Method for producing hydrotreated oil

Abstract

[Problem] To provide a method for producing a hydrotreated oil suitable for a series of processes for producing a chemical product using an oil obtained by the hydrotreatment of a pyrolysis oil. [Solution] This method for producing a hydrotreated oil comprises: a pyrolysis step for obtaining a pyrolysis oil by means of the pyrolysis of a waste material containing at least one among waste tires and waste plastics; a mixing step for mixing the pyrolysis oil with a diluent oil to obtain a mixed oil; and a hydrogenation step for subjecting the mixed oil to a hydrotreatment to obtain a hydrotreated oil having a nitrogen content of at most 300 ppm by mass and a sulfur content of at most 1,000 ppm by mass.

Description

Method for producing hydrogenated oil

[0001] The present invention relates to a method for producing a hydrogenated oil of a pyrolysis oil using waste materials as a raw material.

[0002] In recent years, as a method for recycling waste materials such as waste plastics, conversion into hydrocarbons by pyrolysis and the like has been studied (for example, Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2019-533041

[0004] In the recycling of waste materials, due to reasons such as the fact that the types and qualities of waste materials are not necessarily constant, and a process that can utilize existing equipment is required, the development of various processes is desired.

[0005] The present inventors have found that in a series of processes for producing chemical products using a hydrogenated oil of a pyrolysis oil, denitrification and desulfurization become difficult depending on the properties of the pyrolysis oil and the hydrogenated oil, and the stability is low, and there is a risk of thermal runaway. As a result, a technical problem of adversely affecting the long-term operation of the above production process has been found.

[0006] Therefore, an object of the present invention is to provide a method for producing a hydrogenated oil suitable for the above production process that enables long-term operation of the above production process.

[0007] As a result of investigations to solve the above problems, the present inventors have found that the above problems can be solved by using a mixed oil obtained by mixing a pyrolysis oil and a diluent oil as a raw material oil for hydrogenation treatment. The present inventors have completed the present invention based on such findings.

[0008] One aspect of the present invention relates, for example, to the following: [1] A method for producing a hydrotreated oil, comprising: a pyrolysis step of obtaining a pyrolysis oil by pyrolysis of waste material including at least one of waste tires and waste plastics; a mixing step of mixing the pyrolysis oil and a diluent oil to obtain a mixed oil; and a hydrogenation step of subjecting the mixed oil to a hydrotreatment to obtain a hydrotreated oil having a nitrogen content of 300 ppm by mass or less and a sulfur content of 1000 ppm by mass or less. [2] The method for producing the hydrotreated oil according to [1], wherein the diluent oil contains hydrocarbons having 5 to 100 carbon atoms. [3] The method for producing the hydrotreated oil according to [1] or [2], wherein the diluent oil contains recycled oil containing at least a portion of the hydrotreated oil. [4] The method for producing the hydrotreated oil according to any one of [1] to [3], wherein the nitrogen content of the mixed oil is 5000 ppm by mass or less. [5] The method for producing the hydrotreated oil according to any one of [1] to [4], wherein the amount of the pyrolysis oil in the mixed oil is 0.1% by mass or more and 80% by mass of the total amount of the mixed oil. [6] The manufacturing method according to any one of [1] to [5], wherein in the mixing step, the pyrolysis oil and the diluent oil are mixed using means different from the hydrogenation treatment apparatus. [7] The manufacturing method according to [6], wherein the different means is a mixing tank installed between the pyrolysis apparatus and the hydrogenation treatment apparatus. [8] The manufacturing method according to [6], wherein the different means is piping installed between the pyrolysis apparatus and the hydrogenation treatment apparatus. [9] A method for producing synthetic rubber, comprising: a step of obtaining a chemical product containing butadiene using a hydrogenation treatment oil obtained by the manufacturing method according to any one of [1] to [8]; and a polymerization step of obtaining synthetic rubber by a polymerization reaction using butadiene as at least a part of the raw material for synthetic rubber.

[10] A tire containing synthetic rubber obtained by the manufacturing method according to [9].

[0009] The present invention provides a method for producing a hydrothermal oil suitable for a series of processes for producing chemical products using a hydrothermal oil derived from pyrolysis. Furthermore, the present invention provides a method for producing chemical products using the hydrothermal oil. Moreover, the present invention provides a method for producing synthetic rubber and tires using the chemical products.

[0010] This is a schematic diagram showing an example of a pyrolysis apparatus. This is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment. This is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment. This is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment. This is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment. This is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment. This is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment. This is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment.

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

[0012] [Method for producing hydrogenated oil] The method for producing hydrogenated oil according to this embodiment includes a thermal decomposition step of obtaining thermal decomposition oil by thermal decomposition of waste material containing at least one of waste tires and waste plastics, a mixing step of mixing the thermal decomposition oil with a diluent oil to obtain a mixed oil, and a hydrogenation step of subjecting the mixed oil to a hydrogenation treatment to obtain hydrogenated oil.

[0013] (Hydrogenated Oil) The hydrogenated oil obtained by the method for producing hydrogenated oil of this embodiment has a nitrogen content of 300 ppm by mass or less and a sulfur content of 1000 ppm by mass or less, which provides high stability, suppresses thermal runaway, and enables long-term operation of a process for producing chemical products using hydrogenated oil from pyrolysis.

[0014] The nitrogen content of the hydrotreated oil is preferably 250 ppm by mass or less, more preferably 200 ppm by mass or less, even more preferably 150 ppm by mass or less, and may also be 10 ppm by mass or more. That is, the nitrogen content of the hydrotreated oil may be, for example, 10 ppm by mass or more and 300 ppm by mass or less, 10 ppm by mass or more and 250 ppm by mass or less, 10 ppm by mass or more and 200 ppm by mass or less, or 10 ppm by mass or more and 150 ppm by mass or less.

[0015] The sulfur content of the hydrotreated oil is preferably 900 ppm by mass or less, more preferably 800 ppm by mass or less, even more preferably 700 ppm by mass or less, and may also be 100 ppm by mass or more. That is, the nitrogen content of the hydrotreated oil may be, for example, 100 ppm by mass or more and 1000 ppm by mass or less, 100 ppm by mass or more and 900 ppm by mass or less, 100 ppm by mass or more and 800 ppm by mass or less, or 100 ppm by mass or more and 700 ppm by mass or less.

[0016] The following details each step in the manufacturing process of hydrogenated oil.

[0017] (Thermal Decomposition Process) The thermal decomposition process is a process of obtaining thermal decomposition oil by thermal decomposition of waste materials. The waste materials include at least one of waste tires and waste plastics. The waste tires and waste plastics include polymer materials. Examples of polymer materials include rubber materials such as natural rubber, BR (butadiene rubber), SBR (styrene-butadiene rubber), NBR (nitrile rubber), IIR (butyl rubber), Cl-IIR (chlorinated butyl rubber), and Br-IIR (brominated butyl rubber), and resin materials such as polyethylene, polypropylene, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, and polyvinyl chloride.

[0018] The waste material may further contain metal components. For example, waste tires may contain metal components such as steel cords and wires, which are the aggregates of the tires. If the waste material contains metal components, the manufacturing method of this embodiment may further include a removal step to remove the metal components from the waste material. The method for removing metal components from the waste material is not particularly limited, and examples include methods using magnets, sieves, etc. Alternatively, metal components may be present in the residue after obtaining pyrolysis oil in the pyrolysis step.

[0019] The waste material may be in the form of crushed material. The method of crushing the waste material is not particularly limited and may include, for example, mechanical crushing using a single-shaft or twin-shaft mill, crushing using a water jet, cryogenic crushing, laser crushing, etc.

[0020] The thermal decomposition of waste materials can be carried out, for example, by placing the waste materials in a thermal decomposition furnace, supplying a high-temperature gas to the furnace, and bringing the crushed waste materials into contact with the high-temperature gas. The high-temperature gas is preferably an oxygen-free gas (for example, a gas with an oxygen content of 1 volume percent or less). The high-temperature gas may be any gas other than oxygen and oxides, such as inert gases such as nitrogen, argon, and helium, hydrogen, or hydrocarbons having 1 to 4 carbon atoms. The thermal decomposition furnace is not particularly limited and may be, for example, a kettle-type thermal decomposition furnace, a fluidized bed-type thermal decomposition furnace, a kiln-type thermal decomposition furnace, etc.

[0021] The thermal decomposition temperature (temperature of the high-temperature gas) in the thermal decomposition process is preferably 250°C or higher, more preferably 300°C or higher, even more preferably 350°C or higher, and also preferably 600°C or lower, more preferably 500°C or lower, and even more preferably 400°C or lower, from the viewpoint of yielding thermally decomposed oil. That is, the thermal decomposition temperature (temperature of the high-temperature gas) in the thermal decomposition process may be, for example, 250°C or higher and 600°C or lower, 250°C or higher and 500°C or lower, 250°C or higher and 400°C or lower, 300°C or higher and 600°C or lower, 300°C or higher and 500°C or lower, 300°C or higher and 400°C or lower, 350°C or higher and 600°C or lower, 350°C or higher and 500°C or lower, or 350°C or higher and 400°C or lower.

[0022] Pyrolysis may be carried out in the presence or absence of a pyrolysis catalyst. Any catalyst commonly used in petrochemical pyrolysis can be used as the pyrolysis catalyst without particular limitations. The pyrolysis catalyst may be an acidic catalyst or a basic catalyst. Examples of acidic catalysts include catalysts containing aluminosilicates. Examples of aluminosilicates include zeolites and smectite groups such as montmorillonite. Examples of montmorillonite-containing catalysts include clays or minerals such as activated clay, acid clay, and bentonite. As a basic catalyst, for example, carbonates such as sodium carbonate can be used.

[0023] The pyrolysis oil may be, for example, a component of the products generated by pyrolysis that is liquid at atmospheric pressure and 20°C. The method for recovering the pyrolysis oil is not particularly limited. The pyrolysis oil can be recovered, for example, as oil distilled from the pyrolysis furnace. That is, the pyrolysis oil can be recovered, for example, as oil condensed by cooling the pyrolysis gas generated by pyrolysis.

[0024] The distillation properties of the pyrolysis oil are not particularly limited; for example, any properties suitable for use as a raw material in a hydrogenation process are acceptable.

[0025] The nitrogen content of the pyrolysis oil may be, for example, 1,000 ppm by mass or more, 2,000 ppm by mass or more, 3,000 ppm by mass or more, or 10,000 ppm by mass or less, 9,000 ppm by mass or less, or 8,000 ppm by mass or less. Even if a large amount of nitrogen is present in the pyrolysis oil, after mixing it with the diluent oil in the mixing step described later, and then subjecting it to hydrogenation treatment in the hydrogenation step described later, the nitrogen can be converted into gaseous components such as ammonia by hydrogenation, thereby significantly reducing the nitrogen content. In other words, the nitrogen content of the pyrolysis oil may be, for example, 1,000 ppm by mass or more and 10,000 ppm by mass or less, 1,000 ppm by mass or more and 9,000 ppm by mass or less, 1,000 ppm by mass or more and 8,000 ppm by mass or less, 2,000 ppm by mass or more and 10,000 ppm by mass or less, 2,000 ppm by mass or more and 9,000 ppm by mass or less, 2,000 ppm by mass or more and 8,000 ppm by mass or less, 3,000 ppm by mass or more and 10,000 ppm by mass or less, 3,000 ppm by mass or more and 9,000 ppm by mass or less, or 3,000 ppm by mass or more and 8,000 ppm by mass or less. The sulfur content of the pyrolysis oil may be, for example, 1,000 ppm by mass or more, 3,000 ppm by mass or more, 5,000 ppm by mass or more, 20,000 ppm by mass or less, 17,000 ppm by mass or less, or 15,000 ppm by mass or less. Even if a large amount of sulfur is present in the pyrolysis oil, after mixing it with the diluent oil in the mixing step described later, the sulfur content can be converted into gaseous components such as hydrogen sulfide by hydrogenation in the hydrogenation step described later, thereby significantly reducing the sulfur content. In other words, the sulfur content of the pyrolysis oil may be, for example, 1,000 ppm by mass or more and 20,000 ppm by mass or less, 1,000 ppm by mass or more and 17,000 ppm by mass or less, 1,000 ppm by mass or more and 15,000 ppm by mass or less, 3,000 ppm by mass or more and 20,000 ppm by mass or less, 3,000 ppm by mass or more and 17,000 ppm by mass or less, 3,000 ppm by mass or more and 15,000 ppm by mass or less, 5,000 ppm by mass or more and 20,000 ppm by mass or less, 5,000 ppm by mass or more and 17,000 ppm by mass or less, or 5,000 ppm by mass or more and 15,000 ppm by mass or less.

[0026] The pyrolysis process may be carried out, for example, by a pyrolysis apparatus equipped with a pyrolysis furnace. The pyrolysis furnace used in the pyrolysis process only needs to be able to pyrolyze the crushed material, and for example, a batch-type pyrolysis furnace, a continuous-type pyrolysis furnace, etc., can be used. For example, a rotary kiln, an auger furnace, etc., can be used as a continuous-type pyrolysis furnace. In the following, a pyrolysis apparatus equipped with a batch-type pyrolysis furnace will be described as an example of a pyrolysis apparatus, but the pyrolysis apparatus is not limited to this.

[0027] Figure 1 is a schematic diagram showing an example of a pyrolysis apparatus. The pyrolysis apparatus in Figure 1 comprises a heat exchanger 1 for heating oxygen-free gas, a decomposition apparatus 7 having a pyrolysis furnace 2 that contains waste material 6 and an external heating means 8 for heating the pyrolysis furnace 2 from the outside, an oil recovery apparatus 5 for cooling the pyrolysis gas generated in the decomposition apparatus 7 and recovering the condensed oil (pyrolysis oil), a circulation path 4 for supplying the remaining gas after the oil has been recovered in the oil recovery apparatus 5 to the heat exchanger 1 as oxygen-free gas, and an oxygen-free gas supply source 3 for supplying oxygen-free gas to the heat exchanger 1.

[0028] Furthermore, the pyrolysis apparatus shown in Figure 1 is equipped with a flow meter 9, a damper 10, and a blower 11 in the piping connecting the oxygen-free gas supply source 3 and the heat exchanger 1 in order to supply oxygen-free gas from the oxygen-free gas supply source 3, and a flow meter 9, a damper 10, a blower 11, and a hot air furnace 14 in the circulation path 4 for circulating the remaining gas after recovery by the oil recovery device 5 back to the heat exchanger 1 as oxygen-free gas.

[0029] Furthermore, the oil recovery apparatus 5 may be equipped with multiple carbonization columns 12a and 12b in order to separate the recovered oil according to its boiling point. Each carbonization column 12 may be connected to a recovery tank 13 through piping at its lower end, allowing the recovered oil to be stored. Although the pyrolysis apparatus in Figure 1 is equipped with multiple carbonization columns 12a and 12b, in this embodiment, since the pyrolysis oil can be used directly as part of the raw material oil for the hydrogenation process, there may be only one carbonization column. Also, in the pyrolysis apparatus in Figure 1, each carbonization column 12 is connected to a different recovery tank 13, but each carbonization column 12 may be connected to the same recovery tank 13.

[0030] In the pyrolysis oil of the present invention, it is preferable to remove at least a portion of the high-boiling-point oil exceeding 350°C by distillation or the like before the subsequent hydrogenation step. By removing at least a portion of the high-boiling-point oil from the pyrolysis oil, the generation of fouling in the hydrogenation step and in heat exchangers and heating furnaces in existing (petroleum refining) processes can be suppressed, enabling long-term operation of the process. Although not limited, it is more preferable to remove at least a portion of the high-boiling-point oil with a boiling point exceeding 450°C, for example.

[0031] One method for removing high-boiling-point oil is to cool the pyrolysis gas immediately after it is produced in the pyrolysis process to separate it into pyrolysis oil containing a large amount of high-boiling-point oil and gas containing a large amount of low-boiling-point oil. Then, by further cooling the gas containing a large amount of low-boiling-point oil, the gas can be separated into gas and pyrolysis oil containing a large amount of low-boiling-point oil. Another method is to heat the pyrolysis oil and separate it into low-boiling-point oil and high-boiling-point oil in a distillation column, but the method is not limited to these.

[0032] (Mixing Process) The mixing process is a process of mixing the pyrolysis oil and the diluent oil to obtain a mixed oil. In the mixing process, the pyrolysis oil and the diluent oil can be mixed using means different from those used in the hydrotreatment apparatus before the hydrogenation process. The mixing means are not particularly limited as long as the pyrolysis oil and the diluent oil are sufficiently mixed, but examples include a mixing tank and piping installed between the pyrolysis apparatus and the hydrotreatment apparatus. Only one type of mixing means may be used, or two or more types may be used in combination.

[0033] The diluent oil preferably contains hydrocarbons with 5 to 100 carbon atoms, such as benzene, butylbenzene, and naphthalene. Examples of such diluent oils include vacuum gas oil (VGO), cracked gas oil (LCO), kerosene fraction, diesel fuel fraction, finished kerosene, finished diesel fuel, naphtha, recycled oil (part of hydrotreated oil), etc. One type of diluent oil may be used, or two or more types may be used in combination. The carbon number of hydrocarbons contained in the diluent oil is preferably 80 or less, more preferably 60 or less, even more preferably 40 or less, and most preferably 30 or less.

[0034] The distillation properties of the diluting oil are not particularly limited; any properties suitable for use as a raw material oil in the hydrogenation process are acceptable.

[0035] The nitrogen content of the diluent oil may be, for example, 10 ppm by mass or more, 20 ppm by mass or more, 30 ppm by mass or more, or 200 ppm by mass or less, 180 ppm by mass or less, or 160 ppm by mass or less. If the nitrogen content of the diluent oil is within the above numerical range, the nitrogen content of the mixed oil can be reduced even if there is a large amount of nitrogen in the pyrolysis oil. That is, the nitrogen content of the diluent oil may be, for example, 10 ppm by mass or more and 200 ppm by mass or less, 10 ppm by mass or more and 180 ppm by mass or less, 10 ppm by mass or more and 160 ppm by mass or less, 20 ppm by mass or more and 200 ppm by mass or less, 20 ppm by mass or more and 180 ppm by mass or less, 20 ppm by mass or more and 160 ppm by mass or less, 30 ppm by mass or more and 200 ppm by mass or less, 30 ppm by mass or more and 180 ppm by mass or less, or 30 ppm by mass or more and 160 ppm by mass or less. The sulfur content of the diluent oil may be, for example, 100 ppm by mass or more, 200 ppm by mass or more, 300 ppm by mass or more, or 1000 ppm by mass or less, 900 ppm by mass or less, or 800 ppm by mass or less. If the sulfur content of the diluent oil is within the above numerical range, the sulfur content of the mixed oil can be reduced even if there is a large amount of sulfur in the pyrolysis oil. In other words, the nitrogen content of the diluent oil may be, for example, 100 ppm by mass or more and 1000 ppm by mass or less, 100 ppm by mass or more and 900 ppm by mass or less, 100 ppm by mass or more and 800 ppm by mass or less, 200 ppm by mass or more and 1000 ppm by mass or less, 200 ppm by mass or more and 900 ppm by mass or less, 200 ppm by mass or more and 800 ppm by mass or less, 300 ppm by mass or more and 1000 ppm by mass or less, 300 ppm by mass or more and 900 ppm by mass or less, or 300 ppm by mass or more and 800 ppm by mass or less.

[0036] The amount of pyrolysis oil in the mixed oil is preferably 0.1% to 80% by mass, more preferably 1% to 70% by mass, even more preferably 10% to 60% by mass, and particularly preferably 20% to 50% by mass, based on the total amount of the mixed oil (total amount of pyrolysis oil and diluent). If the amount of pyrolysis oil in the mixed oil is within the above numerical range, it is easy to adjust the nitrogen and sulfur content of the mixed oil to the desired range.

[0037] The nitrogen content of the mixed oil may be, for example, 100 ppm by mass or more, 500 ppm by mass or more, 1000 ppm by mass or more, 5000 ppm by mass or less, 4500 ppm by mass or less, or 4000 ppm by mass or less. If the nitrogen content of the mixed oil is within the above numerical range, it is easy to adjust the nitrogen content of the hydrotreated oil after hydrotreatment to a desired range. In other words, the nitrogen content of the mixed oil may be, for example, 100 ppm by mass or more and 5000 ppm by mass or less, 100 ppm by mass or more and 4500 ppm by mass or less, 100 ppm by mass or more and 4000 ppm by mass or less, 500 ppm by mass or more and 5000 ppm by mass or less, 500 ppm by mass or more and 4500 ppm by mass or less, 500 ppm by mass or more and 4000 ppm by mass or less, 1000 ppm by mass or more and 5000 ppm by mass or less, 1000 ppm by mass or more and 4500 ppm by mass or less, or 1000 ppm by mass or more and 4000 ppm by mass or less. The sulfur content of the mixed oil may be, for example, 1,000 ppm by mass or more, 1,500 ppm by mass or more, 2,000 ppm by mass or more, or 9,000 ppm by mass or less, 8,000 ppm by mass or less, or 7,000 ppm by mass or less. If the sulfur content of the mixed oil is within the above numerical range, it is easy to adjust the sulfur content of the hydrotreated oil after hydrotreatment to a desired range. In other words, the sulfur content of the mixed oil may be, for example, 1,000 ppm by mass or more and 9,000 ppm by mass or less, 1,000 ppm by mass or more and 8,000 ppm by mass or less, 1,000 ppm by mass or more and 7,000 ppm by mass or less, 1,500 ppm by mass or more and 9,000 ppm by mass or less, 1,500 ppm by mass or more and 8,000 ppm by mass or less, 1,500 ppm by mass or more and 7,000 ppm by mass or less, 2,000 ppm by mass or more and 9,000 ppm by mass or less, 2,000 ppm by mass or more and 8,000 ppm by mass or less, or 2,000 ppm by mass or more and 7,000 ppm by mass or less.

[0038] In this embodiment, when hydrogenating the mixed oil, from the viewpoint that the hydrogenation treatment temperature condition is preferably 500°C or lower, the temperature (ADT24) measured by the accelerated rate calorimetry method of the mixed oil is preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, and even more preferably 450°C or higher. Furthermore, it is particularly preferable that ADT24 is not detected below 500°C, and most preferably that it is not detected below 400°C. If the ADT24 of the mixed oil is not detected, thermal runaway will not occur, and it can be said that the safety is high. Even if the ADT24 of the mixed oil is detected, the hydrogenation treatment can be performed at a value below the above ADT24 value, and it is preferable that the higher the ADT24 value, the higher the process temperature can be set. The ADT24 of the mixed oil can be measured by the following method. Equipment used: ARC (Accelerating Rate Calorimeter) Measurement method: The mixed oil is held at the starting temperature for 10 minutes. If no heat generation is detected, the temperature is raised by 5°C from that temperature, held for 10 minutes, and the presence or absence of heat generation is checked. This process is repeated until self-heating is confirmed. Once self-heating is confirmed, the device switches from heat generation detection mode to adiabatic control mode and begins measuring the heat generation behavior in an adiabatic state. Analysis method: The obtained time, temperature, and pressure data are corrected to calculate the heat generation start temperature, self-heating rate, TMR (time remaining until runaway in the adiabatic system (when the self-heating rate is at its maximum)), ADT24 (temperature at which the TMR is 24 hours), maximum pressure and pressure rise rate during heat generation, etc.

[0039] (Hydrogenation Process) The hydrogenation process is a process in which the mixed oil is subjected to hydrogenation treatment to obtain hydrogenated oil in which the nitrogen and sulfur content is within the specified range described above. The hydrogenation process may consist of only the high-temperature hydrogenation process described below, or both the low-temperature hydrogenation process and the high-temperature hydrogenation process described below may be performed.

[0040] (Low-temperature hydrogenation process) The low-temperature hydrogenation process is a process in which the above-mentioned mixed oil is subjected to low-temperature hydrogenation treatment to obtain low-temperature hydrogenated oil.

[0041] The low-temperature hydrogenation process may be carried out using one type of hydrogenation catalyst, or it may be carried out using multiple types of hydrogenation catalysts. For example, in the low-temperature hydrogenation process, the hydrogenation catalysts can be appropriately combined and used from the desulfurization / denitrification catalysts, high-resolution catalysts, low-resolution catalysts, etc., as described later.

[0042] The reaction temperature in the low-temperature hydrogenation process is, for example, 180°C to 300°C, preferably 190°C or higher, more preferably 200°C or higher, also preferably 280°C or lower, more preferably 260°C or lower, and even more preferably 240°C or lower. That is, the reaction temperature in the low-temperature hydrogenation process may be, for example, 180°C to 280°C, 180°C to 260°C, 180°C to 240°C, 190°C to 300°C, 190°C to 280°C, 190°C to 260°C, 190°C to 240°C, 200°C to 300°C, 200°C to 280°C, 200°C to 260°C, or 200°C to 240°C. By adjusting the reaction temperature in the low-temperature hydrogenation process within the above numerical range, the amount of dienes that can cause problems in the manufacturing process can be reduced.

[0043] The reaction pressure in the low-temperature hydrogenation process is, for example, 1.0 MPaG or more and 20 MPaG or less, preferably 2.0 MPaG or more, more preferably 3.0 MPaG or more, still more preferably 4.0 MPaG or more, and also preferably 15 MPaG or less, more preferably 10 MPaG or less, still more preferably 7.0 MPaG or less. That is, the reaction pressure in the low-temperature hydrogenation process may be, for example, 1.0 MPaG or more and 15 MPaG or less, 1.0 MPaG or more and 10 MPaG or less, 1.0 MPaG or more and 7.0 MPaG or less, 2.0 MPaG or more and 20 MPaG or less, 2.0 MPaG or more and 15 MPaG or less, 2.0 MPaG or more and 10 MPaG or less, 2.0 MPaG or more and 7.0 MPaG or less, 3.0 MPaG or more and 20 MPaG or less, 3.0 MPaG or more and 15 MPaG or less, 3.0 MPaG or more and 10 MPaG or less, 3.0 MPaG or more and 7.0 MPaG or less, 4.0 MPaG or more and 20 MPaG or less, 4.0 MPaG or more and 15 MPaG or less, 4.0 MPaG or more and 10 MPaG or less, or 4.0 MPaG or more and 7.0 MPaG or less. By adjusting the reaction temperature in the low-temperature hydrogenation process within the above numerical range, dienes that can cause problems in the manufacturing process can be reduced.

[0044] When the low-temperature hydrogenation process is carried out using a flow reactor, the weight hourly space velocity (WHSV) of the feed oil is, for example, 0.1 h －１ or more and 5.0 h －１ or less, preferably 0.3 h －１ or more, more preferably 0.5 h －１ or more, still more preferably 0.7 h －１ or more, and also preferably 4.0 h －１ or less, more preferably 3.0 h －１ or less, still more preferably 2.0 h －１ or less. That is, the weight hourly space velocity (WHSV) of the feed oil is, for example, 0.1 h －１ or more and 4.0 h －１ or less, 0.1 h －１ or more and 3.0 h －１ or less, 0.1 h －１ or more and 2.0 h －１ or less, 0.3 h －１Total 5.0h －１ Below, 0.3h －１ Total 4.0h －１ Below, 0.3h －１ 3.0 hours －１ Below, 0.3h －１ Total 2.0h －１ Below, 0.5h －１ Total 5.0h －１ Below, 0.5h －１ Total 4.0h －１ Below, 0.5h －１ 3.0 hours －１ Below, 0.5h －１ Total 2.0h －１ Below, 0.7 hours －１ Total 5.0h －１ Below, 0.7 hours －１ Total 4.0h －１ Below, 0.7 hours －１ 3.0 hours －１ The following, or 0.7h －１ Total 2.0h －１ The following may also apply. By adjusting the reaction temperature in the low-temperature hydrogenation process to within the above numerical range, the amount of dienes that can cause problems in the manufacturing process can be reduced.

[0045] (High-Temperature Hydrogenation Process) The high-temperature hydrogenation process is a process in which a feed oil containing at least a portion of the low-temperature hydrogenated oil is subjected to a hydrogenation treatment to obtain hydrogenated oil. Alternatively, if the low-temperature hydrogenation process is not performed, the high-temperature hydrogenation process is a process in which a feed oil containing at least a portion of the mixed oil is subjected to a hydrogenation treatment to obtain hydrogenated oil. Alternatively, both mixed oil and low-temperature hydrogenated oil may be used as the feed oil for the high-temperature hydrogenation process. Hydrogenated oil is described in detail above.

[0046] The raw material oil in the high-temperature hydrogenation process includes low-temperature hydrogenated oil and / or mixed oil, and may further contain components other than low-temperature hydrogenated oil (e.g., pyrolysis oil or fractionally distilled pyrolysis oil). In addition, low-temperature hydrogenated oil or mixed oil may be used as raw material oil in the high-temperature hydrogenation process.

[0047] The high-temperature hydrogenation step may be a step of hydrogenating the feed oil in the presence of a hydrogenation catalyst. Hydrogenation can be carried out, for example, by supplying the feed oil to a reactor containing a hydrogenation catalyst and bringing it into contact with the hydrogenation catalyst in the reactor. As the hydrogenation catalyst, for example, known hydrogenation catalysts used for the hydrogenation of hydrocarbon oils can be used. From the viewpoint of hydrogenation capacity, it is preferable that the hydrogenation catalyst includes, for example, a Ni-based catalyst. A Ni-based catalyst is a catalyst having Ni as the active metal.

[0048] The high-temperature hydrogenation process may be carried out using one type of hydrogenation catalyst, or it may be carried out using multiple types of hydrogenation catalysts. For example, in the high-temperature hydrogenation process, the hydrogenation catalysts can be appropriately combined and used from the desulfurization / denitrification catalysts, high-resolution catalysts, low-resolution catalysts, etc., as described later.

[0049] A desulfurization and denitrification catalyst can be any hydrogenation catalyst that exhibits excellent desulfurization and denitrification performance. Examples of such catalysts include hydrocracking catalysts, which consist of an active metal supported on an alumina-containing carrier. Such hydrogenation catalysts tend to exhibit excellent desulfurization and denitrification performance.

[0050] The support for the desulfurization / denitrification catalyst may contain components other than alumina. For example, the support for the desulfurization / denitrification catalyst may contain oxides of elements from groups 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support for the desulfurization / denitrification catalyst may contain at least one oxide of, for example, silica, phosphorus, magnesia, zirconia, boria, titania, calcia, or zinc. Furthermore, from the viewpoint of desulfurization / denitrification performance, industrial manufacturing, and catalyst strength, it is preferable that the support for the desulfurization / denitrification catalyst contains silica, silica-alumina, silica-alumina-phosphorus, silica-magnesia, alumina-silica-magnesia, alumina-silica-zirconia, etc. The support for the desulfurization / denitrification catalyst may be crystalline or amorphous. The shape of the support for the desulfurization / denitrification catalyst is not particularly limited and may be spherical, cylindrical, trilobed, quadrupedal, etc.

[0051] Examples of active metals in desulfurization and denitrification catalysts include Ni, Mo, Co, W, and P. A desulfurization and denitrification catalyst may contain one active metal, or two or more. From the viewpoint of easily achieving excellent hydrogenation ability and enabling more efficient desulfurization and denitrification, it is preferable that the desulfurization and denitrification catalyst contains at least Ni, and more preferably Ni and Mo or W. The active metal may be activated by sulfidation treatment. Among the above metals, the inclusion of Ni sulfide in particular makes it easier for the desulfurization and denitrification catalyst to achieve excellent hydrogenation ability.

[0052] Examples of high-resolution catalysts include hydrogenation catalysts in which an active metal is supported on a zeolite-containing support. Such hydrogenation catalysts tend to have small pores and excellent hydrogenation resolution capabilities.

[0053] The support for the high-resolution catalyst may contain components other than zeolite. The support for the high-resolution catalyst may, for example, contain oxides of elements from groups 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support for the high-resolution catalyst may contain at least one oxide of, for example, silica, alumina, phosphorus, magnesia, zirconia, boria, titania, calcia, zinc, etc. From the viewpoint of decomposition performance, desulfurization / denitrification performance, industrial manufacture, and catalyst strength, it is preferable that the support for the high-resolution catalyst contains alumina, silica, silica-alumina, silica-alumina-phosphorus, silica-magnesia, alumina-silica-magnesia, alumina-silica-zirconia, etc. The support for the high-resolution catalyst may be crystalline or amorphous. The shape of the support for the high-resolution catalyst is not particularly limited and may be spherical, cylindrical, trilobed, quadrupedal, etc.

[0054] Examples of active metals in high-resolution catalysts include Ni, Mo, Co, W, and P. A high-resolution catalyst may contain one active metal, or two or more. High-resolution catalysts are more likely to achieve excellent hydrogenation capacity and, from the viewpoint of more efficiently hydrogenating high-boiling-point oils, preferably contain at least Ni, and more preferably contain Ni and Mo or W. The active metals may be activated by sulfidation treatment. Among the above metals, the inclusion of Ni sulfide in particular makes it easier for desulfurization and denitrification catalysts to achieve excellent hydrogenation capacity.

[0055] Examples of low-resolution catalysts include hydrogenation catalysts in which an active metal is supported on a carrier containing alumina. Such hydrogenation catalysts have many large pores compared to high-resolution catalysts and tend to have milder hydrogenation resolution compared to high-resolution catalysts.

[0056] The support for the low-resolution catalyst may contain components other than alumina. For example, the support for the low-resolution catalyst may contain oxides of elements from groups 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support for the low-resolution catalyst may contain at least one oxide of, for example, silica, phosphorus, magnesia, zirconia, boria, titania, calcia, zinc, etc. From the viewpoint of decomposition performance, desulfurization / denitrification performance, industrial manufacture, and catalyst strength, it is preferable that the support for the low-resolution catalyst contains silica, silica-alumina, silica-alumina-phosphorus, silica-magnesia, alumina-silica-magnesia, alumina-silica-zirconia, etc. The support for the low-resolution catalyst may be crystalline or amorphous. The shape of the support for the low-resolution catalyst is not particularly limited and may be spherical, cylindrical, trilobed, quadrupedal, etc.

[0057] Examples of active metals in low-resolution catalysts include Ni, Mo, Co, W, and P. A low-resolution catalyst may contain one active metal, or two or more. From the viewpoint of more efficiently hydrogenating high-boiling point oils, it is preferable that the low-resolution catalyst contains at least Ni, and more preferably Ni and Mo or W. The active metals may be activated by sulfidation treatment. Among the above metals, the inclusion of Ni sulfide in particular makes it easier for the desulfurization / denitrification catalyst to achieve superior hydrogenation ability.

[0058] In the high-temperature hydrogenation process, a combination of desulfurization / denitrification catalysts and decomposition catalysts may be used. The decomposition catalyst may be a combination of a high-resolution catalyst and a low-resolution catalyst, or it may be a high-resolution catalyst alone, or it may be a low-resolution catalyst alone. The desulfurization / denitrification catalyst may be placed at least before the high-resolution catalyst and the low-resolution catalyst, or it may be placed both before and after the high-resolution catalyst and the low-resolution catalyst.

[0059] When the feed oil in the high-temperature hydrogenation process contains large amounts of nitrogen and sulfur, these elements can adhere to the active sites of high-resolution and low-resolution catalysts, potentially reducing their decomposition performance. When the feed oil comes into contact with a desulfurization / denitrification catalyst, the nitrogen in the feed oil is converted into gaseous components such as ammonia, reducing its nitrogen content, and the sulfur in the feed oil is converted into gaseous components such as hydrogen sulfide, reducing its sulfur content. Therefore, in the high-temperature hydrogenation process, it is preferable to place the desulfurization / denitrification catalyst before the high-resolution and low-resolution catalysts. Specifically, it is preferable to place the desulfurization / denitrification catalyst before the high-temperature hydrogenation unit described later. This arrangement suppresses the reduction in the decomposition performance of high-resolution and low-resolution catalysts, even when the feed oil contains large amounts of nitrogen and sulfur.

[0060] The high-temperature hydrogenation process may be carried out, for example, using a flow-through reactor. In this case, it is preferable to arrange, from the inlet side, a first catalyst layer containing a desulfurization / denitrification catalyst and a second catalyst layer containing a decomposition catalyst in this order within the flow-through reactor. Furthermore, a third catalyst layer containing a decomposition catalyst of a different type with different decomposition capabilities and a fourth catalyst layer containing a desulfurization / denitrification catalyst may be further arranged after the second catalyst layer.

[0061] The reaction temperature in the high-temperature hydrogenation process is, for example, higher than the reaction temperature in the low-temperature hydrogenation process and 500°C or lower, preferably 280°C or higher, more preferably 290°C or higher, even more preferably 300°C or higher, also preferably 450°C or lower, more preferably 430°C or lower, and even more preferably 410°C or lower. That is, the reaction temperature in the high-temperature hydrogenation process may be, for example, 280°C or higher and 450°C or lower, 280°C or higher and 430°C or lower, 280°C or higher and 410°C or lower, 290°C or higher and 450°C or lower, 290°C or higher and 430°C or lower, 290°C or higher and 410°C or lower, 300°C or higher and 450°C or lower, 300°C or higher and 430°C or lower, or 300°C or higher and 410°C or lower. By adjusting the reaction temperature in the high-temperature hydrogenation process within the above numerical range, hydrogenated oil with nitrogen and sulfur content adjusted to a specific numerical range can be obtained.

[0062] The reaction pressure in the high-temperature hydrogenation step is, for example, 2.0 MPaG or more and 15 MPaG or less, preferably 3.0 MPaG or more, more preferably 4.0 MPaG or more, also preferably 12 MPaG or less, more preferably 10 MPaG or less, and even more preferably 8 MPaG or less. That is, the reaction pressure in the high-temperature hydrogenation step may be, for example, 2.0 MPaG or more and 12 MPaG or less, 2.0 MPaG or more and 10 MPaG or less, 2.0 MPaG or more and 8 MPaG or less, 3.0 MPaG or more and 15 MPaG or less, 3.0 MPaG or more and 12 MPaG or less, 3.0 MPaG or more and 10 MPaG or less, 3.0 MPaG or more and 8 MPaG or less, 4.0 MPaG or more and 15 MPaG or less, 4.0 MPaG or more and 12 MPaG or less, 4.0 MPaG or more and 10 MPaG or less, or 4.0 MPaG or more and 8 MPaG or less. By adjusting the reaction pressure in the high-temperature hydrogenation process to within the above numerical range, hydrogenated oil can be obtained in which the nitrogen and sulfur content is adjusted to a specific numerical range.

[0063] When the high-temperature hydrogenation process is carried out using a flow-through reactor, the weight space velocity (WHSV) of the feedstock oil is, for example, 0.1h. －１ Total 5.0h －１ The following, preferably 0.3h －１ The above is more preferable, and 0.5h －１ The above, and more preferably 0.7h －１ The above is true, and preferably 4.0h －１ The following, and more preferably 3.0h －１ The following, and more preferably 2.0h －１ The following applies: That is, the weight space velocity (WHSV) of the raw material oil is, for example, 0.1h. －１ Total 4.0h －１ Below, 0.1h －１ 3.0 hours －１ Below, 0.1h －１ Total 2.0h －１ Below, 0.3h －１ Total 5.0h －１ Below, 0.3h －１ Total 4.0h －１ Below, 0.3h －１ 3.0 hours －１Below, 0.3h －１ Total 2.0h －１ Below, 0.5h －１ Total 5.0h －１ Below, 0.5h －１ Total 4.0h －１ Below, 0.5h －１ 3.0 hours －１ Below, 0.5h －１ Total 2.0h －１ Below, 0.7 hours －１ Total 5.0h －１ Below, 0.7 hours －１ Total 4.0h －１ Below, 0.7 hours －１ 3.0 hours －１ The following, or 0.7h －１ Total 2.0h －１ The following is also possible: By adjusting the weight space velocity of the raw material oil in the high-temperature hydrogenation process to within the above numerical range, hydrogenated oil can be obtained in which the nitrogen and sulfur content is adjusted to a specific numerical range.

[0064] [Method for Manufacturing Chemical Products] The method for manufacturing chemical products from the hydrothermally treated oil of pyrolysis oil derived from waste materials obtained in the present invention is not particularly limited, but for example, it includes an atmospheric distillation step in which a naphtha fraction is obtained by atmospheric distillation of a feedstock oil for atmospheric distillation containing at least a portion of the hydrothermally treated oil and crude oil, and a steam cracking step in which a steam cracking feedstock oil containing at least a portion of the naphtha fraction is subjected to steam cracking to obtain chemical products. Each step will be described in detail below.

[0065] (Atmospheric Distillation Process) The atmospheric distillation process is a process in which a naphtha fraction is obtained by atmospheric distillation of a feedstock oil for atmospheric distillation containing at least a portion of the hydrotreated oil and crude oil. The crude oil used in the atmospheric distillation process is not particularly limited, and conventionally known crude oil can be used, but it is preferable to use crude oil with low nitrogen and sulfur content. By using a feedstock oil for atmospheric distillation which is a mixture of hydrotreated oil and crude oil with low nitrogen and sulfur content, high stability can be achieved, thermal runaway can be suppressed, and the manufacturing process can be operated for a long period of time. The naphtha fraction may contain light naphtha and heavy naphtha, but it is particularly preferable to include light naphtha. The type of atmospheric distillation apparatus and operating conditions used in the atmospheric distillation process are not particularly limited, and the same apparatus and operating conditions as in the past can be used, and the equipment that has been installed in the refinery since the past can be used as is.

[0066] (Steam Cracking Process) The steam cracking process is a process in which a steam cracking feedstock oil containing at least a portion of the naphtha fraction and / or other fractions obtained in the atmospheric distillation process is subjected to steam cracking to obtain a chemical product. In the steam cracking process, the steam cracking feedstock oil is heat-treated with steam, which decomposes the naphtha fraction (light naphtha, etc.) and generates components useful as a chemical product.

[0067] In the steam cracking process, at least a portion of the naphtha fraction and / or other fractions obtained in the atmospheric distillation process may be subjected to steam cracking treatment, or all of it may be subjected to steam cracking treatment. Furthermore, the steam cracking feed oil in the steam cracking process may contain, in addition to the naphtha fraction, ethane, naphtha, kerosene, light oil fractions derived from petroleum, etc. In the steam cracking process, the naphtha fraction may be used as the steam cracking feed oil as is, or the naphtha fraction may be used as the steam cracking feed oil after additional treatment such as desulfurization treatment.

[0068] The conditions for the steam cracking treatment are not particularly limited and may be appropriately selected from known conditions used in the steam cracking treatment of ethane, naphtha, kerosene, etc.

[0069] Examples of chemical products obtained in the steam cracking process include ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, indene, and olefin-containing C9 aromatics for resin conversion such as methylstyrene.

[0070] In the steam cracking process, light fractions may be obtained in addition to the chemical products. Examples of light fractions include methane, ethane, butane, pentane, propane, and hexane.

[0071] (Method for producing synthetic rubber) The method for producing synthetic rubber of this embodiment includes a polymerization step in which synthetic rubber is obtained by a polymerization reaction using butadiene obtained by the above-described method as at least a part of the raw materials for synthetic rubber.

[0072] In the polymerization process, a polymerization composition containing at least butadiene as a monomer can be polymerized by conventionally known methods to obtain synthetic rubber. The polymerization method is not particularly limited, and conventionally known methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization can be used. The polymerization conditions are not particularly limited and can be adjusted as appropriate depending on the polymerization method, the composition of the polymerization composition, etc.

[0073] The monomer may be butadiene alone, or, in addition to butadiene, other monomers conventionally known for synthetic rubber may be used depending on the composition and properties of the desired synthetic rubber. Other monomers for synthetic rubber include conjugated diene compounds other than butadiene and aromatic vinyl compounds.

[0074] Examples of conjugated diene compounds other than butadiene include isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, and 2-chloro-1,3-butadiene. The conjugated diene compounds other than butadiene may be used individually or in combination of two or more.

[0075] Examples of aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, diphenylethylene, and tertiary amino group-containing diphenylethylene (e.g., 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene). Aromatic vinyl compounds may be used individually or in combination of two or more.

[0076] Polymerization compositions may contain not only monomers but also conventionally known additives and solvents. Examples of additives include polymerization initiators, emulsifiers, and surfactants.

[0077] For example, alkali metal compounds are used as polymerization initiators. Specific examples of alkali metal compounds include alkyllithium compounds such as methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium; 1,4-dilithiobutane, phenyllithium, stilbenithium, naphthyllithium, 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentylidene)dilithium, sodium naphthyl, potassium naphthyl, and potassium ethoxy.

[0078] (Tire) The tire of this embodiment contains synthetic rubber obtained by the synthetic rubber manufacturing method described above.

[0079] (Tire manufacturing method) The tire manufacturing method of this embodiment includes a vulcanization step in which a tire is obtained by a vulcanization reaction using synthetic rubber obtained by the above-described synthetic rubber manufacturing method as at least a part of the tire raw materials.

[0080] In the vulcanization process, a vulcanizing composition containing at least synthetic rubber can be vulcanized by conventionally known methods to obtain a tire. The vulcanization conditions are not particularly limited and can be adjusted as appropriate depending on the composition of the vulcanizing composition, the shape and structure of the target tire, etc.

[0081] The vulcanization composition may contain conventionally known additives in addition to synthetic rubber. Examples of additives include vulcanizing agents, vulcanization accelerators, vulcanization accelerators, antioxidants, softeners, antioxidants, and colorants. These additives may be used individually or in combination of two or more.

[0082] Examples of vulcanizing agents include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholin disulfide, and alkylphenol disulfide, as well as zinc oxide, magnesium oxide, LISSAGE, p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylenedianiline, phenol resins, brominated alkylphenol resins, and chlorinated alkylphenol resins.

[0083] Examples of vulcanization accelerators include thiram-based compounds such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM); aldehyde / ammonia-based compounds such as hexamethylenetetramine; guanidine-based compounds such as diphenylguanidine (DPG); thiazole-based compounds such as 2-mercaptobenzothiazole (MBT) and dibenzothiadyl disulfide (DM); sulfenamide-based compounds such as N-cyclohexyl-2-benzothiadylsulfenamide (CBS) and N-t-butyl-2-benzothiadylsulfenamide (BBS); and dithiocarbamate-based compounds such as zinc dimethyldithiocarbamate (ZnPDC).

[0084] Examples of vulcanization accelerators include fatty acids, zinc fatty acids, zinc fatty acid salts, and zinc oxide. Examples of fatty acids include acetic acid, propionic acid, butanoic 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.

[0085] Examples of anti-aging agents include aliphatic and aromatic hindered amines and hindered phenols.

[0086] Examples of antioxidants include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

[0087] Examples of colorants include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, red iron oxide, lithopon, lead, cadmium, iron, cobalt, aluminum, hydrochloride salts, and sulfates, as well as azo pigments and copper phthalocyanine pigments.

[0088] There are no particular restrictions on the shape, structure, size, and material of tires, and they can be appropriately selected according to the purpose. Furthermore, there are no particular restrictions on the use of tires, and examples include passenger car tires, heavy-duty tires, motorcycle tires, and studless tires.

[0089] Figures 2 to 9 are schematic diagrams showing an example of a system for carrying out the manufacturing method of this embodiment. Details of each apparatus and product described in Figures 2 to 9 are as described above.

[0090] The system 20 shown in Figure 2 comprises a pyrolysis unit 21 and a hydrogenation unit 22, and may further comprise an atmospheric distillation unit 24 and a steam cracking unit 25. In system 20, first, waste material S21 is supplied to the pyrolysis unit 21. In the pyrolysis unit 21, the waste material S21 is pyrolyzed to obtain pyrolysis oil S22. Subsequently, the pyrolysis oil S22 is supplied to a pipe 23 installed between the pyrolysis unit 21 and the hydrogenation unit 22. In the pipe 23, the pyrolysis oil S22 and a separately added diluent S23 are mixed to obtain mixed oil S24. Subsequently, the mixed oil S24 is supplied to the hydrogenation unit 22. In the hydrogenation unit 22, the mixed oil S24 is hydrogenated to obtain hydrogenated oil S25. Subsequently, the hydrogenated oil S25 is supplied to the atmospheric distillation unit 24. In the atmospheric distillation apparatus 24, naphtha fraction S26 is obtained by atmospheric distillation of the hydrogenated oil S25. Subsequently, the naphtha fraction S26 is supplied to the steam cracking apparatus 25. In the steam cracking apparatus 25, chemical product S27 is obtained by steam cracking treatment of the steam cracking feed oil containing the naphtha fraction S26.

[0091] The system 30 shown in Figure 3 comprises a pyrolysis unit 31 and a hydrogenation unit 32, and may further comprise an atmospheric distillation unit 34 and a steam cracking unit 35. In system 30, first, waste material S31 is supplied to the pyrolysis unit 31. In the pyrolysis unit 31, the waste material S31 is pyrolyzed to obtain pyrolysis oil S32. Subsequently, the pyrolysis oil S32 is supplied to a pipe 33 installed between the pyrolysis unit 31 and the hydrogenation unit 32. In the pipe 33, the pyrolysis oil S32 and a separately added diluent (recycled oil) S33 are mixed to obtain mixed oil S34. Subsequently, the mixed oil S34 is supplied to the hydrogenation unit 32. In the hydrogenation unit 32, the mixed oil S34 is hydrogenated to obtain hydrogenated oil S35. A portion of the hydrogenated oil S35 is reused as recycled oil (diluent S33). Subsequently, the hydrogenated oil S35 is supplied to the atmospheric distillation unit 34. In the atmospheric distillation apparatus 34, naphtha fraction S36 is obtained by atmospheric distillation of the hydrogenated oil S35. Subsequently, the naphtha fraction S36 is supplied to the steam cracking apparatus 35. In the steam cracking apparatus 35, chemical product S37 is obtained by steam cracking treatment of the steam cracking feed oil containing the naphtha fraction S36.

[0092] The system 40 shown in Figure 4 comprises a pyrolysis unit 41, a mixing tank 42, and a hydrogenation unit 43, and may further include an atmospheric distillation unit 44 and a steam cracking unit 45. In system 40, first, waste material S41 is supplied to the pyrolysis unit 41. In the pyrolysis unit 41, the waste material S41 is pyrolyzed to obtain pyrolysis oil S42. Next, the pyrolysis oil S42 is supplied to the mixing tank 42. In the mixing tank 42, the pyrolysis oil S42 is mixed with a separately added diluent S43 to obtain mixed oil S44. Next, the mixed oil S44 is supplied to the hydrogenation unit 43. In the hydrogenation unit 43, the mixed oil S44 is hydrogenated to obtain hydrogenated oil S45. Next, the hydrogenated oil S45 is supplied to the atmospheric distillation unit 44. In the atmospheric distillation unit 44, the hydrogenated oil S45 is distilled at atmospheric pressure to obtain naphtha fraction S46. Next, the naphtha fraction S46 is supplied to the steam cracking apparatus 45. In the steam cracking apparatus 45, the steam cracking feed oil containing the naphtha fraction S46 is subjected to steam cracking treatment to obtain the chemical product S47.

[0093] The system 50 shown in Figure 5 comprises a pyrolysis unit 51, a mixing tank 52, and a hydrogenation unit 53, and may further include an atmospheric distillation unit 54 and a steam cracking unit 55. In the system 50, first, waste material S51 is supplied to the pyrolysis unit 51, where the waste material S51 is pyrolyzed to obtain pyrolysis oil S52. Next, the pyrolysis oil S52 is supplied to the mixing tank 52. In the mixing tank 52, the pyrolysis oil S52 is mixed with a separately added diluent (recycled oil) S53 to obtain mixed oil S54. Next, the mixed oil S54 is supplied to the hydrogenation unit 53. In the hydrogenation unit 53, the mixed oil S54 is hydrogenated to obtain hydrogenated oil S55. A portion of the hydrogenated oil S55 is reused as recycled oil (diluent S53). Next, the hydrogenated oil S55 is supplied to the atmospheric distillation unit 54. In the atmospheric distillation unit 54, naphtha fraction S56 is obtained by atmospheric distillation of the hydrogenated oil S55. Subsequently, the naphtha fraction S56 is supplied to the steam cracking unit 55. In the steam cracking unit 55, chemical product S57 is obtained by steam cracking treatment of the steam cracking feed oil containing the naphtha fraction S56.

[0094] The system 60 shown in Figure 6 comprises a pyrolysis unit 61, a low-temperature hydrogenation unit 62, and a high-temperature hydrogenation unit 64, and may further include an atmospheric distillation unit 65 and a steam cracking unit 66. In system 60, first, waste material S61 is supplied to the pyrolysis unit 61. In the pyrolysis unit 61, the waste material S61 is pyrolyzed to obtain pyrolysis oil S62. Subsequently, the pyrolysis oil S62 is supplied to a pipe 63 installed between the pyrolysis unit 61 and the low-temperature hydrogenation unit 62. In the pipe 63, the pyrolysis oil S62 and a separately added diluent S63 are mixed to obtain mixed oil S64. Subsequently, the mixed oil S64 is supplied to the low-temperature hydrogenation unit 62. In the low-temperature hydrogenation unit 62, the mixed oil S64 is subjected to low-temperature hydrogenation to obtain low-temperature hydrogenated oil S65. Subsequently, the low-temperature hydrogenated oil S65 is supplied to the high-temperature hydrogenation unit 64. In the high-temperature hydrogenation unit 64, hydrogenated oil S66 is obtained by high-temperature hydrogenation treatment of low-temperature hydrogenated oil S65. Subsequently, the hydrogenated oil S66 is supplied to the atmospheric distillation unit 65. In the atmospheric distillation unit 65, naphtha fraction S67 is obtained by atmospheric distillation of the hydrogenated oil S66. Subsequently, the naphtha fraction S67 is supplied to the steam cracking unit 66. In the steam cracking unit 66, chemical product S68 is obtained by steam cracking treatment of the steam cracking feed oil containing naphtha fraction S67.

[0095] The system 70 shown in Figure 7 comprises a pyrolysis unit 71, a low-temperature hydrogenation unit 72, and a high-temperature hydrogenation unit 74, and may further include an atmospheric distillation unit 75 and a steam cracking unit 76. In the system 70, first, waste material S71 is supplied to the pyrolysis unit 71. In the pyrolysis unit 71, the waste material S71 is pyrolyzed to obtain pyrolysis oil S72. Subsequently, the pyrolysis oil S72 is supplied to a pipe 73 installed between the pyrolysis unit 71 and the low-temperature hydrogenation unit 72. In the pipe 73, the pyrolysis oil S72 and a separately added diluent oil (recycled oil) S73 are mixed to obtain mixed oil S74. Subsequently, the mixed oil S74 is supplied to the low-temperature hydrogenation unit 72. In the low-temperature hydrogenation unit 72, low-temperature hydrogenated oil S75 is obtained by low-temperature hydrogenation treatment of the mixed oil S74. Subsequently, the low-temperature hydrogenated oil S75 is supplied to the high-temperature hydrogenation unit 74. In the high-temperature hydrogenation unit 74, hydrotreated oil S76 is obtained by high-temperature hydrogenation treatment of low-temperature hydrogenated oil S75. A portion of the hydrotreated oil S76 is reused as recycled oil (diluting oil S73). Subsequently, the hydrotreated oil S76 is supplied to the atmospheric distillation unit 75. In the atmospheric distillation unit 75, naphtha fraction S77 is obtained by atmospheric distillation of the hydrotreated oil S76. Subsequently, the naphtha fraction S77 is supplied to the steam cracking unit 76. In the steam cracking unit 76, chemical product S78 is obtained by steam cracking treatment of the steam cracking feed oil containing the naphtha fraction S77.

[0096] The system 80 shown in Figure 8 comprises a pyrolysis unit 81, a mixing tank 82, a low-temperature hydrogenation unit 83, and a high-temperature hydrogenation unit 84, and may further include an atmospheric distillation unit 85 and a steam cracking unit 86. In system 80, first, waste material S81 is supplied to the pyrolysis unit 81. In the pyrolysis unit 81, the waste material S81 is pyrolyzed to obtain pyrolysis oil S82. Next, the pyrolysis oil S82 is supplied to the mixing tank 82. In the mixing tank 82, the pyrolysis oil S82 is mixed with a separately added diluent S83 to obtain mixed oil S84. Next, the mixed oil S84 is supplied to the low-temperature hydrogenation unit 83. In the low-temperature hydrogenation unit 83, the mixed oil S84 is subjected to low-temperature hydrogenation to obtain low-temperature hydrogenated oil S85. Next, the low-temperature hydrogenated oil S85 is supplied to the high-temperature hydrogenation unit 84. In the high-temperature hydrogenation unit 84, hydrotreated oil S86 is obtained by high-temperature hydrogenation treatment of low-temperature hydrogenated oil S85. Subsequently, the hydrotreated oil S86 is supplied to the atmospheric distillation unit 85. In the atmospheric distillation unit 85, naphtha fraction S87 is obtained by atmospheric distillation of the hydrotreated oil S86. Subsequently, the naphtha fraction S87 is supplied to the steam cracking unit 86. In the steam cracking unit 86, chemical product S88 is obtained by steam cracking treatment of the steam cracking feed oil containing naphtha fraction S87.

[0097] The system 90 shown in Figure 9 comprises a pyrolysis unit 91, a mixing tank 92, a low-temperature hydrogenation unit 93, and a high-temperature hydrogenation unit 94, and may further include an atmospheric distillation unit 95 and a steam cracking unit 96. In system 90, first, waste material S91 is supplied to the pyrolysis unit 91, where the waste material S91 is pyrolyzed to obtain pyrolysis oil S92. Next, the pyrolysis oil S92 is supplied to the mixing tank 92. In the mixing tank 92, the pyrolysis oil S92 is mixed with a separately added diluent oil (recycled oil) S93 to obtain mixed oil S94. Next, the mixed oil S94 is supplied to the low-temperature hydrogenation unit 93. In the low-temperature hydrogenation unit 93, the mixed oil S94 is subjected to low-temperature hydrogenation to obtain low-temperature hydrogenated oil S95. Next, the low-temperature hydrogenated oil S95 is supplied to the high-temperature hydrogenation unit 94. In the high-temperature hydrogenation unit 94, hydrotreated oil S96 is obtained by high-temperature hydrogenation treatment of low-temperature hydrogenated oil S95. A portion of the hydrotreated oil S96 is reused as recycled oil (diluting oil S93). Subsequently, the hydrotreated oil S96 is supplied to the atmospheric distillation unit 95. In the atmospheric distillation unit 95, naphtha fraction S97 is obtained by atmospheric distillation of the hydrotreated oil S96. Subsequently, the naphtha fraction S97 is supplied to the steam cracking unit 96. In the steam cracking unit 96, chemical product S98 is obtained by steam cracking treatment of the steam cracking feed oil containing the naphtha fraction S97.

[0098] Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0099] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0100] In the following examples, component analysis and evaluation are performed by the following methods: • Nitrogen content: JIS K 2609 (Crude oil and petroleum products - Test method for nitrogen content) • Sulfur content: JIS K 2541-7 (Crude oil and petroleum products - Test method for sulfur content, Part 7: Wavelength-dispersive X-ray fluorescence method (calibration curve method)) • Temperature measured by accelerated velocity calorimetry (ADT) ２４) Equipment used: ARC (Accelerating Rate Calorimeter, adiabatic calorimeter) Measurement method: The mixed oil is held at the measurement start temperature for 10 minutes. If no heat generation is detected, the temperature is raised by 5°C from that temperature, held for 10 minutes, and the presence or absence of heat generation is checked. This process is repeated until self-heating is confirmed. Once self-heating is confirmed, the device switches from heat generation detection mode to adiabatic control mode and starts measuring the heat generation behavior in an adiabatic state. Analysis method: The obtained time, temperature, and pressure data are corrected to calculate the heat generation start temperature, self-heating rate, TMR (time remaining until runaway in the adiabatic system (when the self-heating rate is at its maximum)), ADT24 (temperature at which TMR is 24 hours), maximum pressure and pressure rise rate during heat generation. ・Suitability evaluation (relative values ​​of frequency factors related to denitrification and desulfurization) When hydrotreating the mixed oil, the reaction rate is measured under multiple temperature conditions and the corresponding reaction rate constant k is determined. Based on this data, the natural logarithm lnk of the reaction rate constant against temperature 1 / T is plotted to create an Arrhenius plot. A regression line is derived using the least squares method, and the frequency factor A is calculated from the intercept of this line based on the following formula: lnA = Ea / RT + lnk. The frequency factor measures how often the reactants are likely to collide under suitable conditions and initiate a reaction. Therefore, by using the relative value of the frequency factor, the reactivity of novel reaction methods under different reaction conditions can be quantitatively compared.

[0101] (Example 1) (1) Pyrolysis process The pyrolysis process is carried out using the pyrolysis apparatus shown in Figure 1. Specifically, the pyrolysis furnace 2 (capacity 0.5 m³ ３ Approximately 100 kg of shredded waste tires (waste material 6) are placed inside the pyrolysis furnace 2, and the inside of the pyrolysis furnace 2 is replaced with nitrogen gas. Then, the nitrogen gas inside the pyrolysis apparatus is circulated and the gas temperature is raised to 500°C by the heat exchanger 1, and this temperature is maintained. The gas flow rate of nitrogen gas introduced into the pyrolysis furnace 2 is 0.005 m³. ３ Set to / s[ntp] and 0.0045m ３ / s[ntp] ~ 0.0055m ３The oxygen concentration is controlled within the range of / s[ntp]. Furthermore, the oxygen concentration within the pyrolysis apparatus is controlled to a range of 1% by volume or less. A zirconia oxygen sensor is used to measure the oxygen concentration within the pyrolysis apparatus. Pyrolysis oil is obtained from the bottom of the carbonization column 12a. The reaction is carried out until the distillation of the pyrolysis oil stops, and after the distillation stops, the heat exchanger 1 is stopped and left to cool for about 12 hours.

[0102] (2) Mixing process In a pipe installed between the pyrolysis apparatus and the hydrogenation apparatus in the low-temperature hydrogenation process described later, the pyrolysis oil and the diluent oil are mixed in a mass ratio of 30:70 to obtain a mixed oil. Vacuum gas oil (VGO) is used as the diluent oil. VGO contains hydrocarbons with 10 to 100 carbon atoms (e.g., butylbenzene).

[0103] (3) Hydrogenation Process (3-1) Production of Hydrogenation Catalyst A-1 A cylindrical support with a diameter of approximately 1.6 mm and a length of approximately 3 mm is prepared using silica-alumina powder with a composition of 97% by mass of alumina and 3% by mass of silica as the oxide. Nickel nitrate and ammonium molybdate are dissolved in deionized water corresponding to the amount of water absorbed by the support, which has been measured in advance, to obtain a nickel nitrate and ammonium molybdate impregnation solution. This impregnation solution is impregnated into the support by the initial wetting method, and the Ni content in terms of oxide is 4% by mass and the Mo content in terms of oxide is 20% by mass, based on the mass of the support. Next, the obtained impregnated material (catalysis precursor) is 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.

[0104] (3-2) 0.9 kg of silica-alumina powder containing 30% by mass of alumina and 70% by mass of silica and SiO as the oxides for the production of hydrogenation catalyst B-1 ２ / Al ２ O ３Using 0.1 kg of USY zeolite with a pH of 30, a cylindrical support with a diameter of approximately 1.6 mm and a length of approximately 3 mm is prepared by addition, kneading, and calcination. Nickel nitrate and ammonium tungstate are dissolved in deionized water corresponding to the amount of water absorbed by the support, which was measured in advance, to obtain a nickel nitrate and ammonium tungstate impregnation solution. This impregnation solution is impregnated into the support by the initial wetting method, and the Ni content in terms of oxide is 10% by mass and the W content in terms of oxide is 20% by mass, based on the mass of the support. Next, the resulting impregnated material (catalysis precursor) is 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.

[0105] (3-3) Hydrogenation-treated hydrogenation catalyst A-1 and hydrogenation catalyst B-1 are packed into a reaction tube (inner diameter 20 mm) in a weight ratio of 8:2. The packing order is hydrogenation catalyst A-1 in the front of the reaction tube and hydrogenation catalyst B-1 in the rear of the reaction tube. After sulfurization treatment with oil in which dimethyl disulfide is dissolved at 1% by mass in light oil, the reaction temperature is 380°C, the reaction pressure is 5.0 MPaG, and the gravitational space velocity is 1.0 h. －１ Under these conditions, a hydrogenation treatment is performed using the mixed oil as a raw material to obtain hydrogenated oil.

[0106] (Example 2) A mixed oil is obtained in the same manner as in Example 1, except that cracked light oil (LCO) is used as a diluent in the mixing step. The LCO contains hydrocarbons with 5 to 30 carbon atoms (e.g., naphthalene). Subsequently, a hydrogenated oil is obtained in the same manner as in Example 1, except that the mixed oil is used in the hydrogenation step and the reaction temperature of the hydrogenation treatment is changed to 300°C.

[0107] (Example 3) A mixed oil is obtained in the same manner as in Example 1, except that naphtha is used as a diluent in the mixing step. The naphtha contains hydrocarbons with 5 to 15 carbon atoms (e.g., benzene). Subsequently, a hydrogenated oil is obtained in the same manner as in Example 1, except that the mixed oil is used in the hydrogenation step and the reaction temperature of the hydrogenation treatment is changed to 300°C.

[0108] (Example 4) A mixed oil is obtained in the same manner as in Example 1, except that recycled oil (hydrogenated oil obtained in the hydrogenation step of this example) is used as the diluent in the mixing step. Subsequently, a hydrogenated oil is obtained in the same manner as in Example 1, except that the mixed oil is used in the hydrogenation step and the reaction temperature of the hydrogenation treatment is changed to 300°C. Note that ADT24 is not detected in the mixed oil obtained in this example at temperatures below 400°C.

[0109] (Example 5) A mixed oil is obtained in the same manner as in Example 4, except that the mixing ratio of the pyrolysis oil and the diluent oil (recycled oil) is changed to 50:50 in the mixing step. Subsequently, a hydrogenated oil is obtained in the same manner as in Example 4, using the mixed oil in the hydrogenation step, except that the reaction temperature of the hydrogenation treatment is changed to 300°C.

[0110] (Example 6) A mixed oil is obtained in the same manner as in Example 4, except that the mixing ratio of the pyrolysis oil and the diluent oil (recycled oil) in the mixing step is changed to 80:20. Subsequently, a hydrogenated oil is obtained in the same manner as in Example 4, except that the mixed oil is used in the hydrogenation step and the reaction temperature of the hydrogenation treatment is changed to 300°C.

[0111] (Example 7) Hydrogenation process: reaction temperature 220°C, reaction pressure 5.0 MPaG, gravimetric space velocity 1.0 h －１ Hydrogenated oil is obtained in the same manner as in Example 1, except that a low-temperature hydrogenation treatment is performed using the mixed oil as a raw material under the specified conditions, and a high-temperature hydrogenation treatment is performed using the resulting oil as a raw material under the conditions of a reaction temperature of 380°C, a reaction pressure of 5.0 MPaG, and a gravimetric space velocity of 1.0 h⁻¹.

[0112] (Example 8) In the hydrogenation process, a low-temperature hydrogenation treatment was performed using the mixed oil as the raw material under the conditions of a reaction temperature of 220°C, a reaction pressure of 5.0 MPaG, and a gravimetric space velocity of 1.0 h⁻¹. The resulting oil was then used as the raw material for a reaction at a reaction temperature of 380°C, a reaction pressure of 5.0 MPaG, and a gravimetric space velocity of 1.0 h⁻¹. －１ Hydrogenated oil is obtained in the same manner as in Example 4, except that high-temperature hydrogenation treatment is performed under the specified conditions.

[0113] (Comparative Example 1) Hydrogenated oil is obtained in the same manner as in Example 1, except that the mixing step is omitted, the pyrolysis oil is used directly as a raw material in the hydrogenation step, and the reaction temperature of the hydrogenation treatment is changed to 300°C. The ADT24 of the mixed oil obtained in this comparative example is 240°C.

[0114] (Comparative Example 2) A mixed oil is obtained in the same manner as in Example 4, except that the mixing ratio of the pyrolysis oil and the diluent oil (recycled oil) is changed to 90:10 in the mixing step. Subsequently, a hydrogenated oil is obtained in the same manner as in Example 4, except that the mixed oil is used in the hydrogenation step and the reaction temperature of the hydrogenation treatment is changed to 300°C.

[0115] (Comparative Example 3) Dilution oil was obtained in the same manner as in Example 1, except that the pyrolysis oil (30 parts by mass) and dilution oil (70 parts by mass) were not mixed in advance, and were supplied directly to the hydrocracking apparatus.

[0116] Table 1 shows the measurement and evaluation results for Examples 1-8 and Comparative Examples 1-3. As shown in Table 1, Comparative Example 1 did not undergo a mixing process, and the nitrogen and sulfur concentrations of the hydrotreated oil were higher than in Examples 1-8, making denitrification and desulfurization difficult. Furthermore, it had low stability and a risk of thermal runaway, indicating that it was unsuitable for the series of processes used to manufacture chemical products. Similarly, in Comparative Example 2, the mixing ratio of the diluent oil was low, and the nitrogen and sulfur concentrations of the hydrotreated oil were higher than in Examples 1-8, making denitrification and desulfurization difficult. Furthermore, it had low stability and a risk of thermal runaway, indicating that it was unsuitable for the series of processes used to manufacture chemical products. In addition, in Comparative Example 3, the pyrolysis oil and diluent oil were not sufficiently mixed, resulting in low reactivity. The nitrogen and sulfur content were not sufficiently reduced compared to Examples 1-8, leading to low stability and a risk of thermal runaway, indicating that it was unsuitable for the series of processes used to manufacture chemical products.

[0117]

[0118] From the above examples, it is confirmed that the present invention makes it possible to produce a hydrogenated oil suitable for a series of processes for manufacturing chemical products from waste materials including at least one of waste tires and waste plastics.

[0119] 1... Heat exchanger, 2... Pyrolysis furnace, 3... Oxygen-free gas supply source, 4... Circulation path, 5... Oil recovery device, 6... Waste material, 7... Decomposition device, 8... External heating means, 9... Flow meter, 10... Damper, 11... Blower, 12... Carbonization tower, 13... Recovery tank, 14... Hot air furnace, 15... Exhaust fan, 16... Exhaust gas treatment device 20... System, 21... Pyrolysis device, 22... Hydrogenation device, 23... Piping, 24... Atmospheric distillation device, 25... Steam cracking device, S21... Waste material, S22... Pyrolysis oil, S23... Dilution oil, S24... Mixed oil, S25... Hydrogenated oil, S26... Naphtha fraction, S27... Chemical products 30...System, 31...Pyrolysis unit, 32...Hydrogenation unit, 33...Piping, 34...Atmospheric distillation unit, 35...Steam cracking unit, S31...Waste material, S32...Pyrolysis oil, S33...Dilution oil (recycled oil), S34...Mixed oil, S35...Hydrogenated oil, S36...Naphtha fraction, S37...Chemical products 40...System, 41...Pyrolysis unit, 42...Mixing tank, 43...Hydrogenation unit, 44...Atmospheric distillation unit, 45...Steam cracking unit, S41...Waste material, S42...Pyrolysis oil, S43...Dilution oil, S44...Mixed oil, S45...Hydrogenated oil, S46...Naphtha fraction, S47...Chemical products 50...System, 51...Pyrolysis unit, 52...Mixing tank, 53...Hydrogenation unit, 54...Atmospheric distillation unit, 55...Steam cracking unit, S51...Waste material, S52...Pyrolysis oil, S53...Diluting oil (recycled oil), S54...Mixed oil, S55...Hydrogenated oil, S56...Naphtha fraction, S57...Chemical products 60...System, 61...Pyrolysis unit, 62...Low-temperature hydrogenation unit, 63...Piping, 64...High-temperature hydrogenation unit, 65...Atmospheric distillation unit, 66...Steam cracking unit, S61...Waste material, S62...Pyrolysis oil, S63...Diluting oil, S64...Mixed oil, S65...Low-temperature hydrogenated oil, S66...Hydrogenated oil, S67...Naphtha fraction, S68...Chemical products 70...System, 71...Pyrolysis unit, 72...Low-temperature hydrogenation unit, 73...Piping, 74...High-temperature hydrogenation unit, 75...Atmospheric distillation unit, 76...Steam cracking unit, S71...Waste material, S72...Pyrolysis oil, S73...Dilution oil (recycled oil), S74...Mixed oil, S75...Low-temperature hydrogenated oil, S76...Hydrogenated oil, S77...Naphtha fraction, S78...Chemical products80...System, 81...Pyrolysis unit, 82...Mixing tank, 83...Low-temperature hydrogenation unit, 84...High-temperature hydrogenation unit, 85...Atmospheric distillation unit, 86...Steam cracking unit, S81...Waste material, S82...Pyrolysis oil, S83...Dilution oil, S84...Mixed oil, S85...Low-temperature hydrogenated oil, S86...Hydrogenated oil, S87...Naphtha fraction, S88...Chemical products 90...System, 91...Pyrolysis unit, 92...Mixing tank, 93...Low-temperature hydrogenation unit, 94...High-temperature hydrogenation unit, 95...Atmospheric distillation unit, 96...Steam cracking unit, S91...Waste material, S92...Pyrolysis oil, S93...Dilution oil (recycled oil), S94...Mixed oil, S95...Low-temperature hydrogenated oil, S96...Hydrogenated oil, S97...Naphtha fraction, S98...Chemical products

Claims

1. A method for producing hydrotreated oil, comprising: a thermal decomposition step of obtaining a thermal decomposition oil by thermal decomposition of waste material containing at least one of waste tires and waste plastics; a mixing step of mixing the thermal decomposition oil with a diluent oil to obtain a mixed oil; and a hydrogenation step of subjecting the mixed oil to a hydrotreatment to obtain a hydrotreated oil having a nitrogen content of 300 ppm by mass or less and a sulfur content of 1000 ppm by mass or less.

2. The manufacturing method according to claim 1, wherein the diluent oil contains hydrocarbons having 5 to 100 carbon atoms.

3. The manufacturing method according to claim 1, wherein the diluent oil includes recycled oil containing at least a portion of the hydrogenated oil.

4. The manufacturing method according to claim 1, wherein the nitrogen content of the mixed oil is 5,000 ppm by mass or less.

5. The manufacturing method according to claim 1, wherein the amount of the pyrolysis oil in the mixed oil is 0.1% by mass or more and 80% by mass of the total amount of the mixed oil.

6. The manufacturing method according to claim 1, wherein in the mixing step, the pyrolysis oil and the diluent oil are mixed using means different from those of the hydrogenation apparatus.

7. The manufacturing method according to claim 6, wherein the different means is a mixing tank installed between the pyrolysis apparatus and the hydrogenation apparatus.

8. The manufacturing method according to claim 6, wherein the different means is piping installed between the pyrolysis apparatus and the hydrogenation apparatus.

9. A method for producing synthetic rubber, comprising: a step of obtaining a chemical product containing butadiene using a hydrogenated oil obtained by a manufacturing method described in any one of claims 1 to 8; and a polymerization step of obtaining synthetic rubber by a polymerization reaction using the butadiene as at least a part of the raw materials for synthetic rubber.

10. A tire comprising synthetic rubber obtained by the manufacturing method described in claim 9.

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