hydrogen and hydrocarbons with 1 to 4 carbon atoms.

[0190] The second gas component can be used, for example, in combustion gases used to heat the pyrolysis section in the pyrolysis process, or in combustion gases from heating furnaces in other processes.

[0191] Light components can be, for example, hydrocarbon oils with a boiling point below 350°C, which are produced by hydrocracking. These light components are supplied to the steam cracking process.

[0192] The sulfur content in the light components is, for example, 1500 ppm by mass or less. From the viewpoint of reducing impurities 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 1000 ppm by mass or less, and more preferably 900 ppm by mass or less.

[0193] The nitrogen content in the light components is, for example, 25 ppm by mass or less. From the viewpoint of reducing impurities 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 20 ppm by mass or less, and more preferably 15 ppm by mass or less.

[0194] The chlorine content in the light components is, for example, 20 ppm by mass or less. From the viewpoint of reducing impurities 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 15 ppm by mass or less, and more preferably 10 ppm by mass or less. In addition, it is preferable that not only the chlorine content but also the content of other halogen elements is within the same range.

[0195] Heavy components may be, for example, hydrocarbon oils with a boiling point exceeding 350°C, which are products generated through hydrogenation cracking.

[0196] Heavy components can be reused, for example, as part or all of the feedstock in low-temperature hydrotreating or hydrocracking processes. Additionally, heavy components can be used, for example, in fuel oil used to heat the pyrolysis section in a pyrolysis process, in fuel oil from furnaces in other processes, or processed using FCC units in other petroleum refining processes.

[0197] (Steam pyrolysis process)

[0198] The steam cracking process is a process of steam cracking feedstock oil containing a portion of the light components obtained in the hydrogenation cracking process to obtain chemical products and a feedstock for carbide manufacturing containing 10% heavy fraction with a distillation temperature of 190°C or higher. In the steam cracking process, by heat-treating the steam cracking feedstock oil together with steam, light components are cracked to generate components useful as chemical products. Furthermore, the 10% heavy fraction with a distillation temperature of 190°C or higher obtained in the steam cracking process can be appropriately used as a feedstock for carbide manufacturing.

[0199] In the steam cracking process, a portion or all of the light components obtained from the hydrogenation cracking process can be used for steam cracking. In addition to light components, the steam cracking feedstock may also contain ethane, naphtha, kerosene, and light oil fractions from petroleum. The light components can also be used directly as the steam cracking feedstock.

[0200] 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, etc.

[0201] 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. That is, the reaction temperature for steam pyrolysis can be, for example, 650–1000°C, 650–950°C, 650–900°C, 700–1000°C, 700–950°C, 700–900°C, 750–1000°C, 750–950°C, or 750–900°C.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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 C9 aromatic compounds containing olefins for resin conversion.

[0209] In the steam cracking process, in addition to chemical products, light fractions can be further obtained. Examples of light fractions include methane, ethane, propane, butane, pentane, and hexane.

[0210] In the steam cracking process, in addition to chemical products, heavy fractions can be further obtained. The heavy fractions obtained in the steam cracking process of this embodiment tend to have higher aromatic content and can be appropriately used as raw materials for the manufacture of carbides (especially carbon black).

[0211] The 10% distillation temperature of the aforementioned heavy fraction can, for example, be above 190°C or above 200°C. The 10% distillation temperature of the aforementioned heavy fraction can, for example, be below 250°C or below 240°C. The 90% distillation temperature of the aforementioned heavy fraction can, for example, be above 450°C or above 500°C. The 90% distillation temperature of the aforementioned heavy fraction can, for example, be below 750°C or below 700°C.

[0212] 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.

[0213] The aromatic content of the aforementioned heavy fraction may be, for example, 30% by mass or more, preferably 35% by mass or more, and more preferably 40% by mass or more. Alternatively, the aromatic content of the aforementioned heavy fraction may be, for example, 90% by mass or less.

[0214] That is, the aromatic components of the above-mentioned heavy fraction can be, for example, 30-90% by mass, 35-90% by mass, or 40-90% by mass.

[0215] The steam cracking process can be carried out, for example, by a steam cracking unit equipped with a reactor.

[0216] (Carbide manufacturing process)

[0217] The manufacturing method of this embodiment may further include a carbide manufacturing process in which carbides are obtained by thermal decomposition or incomplete combustion of raw materials for carbide manufacturing.

[0218] The raw materials for carbide manufacturing obtained from the steam cracking process have a high content of aromatic components, so there is a tendency to obtain carbides (especially carbon black) with excellent production yields.

[0219] Thermal pyrolysis or incomplete combustion in the carbide manufacturing process can be implemented, for example, by using the soft carbon black manufacturing apparatus disclosed in Japanese Patent Application Publication No. 61-34071 (applicant: Asahi Carbon Co., Ltd.), spraying the heavy fraction obtained in the steam pyrolysis process into a combustion reaction chamber containing high-temperature oxygen, and then quenching it with water or the like. It should be noted that incomplete combustion can refer to combustion in a low-oxygen concentration atmosphere. Low oxygen concentration refers to a concentration lower than the atmospheric oxygen concentration (approximately 21% by volume).

[0220] There is no particular limitation on the temperature of thermal decomposition or incomplete combustion in the carbide manufacturing process. For example, it can be above 1200°C, or above 1300°C, 1400°C, or 1500°C. In addition, the temperature of thermal decomposition or incomplete combustion in the carbide manufacturing process can be below 1900°C, or below 1800°C, 1700°C, or 1600°C.

[0221] That is, the temperature of thermal decomposition or incomplete combustion in the carbide manufacturing process can be, for example, 1200–1900℃, 1200–1800℃, 1200–1700℃, 1200–1600℃, 1300–1900℃, 1300–1800℃, 1300–1700℃, 1300–1600℃, 1400–1900℃, 1400–1800℃, 1400–1700℃, 1400–1600℃, 1500–1900℃, 1500–1800℃, 1500–1700℃, or 1500–1600℃.

[0222] The carbides obtained in the carbide manufacturing process are, for example, carbon black.

[0223] Figure 2 This is a schematic diagram illustrating an example of a system for implementing the manufacturing method of this embodiment. Figure 2 The system 100 shown includes a thermal cracking unit 110, a first separation unit 111, a fine pulverization unit 112, a low-temperature hydrogenation unit 115, a hydrogenation cracking unit 120, a second separation unit 121, a steam cracker 130, and a carbide manufacturing unit 140.

[0224] In the aforementioned system 100, waste S1 is first supplied to a pyrolysis unit 110, where it undergoes pyrolysis. In the pyrolysis unit 110, a mixture S4 is generated, consisting of a first gaseous component S2, pyrolysis oil S3, residue components, and metallic components. The first gaseous component S2 can be discharged outside the system or reused as oxygen-free gas in the pyrolysis unit 110. The pyrolysis oil S3 is supplied to a hydrogenation pyrolysis unit 120. The mixture S4 is supplied to a first separation unit 111, where it is separated into residue components S5 and metallic components S6. The residue component S5 is then pulverized in a fine pulverization unit 112 and recovered as powdered carbide S7.

[0225] In the cryogenic hydrogenation unit 115, cryogenic hydrogenated oil S8 is produced by cryogenic hydrogenation of thermally cracked oil S3. Cryogenic hydrogenated oil S8 is then supplied to the hydrogenation cracking unit 120.

[0226] In the hydrocracking unit 120, a second gaseous component S9 and a hydrocracking oil S10 are produced through the hydrocracking of the thermal cracking oil S3. The second gaseous component S9 can be discharged outside the system or used as combustion gas for heating the thermal cracking section in the thermal cracking process or as combustion gas for furnaces in other processes. The hydrocracking oil S10 is supplied to the second separation unit 121, where it is fractionated into a light component S11 and a heavy component S12. The light component S11 is supplied to the steam cracker 130. The heavy component S12 can be recovered as a heavy oil fraction and reused in the hydrocracking unit 120, or used as combustion oil for heating the thermal cracking section in the thermal cracking process or as combustion oil for furnaces in other processes. Furthermore, the recycled oil S17 containing the light component S11 and the heavy component S12 can be reused in the cryogenic hydrotreating unit 115.

[0227] In steam pyrolysis unit 130, the light component S11 is steam-cracked to form product gas S13, product oil S14, and heavy fraction S15. Product gas S13 and product oil S14 contain C9 aromatic components containing olefins used for resin conversion, such as ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, indene, and methylstyrene, which are useful as chemical products. Chemical products are obtained by appropriately separating and recovering product gas S13 and product oil S14. Heavy fraction S15 is fed to carbide manufacturing unit 140. In carbide manufacturing unit 140, carbide S16 is formed by thermal cracking of heavy fraction S15.

[0228] (Manufacturing method of synthetic rubber)

[0229] The butadiene manufacturing method of this embodiment includes a polymerization step, which obtains synthetic rubber by using the butadiene obtained by the above manufacturing method as a raw material for synthetic rubber through a polymerization reaction.

[0230] 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.

[0231] The monomer can be butadiene alone, or other monomers known for use in synthetic rubbers, in addition to butadiene, can be used depending on the composition and properties of the target synthetic rubber. Other monomers for synthetic rubbers include conjugated diene compounds other than butadiene and aromatic vinyl compounds.

[0232] 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.

[0233] 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, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, tert-butoxystyrene, vinylbenzyldimethylamine, (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.). One or more aromatic vinyl compounds may be used.

[0234] In addition to monomers, polymerization compositions may also contain conventionally known additives, solvents, etc. Examples of additives include polymerization initiators, emulsifiers, and surfactants.

[0235] 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, arsenic lithium, naphthyl lithium, 1,3-bis(1-lithium-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentyl)dilithium, sodium naphthyl, potassium naphthyl, and potassium ethoxy.

[0236] (tire)

[0237] The tire of this embodiment comprises synthetic rubber obtained by the above-described method for manufacturing synthetic rubber.

[0238] (Tire manufacturing method)

[0239] The tire manufacturing method of this embodiment includes a vulcanization process, in which a tire is obtained by vulcanizing at least a portion of the synthetic rubber obtained by the above-described synthetic rubber manufacturing method as a raw material for the tire.

[0240] In the vulcanization process, a tire can be obtained by vulcanizing a vulcanizing composition containing at least synthetic rubber using conventionally known methods. 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.

[0241] 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.

[0242] Examples of sulfur-based sulfur-containing agents include powdered sulfur, precipitated sulfur, highly dispersed sulfur, surface-treated sulfur, insoluble sulfur, dithiodimorpholine, disulfide alkylphenol, zinc oxide, magnesium oxide, lead oxide, p-quinone dioxime, p-benzoylquinone dioxime, tetrachlorop-benzoquinone, poly(p-dinitrobenzene), methylene diphenylamine, phenolic resin, brominated alkylphenol resin, and chlorinated alkylphenol resin.

[0243] Examples of vulcanization accelerators include thiuram-based accelerators such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM); aldehyde-amine-based accelerators such as hexamethylenetetramine; guanidine-based accelerators such as diphenylguanidine (DPG); thiazole-based accelerators such as 2-mercaptobenzothiazole (MBT) and dibenzothiazole disulfide (DM); sulfonamide-based accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and N-tert-butyl-2-benzothiazole sulfenamide (BBS); and dithiocarbamate-based accelerators such as zinc dimethyl dithiocarbamate (ZnPDC).

[0244] 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.

[0245] Examples of anti-aging agents include, for example, hindered amine and hindered phenolic compounds of aliphatic and aromatic types.

[0246] Examples of antioxidants include butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA).

[0247] Examples of colorants include titanium dioxide, zinc oxide, ultramarine, Indian red, zinc barium white, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, inorganic pigments, azo pigments, and copper phthalocyanine pigments.

[0248] There are no particular restrictions on the shape, structure, size, and material of tires; they can be selected appropriately according to their purpose. Furthermore, there are no particular restrictions on the uses of tires; examples include tires for passenger cars, high-load tires, motorcycle (motorized two-wheeled vehicle) tires, and studless anti-skid tires.

[0249] (Management methods for renewable products)

[0250] In recent years, in order to sell environmentally friendly products that use plant-based raw materials, recycled materials, etc. in a more attractive manner, the quality balance method (hereinafter also known as the material balance method) has attracted much attention in various industries such as the chemical industry, the iron and steel industry, and the aluminum industry.

[0251] It is hoped that the value of each product generated using the manufacturing method of the present invention, which utilizes waste tires, can be allocated as a renewable product using a simple and reliable method and by means of mass balance.

[0252] Therefore, the present invention provides a management method in which, when manufacturing chemical products using the manufacturing method of the present invention described above, the value of each product as a renewable product can be allocated according to the proportion of renewable raw materials contained in waste tires using a simple and reliable method.

[0253] In this specification, "renewable raw materials" refers to raw materials from renewable organic resources. Renewable raw materials are not intended to be limited to bio-derived products, but should be broadly understood as raw materials belonging to renewable organic resources. For example, the main point is that even petroleum derivatives include raw materials derived from recycled products using petroleum derivatives, such as waste tires.

[0254] Here, the quality balancing method refers to the following approach: for example, in the circulation / processing process from raw materials to products, when raw materials with specific characteristics, such as biomass raw materials, are mixed with raw materials that do not have such characteristics, a portion of the product is allocated a certificate (Credit) based on the proportion of the raw material with that characteristic.

[0255] Because the mass balance method (material balance method) allows manufacturers to arbitrarily allocate biomass fractions as certificates, its legitimacy is usually proven through certification by a third-party certification body. Examples of such third-party certification bodies include ISCC (International Sustainable Development and Carbon Certification) and RSB (Roundtable on Sustainable Biomaterials).

[0256] (Management methods for chemical products implemented using management devices)

[0257] The chemical product management method of the present invention can be used when manufacturing chemical products using waste tires.

[0258] The management method of the present invention is to use a management device to allocate the value of chemical products as renewable products based on the proportion of renewable raw materials contained in waste tires using a mass balance method.

[0259] The management method of the present invention includes, for example, a step (V), in which a management device, described later, confirms that a chemical product has been obtained (the management device acquires information showing that a chemical product has been obtained using waste tires); and a step (Z), in which the management device confirms the proportion of the product allocated as a value of a renewable product (the management device acquires information showing the proportion of the product allocated as a value of a renewable product).

[0260] The process (V) that confirms the chemical product includes the following processes (V-1), (V-2), (V-3), (V-4), and (V-5).

[0261] Process (V-1) is the process by which the management device confirms that the aforementioned waste tires, which are fed into a thermal pyrolysis unit to obtain thermal pyrolysis oil through thermal pyrolysis treatment at 350°C to 750°C, have generated the aforementioned thermal pyrolysis oil.

[0262] Step (V-2) is the process by which the management device confirms that the aforementioned thermally cracked oil is generated from the aforementioned low-temperature hydrogenated oil in a low-temperature hydrogenation unit where at least a portion of the feedstock containing the aforementioned thermally cracked oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0263] Step (V-3) is the process by which the management device confirms that the light components are generated from the low-temperature hydrogenated oil fed into a hydrogenation cracking unit that performs hydrogenation cracking treatment on feedstock oil containing at least a portion of the low-temperature hydrogenated oil at a temperature higher than the low-temperature hydrogenation treatment.

[0264] Step (V-4) is the process by which the management device confirms that the aforementioned light components are obtained from the aforementioned chemical products by steam cracking the steam cracking feedstock containing at least a portion of the aforementioned light components in a steam cracker.

[0265] Step (V-5) is the process by which the management device confirms that the aforementioned chemical product is obtained from the aforementioned waste tires through sequential processing using the aforementioned thermal cracking unit, the aforementioned hydrogen cracking unit, the aforementioned hydrogen cracking unit, and the aforementioned steam cracker.

[0266] The process (Z) for determining the proportion of products allocated as renewable products includes the following processes (Z-1), (Z-2), (Z-3), and (Z-4).

[0267] Process (Z-1) is the process by which the management device selects products from the products obtained from the steam pyrolysis unit above as renewable products for distribution.

[0268] 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) relative to the product obtained from the steam pyrolyzer, and allocates it as a renewable product.

[0269] 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 tires.

[0270] Step (Z-4) is the process by which the management device compares the value of the aforementioned ratio (P) with the value of the aforementioned ratio (Q) and confirms that the value of the aforementioned ratio (P) is less than or equal to the value of the aforementioned ratio (Q).

[0271] 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.

[0272] Process (Z-1): If the products obtained from the steam cracker are ethylene, propylene, butadiene and other products, butadiene is selected.

[0273] Process (Z-2): The products obtained from the steam cracker are ethylene, propylene, butadiene, and other products, with each product accounting for 10% by mass of ethylene, 10% by mass of propylene, 10% by mass of butadiene, and 70% by mass of other products. Therefore, the proportion (P) allocated as a renewable product is determined within the 10% by mass of butadiene product.

[0274] Process (Z-3): When the waste tires contain 5% by mass of recyclable materials and 95% by mass of non-recyclable materials, ensure that the proportion (Q) of recyclable materials is 5% by mass.

[0275] Step (Z-4): Compare the value of the proportion (P) with the value of the content proportion (Q) and confirm that the value of the proportion (P) is less than or equal to 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 5% by mass or less.

[0276] That is, if the proportion (Q) of renewable raw materials is 5% by mass, then 5% by mass of the butadiene product allocated as a renewable product can be allocated as renewable butadiene.

[0277] 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 waste tires.

[0278] It should be noted that, according to third-party certification bodies, in the quality balance method (material balance method), the butadiene products other than (P) mass% in 10% mass of butadiene products (10-(P) mass% butadiene products) actually also contain renewable components. However, since a certificate for 100% renewable butadiene has been assigned to (P) mass% butadiene, it is not considered as renewable butadiene.

[0279] 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 values ​​set for convenience in order to make the present invention easy to understand, but are not limited to these values.

[0280] <Management Devices and Procedures>

[0281] 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 can be executed by a computer having a control unit constituting the management device.

[0282] 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 on the management device.

[0283] As a preferred embodiment of the management device of the present invention, the following management devices can be cited.

[0284] "A management device for chemical products, used when manufacturing chemical products from waste tires."

[0285] The aforementioned management device is a device that allocates the value of the aforementioned chemical products as renewable products using a mass balance method based on the proportion of renewable raw materials contained in the aforementioned waste tires.

[0286] The aforementioned management device has a confirmation unit (I) that confirms the receipt of the aforementioned chemical product.

[0287] The aforementioned confirmation unit (I) includes the following mechanisms (V-1), (V-2), (V-3), (V-4), and (V-5).

[0288] The aforementioned mechanism (V-1) is the mechanism that confirms the generation of the aforementioned pyrolysis oil from the aforementioned waste tires in a pyrolysis unit that performs pyrolysis treatment on the aforementioned waste tires at 350°C to 750°C to obtain pyrolysis oil.

[0289] The aforementioned mechanism (V-2) is the mechanism that confirms the generation of the aforementioned low-temperature hydrogenated oil from the aforementioned thermally cracked oil in a low-temperature hydrogenation unit where at least a portion of the feedstock containing the aforementioned thermally cracked oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0290] The aforementioned apparatus (V-3) is an apparatus that confirms the generation of the aforementioned light components from the aforementioned low-temperature hydrogenated oil in a hydrogenation cracking unit whereby a feedstock containing at least a portion of the aforementioned low-temperature hydrogenated oil is subjected to hydrogenation cracking treatment at a temperature higher than the aforementioned low-temperature hydrogenation treatment to obtain light components with a boiling point of less than 350°C.

[0291] The aforementioned organization (V-4) is the organization that confirms that the aforementioned chemical product is obtained from the aforementioned light components fed into a steam pyrolysis unit that performs steam pyrolysis treatment on steam pyrolysis feedstock containing at least a portion of the aforementioned light components.

[0292] The aforementioned organization (V-5) is the one that confirms that the aforementioned chemical products can be obtained from the aforementioned waste tires by sequentially processing them using the aforementioned pyrolysis unit, the aforementioned low-temperature hydrogenation unit, the aforementioned hydrogenation pyrolysis unit, and the aforementioned steam pyrolysis unit.

[0293] The aforementioned management device has a confirmation unit (I) that confirms the proportion of products allocated as renewable products.

[0294] The aforementioned confirmation department (I) includes the following mechanisms (Z-1), (Z-2), (Z-3), and (Z-4).

[0295] The aforementioned mechanism (Z-1) is a mechanism for selecting and distributing products as renewable products from the products obtained by the aforementioned steam pyrolysis unit.

[0296] The aforementioned mechanism (Z-2) is a mechanism that determines the value of the proportion (P) to be allocated as a renewable product from the proportion of the product selected in the aforementioned mechanism (Z-1) relative to the product obtained from the aforementioned steam pyrolyzer.

[0297] The aforementioned organization (Z-3) is responsible for determining the proportion (Q) of renewable raw materials contained in the aforementioned waste tires.

[0298] The aforementioned mechanism (Z-4) compares the value of the aforementioned proportion (P) with the aforementioned value containing proportion (Q) and confirms that the value of the aforementioned proportion (P) is lower than or equal to the value containing proportion (Q).

[0299] As a preferred embodiment of the management procedure of the present invention, the following management procedure can be cited.

[0300] "A management procedure for chemical products, which is a management procedure for chemical products implemented using management devices when manufacturing chemical products from waste tires."

[0301] The aforementioned management procedure is a process that uses the aforementioned management device to allocate the value of the aforementioned chemical products as renewable products based on the proportion of renewable raw materials contained in the aforementioned waste tires, using a mass balance method.

[0302] The above management procedures cause the computer to perform the following processes:

[0303] (V-1): It is confirmed that the aforementioned waste tires, when fed into a pyrolysis unit that performs pyrolysis treatment on the aforementioned waste tires at 350°C to 750°C to obtain pyrolysis oil, generate the aforementioned pyrolysis oil.

[0304] (V-2): This refers to the process of generating the aforementioned low-temperature hydrogenated oil from the aforementioned thermally cracked oil in a low-temperature hydrogenation unit where at least a portion of the feedstock containing the aforementioned thermally cracked oil is subjected to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil.

[0305] (V-3): This is the process of generating the light components from the low-temperature hydrogenated oil in a hydrogenation cracking unit where at least a portion of the feedstock oil containing the low-temperature hydrogenated oil is subjected to hydrogenation cracking at a temperature higher than the low-temperature hydrogenation treatment to obtain light components with a boiling point of less than 350°C.

[0306] (V-4): This is the process of obtaining the chemical product from the light components fed into a steam pyrolysis reactor that performs steam pyrolysis on at least a portion of the steam pyrolysis feedstock containing the light components described above.

[0307] (V-5): This refers to the process of obtaining the chemical product from the waste tires by sequentially processing them using the aforementioned thermal cracking unit, the aforementioned low-temperature hydrogenation unit, the aforementioned hydrogenation cracking unit, and the aforementioned steam cracker.

[0308] The above management procedures cause the computer to perform the following processes:

[0309] The aforementioned management method includes a process (Z) for determining the proportion of products allocated as renewable resources.

[0310] (Z-1): The product selected as a renewable product for allocation from the products obtained from the steam pyrolysis unit described above.

[0311] (Z-2): The value of the proportion (P) to be allocated as a renewable product from the proportion of the product selected in the above process (Z-1) relative to the product obtained from the above steam pyrolysis unit.

[0312] (Z-3): Determine the value of the proportion (Q) of renewable raw materials contained in the above-mentioned waste tires.

[0313] (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 lower than the value of the above containing proportion (Q).

[0314] <<Management Device>>

[0315] As described above, the management device is an apparatus for performing the management method of the present invention.

[0316] according to Figure 3 A preferred embodiment of the management device will be described.

[0317] The management device 100 has a control unit 110 and a storage unit 120.

[0318] 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.

[0319] The hardware and functional configuration of the management device 100 will be described.

[0320] <<Hardware Composition of the Management Device>>

[0321] Figure 4 This is a block diagram illustrating an example of the hardware configuration of the management device 100.

[0322] like Figure 4 As shown, the management device 100 has the following components. Each component is connected via a bus 207.

[0323] CPU 201 is a processing device (computer) that performs various controls and calculations. CPU 201 performs 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.

[0324] In addition, CPU 201 controls the operation of the entire management device 100. It should be noted that in this embodiment, the device that controls the operation of the entire management device 100 is CPU 201, but it is not limited to this. For example, it can also be FPGA (Field Programmable Gate Array), etc.

[0325] 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 a network, LAN (Local Area Network), WAN (Wide Area Network), etc. The management device 100 can retrieve and execute the management program and various databases from these other information processing devices.

[0326] The main storage device 202 is a computer-readable storage medium that stores various programs and data required to execute those programs.

[0327] The main storage device 202 has ROM and RAM (not shown).

[0328] ROM stores various programs such as BIOS.

[0329] RAM functions as the scope of work that the CPU 201 can execute when various programs stored in ROM are run. 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.

[0330] 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 be a removable storage device such as a CD drive, DVD drive, or BD drive.

[0331] 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 (LCD) or an organic EL display.

[0332] The input device 205 is not particularly restricted as long as it can accept the various requirements of the management device 100, and can appropriately use known input devices, such as keyboards, mice, touch panels, etc.

[0333] The communication interface (communication I / F) 206 is not particularly restricted and can be any known communication interface, such as wireless or wired communication equipment.

[0334] The processing function of the management device 100 can be realized through the hardware configuration described above.

[0335] <<Functional Composition of Management Device>>

[0336] Return to Figure 3The management device 100 has a control unit 110 and a storage unit 120. The control unit 110 controls the entire management device 100.

[0337] The control unit 110 has a confirmation unit (I) 130, a comparison unit 140, and a notification unit (output unit) 150.

[0338] The confirmation unit (I) of the control unit 110 performs the confirmation operations described in the above mechanisms (V-1) to (V-5).

[0339] 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 from the steam pyrolysis unit to be allocated as a renewable product; in the above-mentioned mechanism (Z-2), the value of the proportion (P) of the product selected in the above-mentioned mechanism (Z-1) relative to the product obtained from the steam pyrolysis unit is determined; in the above-mentioned mechanism (Z-3), the value of the proportion (Q) of renewable raw materials contained in waste tires is obtained; in the above-mentioned mechanism (Z-4), the value of the proportion (P) is compared with the value of the proportion (Q), and the value of the proportion (P) is confirmed to be less than or equal to the value of the proportion (Q) (the information that the value of the proportion (P) is less than or equal to the value of the proportion (Q) is obtained).

[0340] The comparison unit 140 of the control unit 110 performs the following comparison operation: in the above mechanism (Z-4), the value of the ratio (P) is compared with the value containing the ratio (Q) so that the confirmation unit (I) can make a confirmation.

[0341] When the value of the proportion (P) is less than or equal to the value of the proportion (Q), the notification unit 150 of the control unit 110 notifies (outputs) that the selected product can be allocated (P) mass% as a renewable product in the product. On the other hand, when the value of the proportion (P) exceeds the value of the proportion (Q), it notifies (outputs) that it has exceeded the limit.

[0342] That is, after the management device 100 executes the management method, it outputs 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 tires.

[0343] 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 that stores a computer program and a management program that causes the control unit 110, which includes a computer, to execute the management method.

[0344] The amount and yield of products obtained from each device can be determined by measurement. However, yield results can be obtained not only by actual measurement, but also theoretically calculated using the reaction database 160, or predicted based on accumulated past data.

[0345] Next, the processing order of the management procedure will be explained. Figure 5 This is a flowchart illustrating an example of the processing sequence of the management procedure of the control unit 110 of the management device 100. Hereinafter, refer to... Figure 5 Please provide an explanation.

[0346] In step S101, the confirmation unit 130 of the control unit 110 of the management device 100 obtains information related to the pyrolysis unit and moves the processing to step S102.

[0347] In step S102, the confirmation unit 130 of the control unit 110 of the management device 100, for example, confirms that thermally pyrolyzed oil (OUT) is generated from waste tires (IN) based on information output from the thermal pyrolysis unit. If it is confirmed that thermally pyrolyzed oil (OUT) has been generated, the processing is moved to step S103.

[0348] In step S103, the confirmation unit 130 of the control unit 110 of the management device 100 obtains information related to the cryogenic hydrogenation unit and moves the processing to step S104.

[0349] In step S104, the confirmation unit 130 of the control unit 110 of the management device 100, for example, confirms that cryogenic hydrogenated oil (OUT) has been generated from thermal cracking oil (IN) based on information output from the cryogenic hydrogenation unit. Then, it similarly confirms that light components have been generated from the cryogenic hydrogenated oil fed into the hydrocracking unit. If it is confirmed that a chemical product is obtained from the light components fed into the steam cracker, the process is moved to step S105.

[0350] In step S105, the confirmation unit 130 of the control unit 110 of the management device 100 confirms, for example, that the thermal cracking unit, the low-temperature hydrogenation unit, the hydrogenation cracking unit, and the steam cracker have been processed sequentially based on information output from the thermal cracking unit, the low-temperature hydrogenation unit, the hydrogenation cracking unit, and the steam cracker. As a result of these processes, it is confirmed that chemical products (OUT) have been generated from waste tires (IN). If it is confirmed that chemical products have been generated, the processing is moved to step S106.

[0351] In step S106, the confirmation unit 130 of the control unit 110 of the management device 100 is activated by the input device within the management device 100. Figure 4The input device 205 receives information selected by the operator when distributing the product generated from the steam pyrolyzer as a renewable product, and moves the processing to step S107.

[0352] In step S107, the confirmation unit 130 of the control unit 110 of the management device 100 is activated by the input device within the management device 100. Figure 4 The input device 205 receives the value of the proportion (P) set by the operator when allocating the selected product as a renewable product, and moves the process to step S108.

[0353] 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 tires fed into the pyrolysis unit, and moves the processing to step S109.

[0354] 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.

[0355] 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 less than or equal to the value containing the ratio (Q) based on the comparison result of the ratio (P) value and the value containing the ratio (Q) performed by the comparison unit 140 of the control unit 110 of the management device 100. If the value of the ratio (P) value is less than or equal to the value containing the ratio (Q), the process ends.

[0356] Upon completion of this process, 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 tires. The allocation result is notified to the user via the notification unit 150 of the control unit 110 of the chemical product management device 100. That is, as described above, after executing the chemical product management method, the chemical product management device 100 outputs the result 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 tires.

[0357] It should be noted that if the conditions are not met in 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 reconsider the type of product selected above, reconsider the value of the proportion (P) of the selected product, reconsider the value of the proportion (Q) of renewable raw materials, and further reconsider various conditions such as reaction conditions, and try to process again.

[0358] The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.

[0359] Example

[0360] The present invention will be described in more detail below through embodiments, but the present invention is not limited to these embodiments.

[0361] In the following embodiments, component analysis and evaluation were performed using the following methods.

[0362] - Distillation properties: JIS K 2254 (Petroleum products - Distillation test methods - Part 7: Gas chromatography)

[0363] - Nitrogen composition: JIS K 2609 (Crude oil and petroleum products - Test method for nitrogen composition)

[0364] - Chlorine content: JPI-5S-64 (Petroleum products - Chlorine content test method - Micro-electromagnetic titration method)

[0365] - 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))

[0366] - Diene value: ASTМ D1961 (Method of Test for Malenic Diene Value of Drying Oils)

[0367] For samples for which the above test method cannot be applied, the method described in Japanese Patent Application Publication No. 2011-80766 can be used. 1 HNMR measurements were performed and inferences were made using the following methods.

[0368] 1. Mix approximately 20 mg of the sample with a known diene value with 500 μL of deuterated chloroform.

[0369] 2. Through 1 The integral value in the range of 6.0 to 6.8 ppm was calculated by HNMR analysis and corrected to the absolute area per 20 mg sample.

[0370] 3. Perform the above measurements on multiple samples and create a calibration curve of total area versus diene value.

[0371] 4. Calculate the total area of ​​the sample with an unknown diene value, and infer the diene value based on the calibration curve in step 3.

[0372] - Iodine value: JIS K 0070 (Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products)

[0373] -Total acid number: JIS K 2501 (Petroleum products and lubricating oils—Neutralization test method)

[0374] - Evaluation of heat exchange fouling in 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 heat exchange fouling.

[0375] 1. From Figure 6 The bottom left side (inlet 62) of the fouling evaluation test apparatus (HLPS) 60 shown allows low-temperature hydrogenated oil at 25°C to circulate for a certain period of time (60 minutes).

[0376] 2. While maintaining the temperature of test piece 61 at a constant 300°C, observe the formation and adhesion of contaminants on the surface of test piece 61. If contaminants adhere to test piece 61, the thermal conductivity between the low-temperature hydrogenated oil and test piece 61 will decrease.

[0377] 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 defined as "the temperature decrease caused by the decrease in electrothermal energy due to fouling".

[0378] (Among them, the results of Comparative Example 3 are an evaluation of thermally cracked oil that has not undergone low-temperature hydrogenation treatment.)

[0379] Here, "Heat Exchanger Fouling Evaluation" is conducted based on the following criteria.

[0380] (Evaluation Criteria)

[0381] 〇: If the temperature decrease is less than 10℃ during the evaluation over a certain period of time (200 minutes), it is judged that the fouling in the heat exchanger has been suppressed.

[0382] ×: If the temperature drop is greater than 10℃ during a certain period of time (200 minutes), it is judged that there is significant fouling in the heat exchanger.

[0383] -Analysis of gas composition of steam cracking products: JIS K2301:2011

[0384] (Fuel gases and natural gas - Analytical / Testing Methods)

[0385] - Analysis of steam cracking product oil: The steam cracking product oil obtained after oil-water separation will be fractionated to obtain a fraction below 250°C, and then analyzed according to JIS K 2536-2 (Petroleum products - Test methods for composition - Part 2: Determination of total composition by gas chromatography).

[0386] (Example 1)

[0387] (1) Thermal pyrolysis process

[0388] use Figure 1 The pyrolysis apparatus shown performs the pyrolysis process.

[0389] Specifically, the pyrolysis furnace 2 (capacity 0.5m³) 3 Approximately 100 kg of cut waste truck tires (waste tire category 6) are introduced into the pyrolysis furnace 2. Nitrogen is then purged within the furnace, and the nitrogen is circulated through the heat exchanger 1 to raise the gas temperature to 500°C, which is then maintained. It should be noted that the nitrogen flow rate introduced into the pyrolysis furnace 2 is set to 0.005 m³ / min. 3 / s[ntp], 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.

[0390] Thermally cracked 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.

[0391] 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 metallic components is removed from the pyrolysis furnace. The metallic components are removed from the mixture using a magnetic separator, yielding the residue. The residue is then pulverized into fine powder with a particle size of less than 1 mm using a hammer mill, and classified using a wind classifier with rotating blades to remove coarse powder with a particle size greater than 50 μm, thereby obtaining carbides with a particle size of less than 10 μm and a modulus of 4 μm.

[0392] The ratios of each component and the properties of the thermally cracked oil are shown in Table 1.

[0393] (2) Low-temperature hydrogenation process

[0394] (2-1) Preparation of hydrogenation catalyst A-1

[0395] A cylindrical support with a diameter of approximately 1.6 mm and a length of approximately 3 mm was prepared using silica-alumina powder, consisting of 97% by mass alumina and 3% by mass silica as oxides. Nickel nitrate and ammonium molybdate were dissolved in ion-exchanged water with a pre-determined water absorption capacity of the support to obtain a nickel nitrate and ammonium molybdate impregnation solution. This impregnation solution was then impregnated onto the support using an initial wetting method, with a Ni content of 4% by mass and a Mo content of 20% by mass based on the mass of the support. Next, the resulting impregnated material (catalyst precursor) was dried at 120°C for 3 hours and then calcined at 500°C for 1 hour under air circulation to obtain hydrogenation catalyst A-1.

[0396] (2-2) Low-temperature hydrogenation treatment

[0397] Hydrogenation catalyst A-1 was packed into the reaction tube (inner diameter 20 mm). After sulfidation treatment using an oil obtained by dissolving dimethyl disulfide in light oil at 1% by mass, the reaction was carried out at a reaction pressure of 11 MPaG, a reaction temperature of 180 °C, and a WHSV of 0.3 h. －1 Low-temperature hydrogenation of thermally cracked oil was carried out under specific conditions to obtain low-temperature hydrogenated oil. The properties of the low-temperature hydrogenated oil are shown in Table 4.

[0398] (3) Hydrogenation cracking process

[0399] (3-1) Preparation of catalyst B-1

[0400] Cylindrical supports with a diameter of approximately 1.6 mm and a length of approximately 3 mm were prepared by adding, mixing, and calcining 0.9 kg of silica-alumina powder (30% by mass of alumina and 70% by mass of silica) and 0.1 kg of USY zeolite with a SiO2 / Al2O3 ratio of 30. Nickel nitrate and ammonium tungstate were dissolved in ion-exchanged water with a pre-determined water absorption capacity of the supports to obtain a nickel nitrate and ammonium tungstate impregnation solution. This impregnation solution was impregnated onto the supports using an initial wetting method, with a Ni content of 10% by mass and a W content of 20% by mass (based on the mass of the supports). The resulting impregnated material (catalyst precursor) was dried at 120°C for 3 hours and then calcined at 500°C for 1 hour under air circulation to obtain hydrogenation catalyst B-1.

[0401] (3-2) Hydrogenation cracking

[0402] Hydrogenation catalyst A-1 and hydrogenation cracking catalyst B-1 were filled into a reaction tube (20 mm inner diameter) at a weight ratio of 8:2. The filling order was to fill the front section of the reaction tube with hydrogenation catalyst A-1 and the rear section with hydrogenation catalyst B-1. Using an oil obtained by dissolving dimethyl disulfide in light oil at 1% by mass, hydrogenation cracking was carried out under conditions of 11 MPaG reaction pressure, 390 °C reaction temperature, and WHSV = 0.3 h⁻¹, using low-temperature hydrogenated oil as feedstock, to obtain a second gas component and hydrogenated cracked oil. The hydrogenated cracked oil was fractionated into light and heavy components, and the ratios of each component were determined. The results are shown in Table 6.

[0403] (4) Steam cracking process

[0404] Using a pyrolysis unit with a tubular reactor (reaction tube), the light components obtained in the hydrogenation cracking process were reacted with steam under the conditions of a reactor outlet reaction temperature of 790°C, a reaction pressure of 0.15 MPaA, and a residence time of 0.25 seconds in the reaction tube. The products after the reaction (product gas, product oil, and raw materials for carbide manufacturing) were recovered. The results are shown in Table 8. It should be noted that the 10% distillation temperature of the heavy fraction was adjusted to above 190°C.

[0405] (Example 2)

[0406] The thermal pyrolysis temperature in the thermal pyrolysis process was changed to 400°C, but the chemical product was otherwise manufactured in the same manner as in Example 1.

[0407] (Example 3)

[0408] The thermal pyrolysis temperature in the thermal pyrolysis process was changed to 700°C, but the chemical product was otherwise manufactured in the same manner as in Example 1.

[0409] (Example 4)

[0410] The feedstock oil (75% by mass of low-boiling oil and 25% by mass of high-boiling oil) from which 18% by mass of high-boiling oil was removed by distillation of thermally cracked oil was used in a low-temperature hydrogenation process. Otherwise, the chemical product was 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 3.

[0411] (Example 5)

[0412] The feedstock oil (67% by mass of low-boiling oil and 33% by mass of high-boiling oil) from which 10% by mass of high-boiling oil was removed by distillation of thermally cracked oil was used in a low-temperature hydrogenation process. Otherwise, the chemical product was 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 3.

[0413] (Example 6)

[0414] The pyrolysis process was carried out in the presence of a catalyst, and the pyrolysis temperature was changed to 350°C. Otherwise, the chemical product was manufactured in the same manner as in Example 1. Acidic clay was used as the catalyst in the pyrolysis process.

[0415] (Comparative Example 1)

[0416] The thermal pyrolysis temperature in the thermal pyrolysis process was changed to 300°C, but the chemical product was otherwise manufactured in the same manner as in Example 1.

[0417] (Comparative Example 2)

[0418] The thermal pyrolysis temperature in the thermal pyrolysis process was changed to 800°C, but the chemical product was otherwise manufactured in the same manner as in Example 1.

[0419] In Examples 1-6 and Comparative Example 2, powdered carbides suitable for use as rubber additives, resin additives, colorants, etc., were obtained from the residue components of the pyrolysis process. On the other hand, in Comparative Example 1, the rubber component remained in the residue components, making it difficult to pulverize and thus impossible to obtain powdered carbides.

[0420] The results of the thermal cracking, cryogenic hydrogenation, hydrogenation cracking, and steam cracking processes in Examples 1-6 and Comparative Examples 1-2 are shown in Tables 1-9. It should be noted that the chemical product yield (mass %) relative to the total amount of thermal cracking products excluding metal 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, thermal cracking oil, and residue components obtained in the thermal cracking process.

[0421] As shown in Tables 8 and 9, in Comparative Examples 1 and 2, the yield of chemical products was lower compared to Examples 1-6, and the chemical products could not be manufactured efficiently.

[0422] As shown in Tables 1 and 2, in Comparative Example 1, the yield of powdered carbide was 0% by mass, and carbide could not be obtained while manufacturing chemical products.

[0423]

[0424]

[0425]

[0426]

[0427]

[0428]

[0429]

[0430]

[0431]

[0432] (Comparative Example 3)

[0433] Without undergoing a low-temperature hydrogenation process, the thermally cracked oil obtained from the thermal cracking process is used as the feedstock oil and subjected to hydrogenation cracking in the hydrogenation cracking process. Otherwise, the chemical products are manufactured in the same manner as in Example 1.

[0434] (Comparative Example 4)

[0435] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 150°C, but the chemical product was otherwise manufactured in the same manner as in Example 1.

[0436] (Example 7)

[0437] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 190°C, but the chemical product was manufactured in the same manner as in Example 1.

[0438] (Example 8)

[0439] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 200°C, but the chemical product was otherwise manufactured in the same manner as in Example 1.

[0440] (Example 9)

[0441] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 210°C, but the chemical product was otherwise manufactured in the same manner as in Example 1.

[0442] (Example 10)

[0443] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 250°C, but the chemical product was manufactured in the same manner as in Example 1.

[0444] (Example 11)

[0445] The low-temperature hydrogenation process in the low-temperature hydrogenation step was changed to 300°C, but the chemical product was manufactured in the same manner as in Example 1.

[0446] The results of the low-temperature hydrogenation process, hydrogenation cracking process, and steam cracking process in Comparative Examples 3 and 4, and Examples 7-11 are shown in Tables 10-12. It should be noted that the results of Example 1 are also recorded for reference.

[0447]

[0448]

[0449]

[0450] (Example 12)

[0451] Using feedstock oil comprising 50% by mass of thermally cracked oil obtained in the thermal cracking process and 50% by mass of recycled oil consisting of hydrogenated cracked oil (light and heavy components) obtained in the hydrogenation cracking process, a low-temperature hydrogenation process is performed, and the chemical product is manufactured in the same manner as in Example 1.

[0452] (Example 13)

[0453] Using feedstock oil comprising 20% ​​by mass of thermally cracked oil obtained in the thermal cracking process and 80% by mass of recycled oil consisting of hydrogenated cracked oil (light and heavy components) obtained in the hydrogenation cracking process, a low-temperature hydrogenation process is performed, and the chemical product is manufactured in the same manner as in Example 1.

[0454] The results of the low-temperature hydrogenation process, hydrogenation cracking process, and steam cracking process in Examples 12 and 13 are shown in Tables 13-15.

[0455]

[0456]

[0457]

[0458] (Example 14)

[0459] Using a feedstock comprising 50% by mass of feedstock oil from which 18% by mass of high-boiling-point oil has been removed by distillation of thermally cracked oil and 50% by mass of recycled oil consisting of hydrogenated cracked oil (light and heavy components) obtained from a hydrogenation cracking process, a low-temperature hydrogenation process is performed, and the chemical product is manufactured in the same manner as in Example 4.

[0460] (Example 15)

[0461] Using a feedstock comprising 20% ​​by mass of feedstock oil from which 10% by mass of high-boiling-point oil has been removed by distillation of thermally cracked oil and 80% by mass of recycled oil consisting of hydrogenated cracked oil (light and heavy components) obtained from a hydrogenation cracking process, a low-temperature hydrogenation process is performed, and the chemical product is manufactured in the same manner as in Example 5.

[0462] The results of the low-temperature hydrogenation process, hydrogenation cracking process, and steam cracking process in Examples 14 and 15 are shown in Tables 16 to 18.

[0463]

[0464]

[0465]

[0466] As can be confirmed from the above embodiments, according to the present invention, excellent chemical product yields can be achieved, and carbides can also be obtained efficiently.

[0467] Symbol Explanation

[0468] 1…Heat exchanger, 2…Pyrolysis furnace, 3…Oxygen-free gas supply source, 4…Circulation path, 5…Oil recovery device, 6…Waste tires, 7…Pyrolysis unit, 8…External heating mechanism, 9…Flow meter, 10…Damper, 11…Blower, 12…Dry distillation unit, 13…Recovery tank, 14…Hot blast furnace, 15…Exhaust fan, 16…Waste gas treatment device, 100…System, 110…Pyrolysis unit, 111…First separation unit, 112…Pulverization unit, 115…Cryogenic hydrogenation unit, 120…Hydrogenation pyrolysis unit, 121…Second separation unit, 130…Steam pyrolysis unit, 140…Carbide Manufacturing unit, S1…waste, S2…first gas component, S3…pyrolysis oil, S4…mixture of residue and metallic components, S5…residue component, S6…metallic component, S7…powdered carbide, S8…low-temperature hydrogenated oil, S9…second gas component, S10…hydrogenated cracked oil, S11…light component, S12…heavy component, S13…product gas, S14…product oil, S15…heavy fraction, S16…carbide, S17…recycled oil (light component + heavy component), 60…measuring device for evaluating heat exchanger fouling, 61…test piece, 62…inlet, 63…outlet

Claims

1. A method for manufacturing a chemical product and a carbide, comprising: The pyrolysis process involves the pyrolysis of waste tire fragments to obtain a primary gaseous component, pyrolysis oil, and residue components. The carbide recovery process recovers carbides from the residue components. The low-temperature hydrogenation process involves subjecting the feedstock containing at least a portion of the thermally cracked oil to low-temperature hydrogenation treatment at 180°C to 350°C to obtain low-temperature hydrogenated oil. The hydrocracking process involves subjecting the feedstock containing at least a portion of the aforementioned low-temperature hydrotreated oil to hydrocracking at a temperature higher than that of the low-temperature hydrotreating treatment, yielding a second gaseous component, light components with a boiling point below 350°C, and heavy components with a boiling point exceeding 350°C. The steam cracking process involves steam cracking of a steam cracking feedstock oil containing at least a portion of the light components to obtain chemical products and a feedstock for carbide manufacturing containing 10% heavy fractions with a distillation temperature of 190°C or higher. The thermal pyrolysis temperature is 350℃~750℃.

2. 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.

3. The manufacturing method according to claim 1, wherein, In the pyrolysis process, 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.

4. The manufacturing method according to claim 1, wherein, The 10% distillation temperature of the thermally cracked oil is above 90°C, and the 90% distillation temperature is above 350°C.

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

6. 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 thermally cracked oil by distillation, it is used as part of the feedstock oil for the low-temperature hydrogenation process.

7. The manufacturing method according to claim 1, wherein, In the hydrogenation cracking 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, and the content of the high-boiling-point oil is less than 50% by mass based on the total amount of the feedstock oil.

8. The manufacturing method according to claim 1, wherein, The recycled oil, comprising at least a portion of the light and heavy components obtained in the hydrogenation cracking process, is used as part of the feedstock for the cryogenic hydrotreating process.

9. The manufacturing method according to claim 8, wherein, In the low-temperature hydrogenation process, the amount of recycle oil is 10% to 99% by mass relative to the total amount of recycle oil and thermally cracked oil in the feedstock.

10. The manufacturing method according to claim 1, wherein, The hydrogenation cracking process is a process of hydrogenating and cracking the feedstock oil in the presence of a hydrogenation cracking catalyst.

11. The manufacturing method according to claim 10, wherein, The hydrogenation cracking catalyst contains a Ni-based catalyst.

12. The manufacturing method according to claim 1, wherein, In the hydrogenation cracking process, the nitrogen content in the feed oil is above 2000 ppm by mass, and the nitrogen content in the light components is below 25 ppm by mass.

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

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

15. 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.

16. 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.

17. The manufacturing method according to any one of claims 1 to 16, wherein, It further includes a carbide manufacturing process in which carbides are obtained by thermal decomposition or incomplete combustion of the raw materials used for carbide manufacturing.

18. A method for manufacturing synthetic rubber, comprising a polymerization step, wherein the polymerization step obtains synthetic rubber by using a polymerization reaction of butadiene obtained by the manufacturing method of claim 16 as a raw material for synthetic rubber.

19. A tire comprising synthetic rubber obtained by the manufacturing method of claim 18.

20. A method of manufacturing a tire, comprising a vulcanization step, wherein the vulcanization step yields the tire by vulcanizing at least a portion of the synthetic rubber obtained by the manufacturing method of claim 18 as a raw material for the tire.

21. A method for managing chemical products, which is a method for managing chemical products using a management device when manufacturing chemical products from waste tires. The management method uses the management device to allocate the value of the chemical product as a renewable product based on the proportion of renewable raw materials contained in the waste tires, using a mass balance method. The management method includes confirming the process (V) for obtaining the chemical product. The process (V) includes the following processes (V-1), (V-2), (V-3), (V-4), and (V-5). The process (V-1) is to confirm that the waste tires fed into the pyrolysis unit, which processes the waste tires at 350°C to 750°C to obtain pyrolysis oil, generate the pyrolysis oil. The process (V-2) is the process of confirming that the thermally cracked oil is produced from the thermally cracked oil in a low-temperature hydrogenation unit where at least a portion of the feedstock containing the thermally cracked 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 a process of confirming that the light components are generated from the low-temperature hydrotreated oil fed into a hydrocracking unit that performs hydrocracking treatment on feedstock containing at least a portion of the low-temperature hydrotreated oil at a temperature higher than that of the low-temperature hydrotreatment. The step (V-4) is the step of confirming that the chemical product is obtained from the light components fed into a steam pyrolysis unit that performs steam pyrolysis treatment on at least a portion of the steam pyrolysis feedstock containing the light components. The process (V-5) confirms that the chemical product is obtained from the waste tires through sequential processing in the thermal cracking unit, the low-temperature hydrogenation unit, the hydrogenation cracking unit, and the steam cracker. The management method includes a process (Z) of determining 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 from the steam pyrolysis unit for distribution as renewable products. The process (Z-2) is the process of determining the value of P, which is the proportion of the product selected in the process (Z-1) relative to the proportion of the product obtained from the steam pyrolysis unit, to be allocated as a renewable product. The process (Z-3) is to determine the value of Q, the proportion of renewable raw materials contained in the waste tires. The process (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.

22. A management device comprising a computer-readable storage medium storing a management program. The management device executes the management method of claim 21 by executing the management program.

23. The management device according to claim 22, 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 tires.

24. A storage medium that is computer-readable and stores a computer program. The storage enables the computer to execute the management program of the management method of claim 21.

25. A management program for causing a computer to perform the management method of claim 21.

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