Hydrotreated oil and method for producing same

Abstract

PROBLEM TO BE SOLVED: To provide a waste-derived hydrotreated pyrolysis oil that enables long-term operation of a process for producing a hydrocarbon by using hydrotreated pyrolysis oil and is suitable for naphtha treatment, etc. in refineries, and a method for producing the same. SOLUTION: A waste-derived hydrotreated pyrolysis oil containing at least one of waste tires and waste plastics, in which the nitrogen content of the hydrotreated oil is from more than 20 mass ppm to 80 mass ppm.

Description

Hydrotreated oil and method for producing the same

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

[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 types and qualities of waste materials not necessarily being constant and the need for a process that can utilize existing equipment, the development of various processes is desired.

[0005] The inventors of the present invention have found that in a process for producing hydrocarbons using a hydrotreated oil of pyrolysis oil, when the nitrogen content in naphtha is high, it has an adverse effect on naphtha treatment and the like in an oil refinery. Further, when the generation of dirt (by-products such as polymers of hydrocarbons) cannot be suppressed from the hydrotreated oil, from the perspective of maintenance, it has an adverse effect on the long-term operation of the above production process.

[0006] Therefore, an object of the present invention is to provide a hydrotreated oil of pyrolysis oil derived from waste materials and a method for producing the same, which enable the long-term operation of the above production process and are suitable for naphtha treatment and the like in an oil refinery.

[0007] As a result of investigations to solve the above problems, the inventors of the present invention have found that the above problems can be solved by using a hydrotreated oil having a nitrogen content within a specific range. Based on such findings, the inventors of the present invention have completed the present invention.

[0008] One aspect of the present invention relates, for example, to the following: [1] A hydrogenated oil of pyrolysis oil derived from waste materials, comprising at least one of waste tires and waste plastics, wherein the nitrogen content of the hydrogenated oil is greater than 20 ppm by mass and 80 ppm by mass or less. [2] The hydrogenated oil according to [1], wherein the nitrogen content of the hydrogenated oil comprises aniline. [3] The hydrogenated oil according to [2], wherein the aniline content of the hydrogenated oil is 10 ppm by mass or more and 50 ppm by mass or less. [4] The hydrogenated oil according to any one of [1] to [3], wherein the nitrogen content of the pyrolysis oil is 1,000 ppm by mass or more and 10,000 ppm by mass or less. [5] A pyrolysis step to obtain pyrolysis oil by pyrolysis of waste materials including at least one of waste tires and waste plastics; and a raw material oil containing at least a portion of the pyrolysis oil, reacted at a reaction temperature of 180°C to 300°C, a reaction pressure of 2.0 MPaG to 20 MPaG, and a gravitational space velocity of 0.1 h. －１ Total 5.0h －１ A low-temperature hydrogenation step to obtain low-temperature hydrogenated oil by performing a low-temperature hydrogenation treatment under the following conditions: and a raw material oil containing at least a portion of the low-temperature hydrogenated oil is subjected to a reaction at a temperature higher than the reaction temperature in the low-temperature hydrogenation treatment but 500°C or lower, a reaction pressure of 2.0 MPaG or higher and 15 MPaG or lower, and a gravitational space velocity of 0.1 h. －１ Total 5.0h －１A method for producing hydrogenated oil, comprising: a high-temperature hydrogenation step of performing a hydrogenation treatment under the following conditions to obtain hydrogenated oil, wherein the nitrogen content of the hydrogenated oil is greater than 20 ppm by mass and 80 ppm by mass or less. [6] The method for producing hydrogenated oil according to [5], wherein the hydrogenation treatment temperature in the high-temperature hydrogenation step is 280°C or more and 450°C or less. [7] The method for producing hydrogenated oil according to [5] or [6], wherein the nitrogen content of the hydrogenated oil contains aniline. [8] The method for producing hydrogenated oil according to [7], wherein the aniline content of the pyrolysis hydrogenated oil is 10 ppm by mass or more and 50 ppm by mass or less. [9] The method for producing hydrogenated oil according to any one of [5] to [8], wherein the nitrogen content of the pyrolysis oil is 1,000 ppm by mass or more and 10,000 ppm by mass or less.

[10] The method for producing hydrogenated oil according to any one of [5] to [9], wherein recycled oil containing at least a portion of the hydrogenated oil is used as part of the raw material oil in the low-temperature hydrogenation step.

[11] The manufacturing method according to

[10] , wherein the amount of recycled oil in the raw material oil used in the low-temperature hydrogenation step is 20% by mass or more and 90% by mass or less with respect to the total amount of recycled oil and pyrolysis oil.

[0009] The present invention provides a hydrogenated oil derived from waste materials, which enables long-term operation of the above-mentioned manufacturing process and is suitable for naphtha treatment in oil refineries, and a method for producing the same.

[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 of the fouling evaluation test apparatus (HLPS) used in the example.

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

[0012] [Hydrogenated Oil] The hydrogenated oil in this embodiment is obtained by hydrogenating pyrolysis oil derived from waste materials. By having a nitrogen content of more than 20 ppm by mass and 80 ppm by mass or less in the hydrogenated oil, it is possible to enable long-term operation of a process that uses hydrogenated pyrolysis oil to produce hydrocarbons, and it is possible to suppress adverse effects on naphtha processing and other processes at the refinery.

[0013] The nitrogen content of the hydrogenated oil is preferably 25 ppm by mass or more, more preferably 27 ppm by mass or more, even more preferably 30 ppm by mass or more, also preferably 75 ppm by mass or less, more preferably 70 ppm by mass or less, and even more preferably 65 ppm by mass or less. In other words, the nitrogen content of the hydrotreated oil may be, for example, more than 20 ppm by mass and 75 ppm by mass or less, more than 20 ppm by mass and 70 ppm by mass or less, more than 20 ppm by mass and 65 ppm by mass, 25 ppm by mass and 80 ppm by mass, 25 ppm by mass and 75 ppm by mass, 25 ppm by mass and 70 ppm by mass, 25 ppm by mass and 65 ppm by mass, 27 ppm by mass and 80 ppm by mass, 27 ppm by mass and 75 ppm by mass, 27 ppm by mass and 70 ppm by mass, 27 ppm by mass and 65 ppm by mass, 30 ppm by mass and 80 ppm by mass, 30 ppm by mass and 75 ppm by mass, 30 ppm by mass and 70 ppm by mass, or 30 ppm by mass and 65 ppm by mass.

[0014] Aniline is a major component of the nitrogen content in hydrotreated oil. It is presumed that the aniline in hydrotreated oil is produced by the thermal decomposition of additives such as antioxidants used in waste materials such as waste tires and waste plastics, or by the subsequent hydrotreatment process. Therefore, the conditions of the hydrotreatment process are important. If the conditions of the hydrotreatment process are insufficient, a large amount of aniline will remain in the hydrotreated oil. Among the nitrogen components, aniline has a boiling point of 184°C and is included in the naphtha fraction during naphtha treatment at the refinery, making it difficult to remove or requiring further treatment. Therefore, it is preferable to reduce the aniline content (aniline content) of hydrotreated oil. The aniline content of the hydrotreated oil is preferably 50 ppm by mass or less, more preferably 45 ppm by mass or less, even more preferably 40 ppm by mass or less, and even more preferably 38 ppm by mass or less, and from the viewpoint of the energy and other costs required for the hydrotreatment, it may be 10 ppm by mass or more, 12 ppm by mass or more, 15 ppm by mass or more, or 17 ppm by mass or more. In other words, the aniline content of the hydrogenated oil is 10 ppm to 50 ppm by mass, 10 ppm to 45 ppm by mass, 10 ppm to 40 ppm by mass, 10 ppm to 38 ppm by mass, 12 ppm to 50 ppm by mass, 12 ppm to 45 ppm by mass, 12 ppm to 40 ppm by mass, and 12 ppm to 38 ppm by mass. pm or less, 15 mass ppm or more and 50 mass ppm or less, 15 mass ppm or more and 45 mass ppm or less, 15 mass ppm or more and 40 mass ppm or less, 15 mass ppm or more and 38 mass ppm or less, 17 It may be at least 17 ppm by mass and at most 45 ppm by mass, at least 17 ppm by mass and at most 40 ppm by mass, or at least 17 ppm by mass and at most 38 ppm by mass.

[0015] [Method for producing hydrogenated oil] The method for producing hydrogenated oil according to this embodiment includes a thermal decomposition step to obtain thermal decomposition oil by thermal decomposition of waste material containing at least one of waste tires and waste plastics; a low-temperature hydrogenation step to obtain low-temperature hydrogenated oil by subjecting a raw material oil containing at least a portion of the thermal decomposition oil to low-temperature hydrogenation treatment; and a high-temperature hydrogenation step to obtain hydrogenated oil by subjecting a raw material oil containing at least a portion of the low-temperature hydrogenated oil to hydrogenation treatment. Each step will be described in detail below.

[0016] (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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] The thermal decomposition temperature (temperature of the high-temperature gas) in the thermal decomposition process is preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, and also preferably 800°C or lower, more preferably 750°C or lower, and even more preferably 700°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, 300°C or higher and 800°C or lower, 300°C or higher and 750°C or lower, 300°C or higher and 700°C or lower, 350°C or higher and 800°C or lower, 350°C or higher and 750°C or lower, 350°C or higher and 700°C or lower, 400°C or higher and 800°C or lower, 400°C or higher and 750°C or lower, or 400°C or higher and 700°C or lower.

[0021] 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.

[0022] 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.

[0023] The distillation properties of the pyrolysis oil are not particularly limited; for example, any properties suitable for use as a feedstock oil in low-temperature hydrogenation and high-temperature hydrogenation processes are acceptable.

[0024] The nitrogen content of the pyrolysis 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 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, the nitrogen content can be significantly reduced by adjusting the hydrogenation treatment conditions in the low-temperature hydrogenation process and the high-temperature hydrogenation process, which converts the nitrogen into gaseous components such as ammonia through hydrogenation. 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, 1,500 ppm by mass or more and 10,000 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, 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, or 2,000 ppm by mass or more and 8,000 ppm by mass or less. The aniline content of the pyrolysis oil may be, for example, 10 ppm by mass or more, 15 ppm by mass or more, 20 ppm by mass or more, or 200 ppm by mass or less, 150 ppm by mass or less, or 100 ppm by mass or less, from the viewpoint of suppressing adverse effects on naphtha processing at the refinery. In other words, the aniline content of the pyrolysis oil may be, for example, 10 ppm to 200 ppm by mass, 10 ppm to 150 ppm by mass, 10 ppm to 100 ppm by mass, 15 ppm to 200 ppm by mass, 15 ppm to 150 ppm by mass, 15 ppm to 100 ppm by mass, 20 ppm to 200 ppm by mass, 20 ppm to 150 ppm by mass, or 20 ppm to 100 ppm by mass. Pyrolysis oil using waste tires as waste material tends to have higher nitrogen and aniline content compared to pyrolysis oil using waste plastics as waste material. This is presumed to be because waste tires use a larger amount of additives such as anti-aging agents compared to waste plastics.Furthermore, depending on the hydrogenation conditions of the subsequent low-temperature and high-temperature hydrogenation processes, aniline may be generated by the decomposition of additive components derived from waste materials contained in the pyrolysis oil, potentially increasing the aniline content of the hydrogenated oil compared to that of the pyrolysis oil.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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 the raw material oil for the low-temperature 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.

[0029] 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 low-temperature 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.

[0030] 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.

[0031] (Low-temperature hydrogenation process) The low-temperature hydrogenation process is a process in which a raw material oil containing at least a portion of the pyrolysis oil is subjected to low-temperature hydrogenation treatment to obtain low-temperature hydrogenated oil.

[0032] The raw material oil used in the low-temperature hydrogenation process includes pyrolysis oil and may also contain other components. Furthermore, pyrolysis oil may be used directly as the raw material oil in the low-temperature hydrogenation process.

[0033] As part of the feedstock oil in the low-temperature hydrogenation process, recycled oil containing at least a portion of the hydrogenated oil obtained in the high-temperature hydrogenation process described later, or any diluent hydrocarbon oil may be used. By using recycled oil or any diluent hydrocarbon oil, various components such as nitrogen and dienes that cause fouling can be diluted, thus preventing fouling. In addition, the heat generated in the reactors during the low-temperature and high-temperature hydrogenation processes can be reduced, improving the stability of process operation. Examples of diluent hydrocarbons include kerosene fractions, light oil fractions, and vacuum light oil fractions obtained from atmospheric distillation units derived from crude oil, LCO obtained from FCC units, and also product kerosene and product light oil.

[0034] In the low-temperature hydrogenation process, the amount of recycled oil relative to the total amount of recycled oil and pyrolysis oil in the raw material oil is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and may also be 90% by mass or less, 85% by mass or less, or 80% by mass or less. That is, the amount of recycled oil relative to the total amount of recycled oil and pyrolysis oil in the raw material oil may be, for example, 20% by mass or more and 90% by mass or less, 20% by mass or more and 85% by mass or less, 20% by mass or more and 80% by mass or less, 30% by mass or more and 90% by mass or less, 30% by mass or more and 85% by mass or less, 30% by mass or more and 80% by mass or less, 40% by mass or more and 90% by mass or less, 40% by mass or more and 85% by mass or less, 40% by mass or more and 80% by mass or less, 50% by mass or more and 90% by mass or less, 50% by mass or more and 85% by mass or less, or 50% by mass or more and 80% by mass or less.

[0035] 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.

[0036] The reaction temperature in the low-temperature hydrogenation process is 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 in the pyrolysis oil that cause fouling in the heat exchanger can be reduced.

[0037] The reaction pressure in the low-temperature hydrogenation process is 2.0 MPaG or more and 20 MPaG or less, preferably 4.0 MPaG or more, more preferably 6.0 MPaG or more, even more preferably 8.0 MPaG or more, also preferably 18 MPaG or less, more preferably 16 MPaG or less, and even more preferably 14 MPaG or less. In other words, the reaction pressure in the low-temperature hydrogenation process may be, for example, 2.0 MPaG to 18 MPaG, 2.0 MPaG to 16 MPaG, 2.0 MPaG to 14 MPaG, 4.0 MPaG to 20 MPaG, 4.0 MPaG to 18 MPaG, 4.0 MPaG to 16 MPaG, 4.0 MPaG to 14 MPaG, 6.0 MPaG to 20 MPaG, 6.0 MPaG to 18 MPaG, 6.0 MPaG to 16 MPaG, 6.0 MPaG to 14 MPaG, 8.0 MPaG to 20 MPaG, 8.0 MPaG to 18 MPaG, 8.0 MPaG to 16 MPaG, or 8.0 MPaG to 14 MPaG. By adjusting the reaction pressure in the low-temperature hydrogenation process to within the above numerical range, the amount of dienes in the pyrolysis oil that cause fouling in the heat exchanger can be reduced.

[0038] When the low-temperature hydrogentemperature －１ temperature hydrogen addition process is carried out using a flow reactor, the weight hourly space velocity (WHSV) of the feedstock oil is 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 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 feedstock 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 －１ or more and 5.0 h －１ or less, 0.3 h －１ or more and 4.0 h －１ or less, 0.3 h －１ or more and 3.0 h －１ or less, 0.3 h －１ or more and 2.0 h －１ or less, 0.5 h －１ or more and 5.0 h －１ or less, 0.5 h －１ or more and 4.0 h －１ or less, 0.5 h －１ or more and 3.0 h －１ or less, 0.5 h －１ or more and 2.0 h －１ or less, 0.7 h －１ or more and 5.0 h －１ or less, 0.7 h －１ or more and 4.0 h －１ or less, 0.7 h －１ or more, or 0.7 h －１ or more and 2.0 h －１ or less may also be acceptable. By adjusting the weight hourly space velocity in the low-temperature hydrogen addition process within the above numerical range, the dienes in the pyrolysis oil that cause fouling in the heat exchanger can be reduced.

[0039] The diene number of the low-temperature hydrogenated oil obtained in the low-temperature hydrogenation process is preferably 14.0 gI ２ Less than 100g, more preferably 12.0g ２ / 100g or less, more preferably 10.0g ２ / 100g or less, and particularly preferably 8.0g ２ The amount is less than 100g. By reducing dienes in the pyrolysis oil through the low-temperature hydrogenation process, fouling in the heat exchangers of the high-temperature hydrogenation process and atmospheric distillation unit can be suppressed, enabling long-term operation of the process.

[0040] (High-Temperature Hydrogenation Process) The high-temperature hydrogenation process is a process in which a raw material oil containing at least a portion of the low-temperature hydrogenated oil is subjected to hydrogenation treatment to obtain hydrogenated oil. Hydrogenated oil is described in detail above.

[0041] The raw material oil used in the high-temperature hydrogenation process includes low-temperature hydrogenated oil and may further contain components other than low-temperature hydrogenated oil (for example, pyrolysis oil or fractionally distilled pyrolysis oil). Alternatively, low-temperature hydrogenated oil may be used directly as the raw material oil in the high-temperature hydrogenation process.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] In the high-temperature hydrogenation process, if the feed oil contains nitrogen, the nitrogen in the feed oil may 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 the desulfurization / denitrification catalyst, the nitrogen contained in the feed oil is converted to ammonia, etc., reducing the nitrogen content in the feed oil. Therefore, in the high-temperature hydrogenation process, it is preferable to place the desulfurization / denitrification catalyst before the high-resolution and low-resolution catalysts. In other words, it is preferable to place the desulfurization / denitrification catalyst before the high-temperature hydrogenation unit described later. With this arrangement, even if the feed oil contains nitrogen, the reduction in the decomposition performance of the high-resolution and low-resolution catalysts can be suppressed.

[0055] 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.

[0056] The reaction temperature in the high-temperature hydrogenation step is higher than the reaction temperature in the low-temperature hydrogenation step 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 step 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 step within the above numerical range, hydrogenated oil with nitrogen content, particularly aniline content, adjusted to a specific numerical range can be obtained.

[0057] The reaction pressure in the high-temperature hydrogenation step is 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, it is possible to obtain hydrogenated oil in which the nitrogen content, particularly the aniline content, is adjusted to a specific numerical range.

[0058] When the high-temperature hydrogenation process is carried out using a flow-through reactor, the weight space velocity (WHSV) of the feedstock oil is 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 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 －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 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, a hydrogenated oil can be obtained in which the nitrogen content, especially the aniline content, is adjusted to a specific numerical range.

[0059] [Method for Producing Hydrocarbons] The method for producing hydrocarbons from hydrotreated oil derived from waste materials obtained in the present invention is not particularly limited, but includes, for example, an atmospheric distillation step of obtaining a naphtha fraction by atmospheric distillation of a feedstock oil for atmospheric distillation containing at least a portion of the hydrotreated oil and crude oil, and a steam cracking step of obtaining hydrocarbons by steam cracking a feedstock oil for steam cracking containing at least a portion of the naphtha fraction. Each step will be described in detail below.

[0060] (Atmospheric Distillation Process) The atmospheric distillation process is a process of obtaining a naphtha fraction 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 a low nitrogen content. By using a feedstock oil for atmospheric distillation which is a mixture of hydrotreated oil and crude oil with a low nitrogen content, it is possible to suppress the occurrence of fouling in the heat exchanger of the atmospheric distillation apparatus and to suppress the influence of impurities such as nitrogen on downstream equipment. 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 may be used, and the equipment that has been installed in the refinery since the past can be used as is.

[0061] (Steam Cracking Process) The steam cracking process is a process in which steam cracking feed 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 hydrocarbons. In the steam cracking process, the steam cracking feed oil is heat-treated with steam, which decomposes the naphtha fraction (light naphtha, etc.) and generates components useful as hydrocarbons.

[0062] 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.

[0063] 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.

[0064] Examples of hydrocarbons obtained in the steam cracking process include ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, and C9 aromatics containing olefins for resin conversion, such as indene and methylstyrene.

[0065] In the steam cracking process, lighter fractions may be obtained as hydrocarbons. Examples of lighter fractions include methane, ethane, butane, pentane, propane, and hexane.

[0066] Figure 2 is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment. The system 20 shown in Figure 2 comprises a pyrolysis unit 21, a low-temperature hydrogenation unit 22, and a high-temperature hydrogenation unit 23, and may further include an atmospheric pressure distillation unit 24 and a steam cracking device 25.

[0067] In system 20, first, waste material S1 is supplied to the pyrolysis unit 21, where it is pyrolyzed. Pyrolysis oil S2 is obtained from the pyrolysis unit 21. Next, the pyrolysis oil S2 is supplied to the low-temperature hydrogenation unit 22. In the low-temperature hydrogenation unit 22, low-temperature hydrogenated oil S3 is obtained by low-temperature hydrogenation treatment of the pyrolysis oil S2. Next, the low-temperature hydrogenated oil S3 is supplied to the high-temperature hydrogenation unit 23. In the high-temperature hydrogenation unit 23, hydrogenated oil S4 is obtained by high-temperature hydrogenation treatment of the low-temperature hydrogenated oil S3. In addition, a portion of the hydrogenated oil S4 may be reused in the low-temperature hydrogenation unit 22 as recycled oil S5.

[0068] Next, the hydrogenated oil S4 is supplied to the atmospheric distillation unit 24. In the atmospheric distillation unit 24, naphtha fraction S6 is obtained by atmospheric distillation of the hydrogenated oil S4. Subsequently, the naphtha fraction S6 is supplied to the steam cracking apparatus 25. In the steam cracking apparatus 25, hydrocarbon S7 is obtained by steam cracking the steam cracking feed oil containing the naphtha fraction S6. Details of each apparatus and each product are as described above.

[0069] Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0070] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0071] 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) • Aniline content: Nitrogen compounds containing aniline are quantitatively analyzed using gas chromatography equipped with a chemiluminescent nitrogen detector (NCD). • Diene number: ASTM D1961 (Method of Test for Malenic Diene Value of Drying Oils) For samples to which the above test methods cannot be applied, refer to the method described in Japanese Patent Application Publication No. 2011-80766. １ The following method is used to estimate the diene titer by HNMR measurement: 1. Mix approximately 20 mg of a sample with a known diene titer in 500 μL of deuterated chloroform. 2. １1. Perform the above measurement on several samples and create a calibration curve of total area minus diene number. 2. Calculate the total area of ​​the sample with an unknown diene number and estimate the diene number from the calibration curve in step 3. 3. Evaluate heat exchanger fouling of low-temperature hydrogenated oil after the low-temperature hydrogenation process: Measure the temperature drop (°C) due to fouling attached to the test piece 31 of the fouling evaluation test apparatus (HLPS) 30 shown in Figure 3 in the following order: 1. Flow 25°C low-temperature hydrogenated oil from the left bottom (inlet 32) of the fouling evaluation test apparatus (HLPS) 30 shown in Figure 3 for a certain period of time (200 minutes). 2. While keeping the temperature of the test piece 31 constant at 300°C, observe whether fouling occurs and adheres to the surface of the test piece 31. When fouling adheres to the test piece 31, the heat transfer between the low-temperature hydrogenated oil and the test piece 31 decreases. 3. Measure the temperature of the low-temperature hydrogenated oil discharged from the upper right side (outlet 33) of the fouling evaluation test apparatus (HLPS) 30. The difference between the initial measured temperature at outlet 33 and the measured temperature after a certain period of time is defined as the "temperature drop caused by reduced heat transfer due to fouling." (However, the results for Comparative Example 1 are an evaluation for pyrolysis oil that has not undergone low-temperature hydrogenation treatment.) Here, the "heat exchanger fouling evaluation" is performed according to the following criteria. (Evaluation criteria) ○: The temperature drop during evaluation for a certain period of time (200 minutes) is 5°C or less, and it is judged that fouling to the heat exchanger is suppressed. ×: The temperature drop during evaluation for a certain period of time (200 minutes) is greater than 5°C, and it is judged that fouling to the heat exchanger is significant. - Refinery Processing Evaluation: The following criteria will be used to evaluate whether the hydrogenated oil obtained in the high-temperature hydrogenation process is applicable to subsequent processing in the refinery (atmospheric distillation process, naphtha fraction steam cracking process). (Evaluation Criteria) ○: If the nitrogen content in the hydrogenated oil is 80 ppm by mass or less, the amount of nitrogen in the naphtha fraction will be low, making it less likely to cause equipment blockage, and therefore it will be judged as applicable. ×: If the nitrogen content in the hydrogenated oil exceeds 80 ppm by mass, the amount of nitrogen in the naphtha fraction will be high, raising concerns about problems such as equipment blockage, and therefore it will be judged as not applicable.

[0072] (Example 1) (1) Pyrolysis process Using the pyrolysis apparatus shown in Fig. 1, the pyrolysis process is carried out. Specifically, about 100 kg of cut waste tires (waste material 6) are charged into the pyrolysis furnace 2 (capacity 0.5 m ３ ), and after replacing the inside of the pyrolysis furnace 2 with nitrogen gas, while circulating the nitrogen gas in the pyrolysis apparatus, the gas temperature is raised to 500 °C by the heat exchanger 1 and this temperature is maintained. The gas flow rate of the nitrogen gas introduced into the pyrolysis furnace 2 is set to 0.005 m ３ / s [ntp] and controlled within the range of 0.0045 m ３ / s [ntp] to 0.0055 m ３ / s [ntp]. Also, the oxygen concentration in the system of the pyrolysis apparatus is controlled within the range of 1% by volume or less. For measuring the oxygen concentration in the pyrolysis apparatus, a zirconia-type oxygen sensor is used. Pyrolysis oil is obtained from the bottom of the retort tower 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.

[0073] (2) Low-temperature hydrogenation process (2-1) Production of hydrogenation catalyst A-1 Using a silica-alumina powder having a composition of 97% by mass of alumina and 3% by mass of silica as an oxide, a columnar carrier with a diameter of about 1.6 mm and a length of about 3 mm is prepared. Nickel nitrate and ammonium molybdate are dissolved in ion-exchanged water corresponding to the water absorption amount of the above-mentioned carrier measured in advance to obtain a nickel nitrate and ammonium molybdate impregnation solution. This impregnation solution is impregnated into the above-mentioned carrier by the initial wetness method, and supported so that 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 above-mentioned carrier. Next, the obtained impregnated material (precursor catalyst) is dried at 120 °C for 3 hours and then calcined at 500 °C for 1 hour under air flow to obtain a hydrogenation catalyst A-1.

[0074] (2-2) Low-temperature hydrogenation treatment The hydrogenation catalyst A-1 is filled into a reaction tube (inner diameter 20 mm). After sulfiding treatment with an oil in which 1% by mass of dimethyldisulfide is dissolved in light oil, low-temperature hydrogenation treatment is carried out using pyrolysis oil as a raw material under the conditions of a reaction temperature of 200 °C, a reaction pressure of 11 MPaG, and a weight hourly space velocity of 1.0 h －１ , to obtain low-temperature hydrogenated oil.

[0075] (3) High-temperature hydrogenation process (3-1) Production of hydrogenation catalyst B-1 0.9 kg of silica-alumina powder containing 30% by mass of alumina and 70% by mass of silica and SiO ２ / Al ２ O ３ Using 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.

[0076] (3-2) High-temperature 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 400°C, the reaction pressure is 5.0 MPaG, and the gravitational space velocity is 1.0 h. －１ Under these conditions, a high-temperature hydrogenation treatment is performed using low-temperature hydrogenated oil as a raw material to obtain hydrogenated oil.

[0077] (Example 2) High-temperature hydrogenation treatment is performed in the same manner as in Example 1, except that the reaction pressure is changed to 10.0 MPaG in the high-temperature hydrogenation process, to obtain hydrogenated oil.

[0078] (Example 3) Low-temperature hydrogenation treatment is performed in the same manner as in Example 1, except that in the low-temperature hydrogenation step, a raw material oil containing 20% ​​by mass of pyrolysis oil obtained in the pyrolysis step and 80% by mass of recycled oil (hydrogenated oil obtained in the high-temperature hydrogenation step) is used to obtain low-temperature hydrogenated oil. Subsequently, in the high-temperature hydrogenation step, high-temperature hydrogenation treatment is performed in the same manner as in Example 1, except that the low-temperature hydrogenated oil is used and the reaction temperature is changed to 350°C to obtain hydrogenated oil.

[0079] (Example 4) In the high-temperature hydrogenation process, the reaction temperature is changed to 400°C and the reaction pressure is changed to 3.0 MPaG, but otherwise the same high-temperature hydrogenation treatment is performed as in Example 3 to obtain hydrogenated oil.

[0080] (Comparative Example 1) Hydrogenated oil is obtained by performing a high-temperature hydrogenation treatment in the same manner as in Example 1, except that the pyrolysis oil obtained in the pyrolysis step is used as a raw material for the high-temperature hydrogenation step without going through the low-temperature hydrogenation step.

[0081] (Comparative Example 2) High-temperature hydrogenation treatment is performed in the same manner as in Example 1, except that the reaction temperature is changed to 240°C in the high-temperature hydrogenation process, to obtain hydrogenated oil.

[0082] (Comparative Example 3) High-temperature hydrogenation treatment is performed in the same manner as in Example 1, except that the reaction pressure is changed to 0.5 MPaG in the high-temperature hydrogenation step, to obtain hydrogenated oil.

[0083] Table 1 shows the measurement and evaluation results for Examples 1-4 and Comparative Examples 1-3. As shown in Table 1, Comparative Example 1 did not undergo a low-temperature hydrogenation process, and therefore, compared to Examples 1-4, the feedstock oil used for high-temperature hydrogenation caused fouling of the heat exchanger, making it unsuitable for long-term operation. Furthermore, in Comparative Examples 2 and 3, the concentrations of nitrogen and aniline in the hydrogenated oil were higher compared to Examples 1-4, making them unsuitable for subsequent processing in the refinery (atmospheric distillation process, steam cracking process for naphtha fraction).

[0084]

[0085] (Example 5) (1) A pyrolysis oil is obtained in the same manner as in Example 1, except that cut waste plastic is used as the waste material for the pyrolysis process. The nitrogen and aniline content in the pyrolysis oil is as shown in Table 2.

[0086] (2) Low-temperature hydrogenation process Low-temperature hydrogenation treatment is performed in the same manner as in Example 1, except that the pyrolysis oil obtained above is used to obtain low-temperature hydrogenated oil.

[0087] (3) High-temperature hydrogenation process A high-temperature hydrogenation treatment is performed in the same manner as in Example 1, except that the low-temperature hydrogenated oil obtained above is used to obtain hydrogenated oil.

[0088] (Example 6) Low-temperature hydrogenation treatment is performed in the same manner as in Example 5, except that in the low-temperature hydrogenation step, a raw material oil containing 50% by mass of pyrolysis oil obtained in the pyrolysis step and 50% by mass of recycled oil (hydrogenated oil obtained in the high-temperature hydrogenation step) is used to obtain low-temperature hydrogenated oil. Subsequently, in the high-temperature hydrogenation step, high-temperature hydrogenation treatment is performed in the same manner as in Example 1, except that the low-temperature hydrogenated oil is used and the reaction temperature is changed to 300°C to obtain hydrogenated oil.

[0089] (Comparative Example 4) High-temperature hydrogenation treatment is performed in the same manner as in Example 4, except that the reaction temperature is changed to 240°C in the high-temperature hydrogenation step, to obtain hydrogenated oil.

[0090] (Comparative Example 5) High-temperature hydrogenation treatment is performed in the same manner as in Example 4, except that the reaction pressure is changed to 0.5 MPaG in the high-temperature hydrogenation step, to obtain hydrogenated oil.

[0091] (Comparative Example 6) In the high-temperature hydrogenation process, the gravitational space velocity was 7.0 h －１ Except for the change, the high-temperature hydrogenation treatment is performed in the same manner as in Example 4 to obtain hydrogenated oil.

[0092] Table 2 shows the measurement and evaluation results for Examples 5-6 and Comparative Examples 4-6. As shown in Table 2, Comparative Examples 4-6 have higher concentrations of nitrogen and aniline in the hydrotreated oil compared to Examples 5-6, indicating that they are unsuitable for subsequent processing at the refinery (atmospheric distillation process, steam cracking process for naphtha fraction).

[0093]

[0094] From the above examples, it is confirmed that the present invention makes it possible to produce hydrotreated oil suitable for naphtha treatment in oil refineries and the like from waste materials including at least one of waste tires and waste plastics.

[0095] 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 unit, 22... Low-temperature hydrogenation unit, 23... High-temperature hydrogenation unit, 24... Atmospheric distillation unit, 25... Steam cracking device, S1... Waste material, S2... Pyrolysis oil, S3... Low-temperature hydrogenated oil, S4... Hydrogenated oil, S5... Recycled oil, S6... Naphtha fraction, S7... Hydrocarbons, 30... Heat exchanger fouling evaluation measuring device, 31... Test piece, 32... Inlet, 33... Outlet

Claims

1. Hydrogenated oil of pyrolysis oil derived from waste materials, including at least one of waste tires and waste plastics, wherein the nitrogen content of the hydrogenated oil is greater than 20 ppm by mass and 80 ppm by mass or less.

2. The hydrogenated oil according to claim 1, wherein the nitrogen content of the hydrogenated oil contains aniline.

3. The hydrogenated oil according to claim 2, wherein the aniline content of the hydrogenated oil is 10 ppm by mass or more and 50 ppm by mass or less.

4. The hydrogenated oil according to claim 1, wherein the nitrogen content of the pyrolysis oil is 1,000 ppm by mass or more and 10,000 ppm by mass or less.

5. A pyrolysis step to obtain pyrolysis oil by pyrolysis of waste materials including at least one of waste tires and waste plastics; and a raw material oil containing at least a portion of the pyrolysis oil, reacted at a reaction temperature of 180°C to 300°C, a reaction pressure of 2.0 MPaG to 20 MPaG, and a gravitational space velocity of 0.1 h. －１ Total 5.0h －１ A low-temperature hydrogenation step to obtain low-temperature hydrogenated oil by performing a low-temperature hydrogenation treatment under the following conditions: and a raw material oil containing at least a portion of the low-temperature hydrogenated oil is subjected to a reaction at a temperature higher than the reaction temperature in the low-temperature hydrogenation treatment but 500°C or lower, a reaction pressure of 2.0 MPaG or higher and 15 MPaG or lower, and a gravimetric space velocity of 0.1 h. －１ Total 5.0h －１ A method for producing hydrogenated oil, comprising: a high-temperature hydrogenation step of performing a hydrogenation treatment under the following conditions to obtain hydrogenated oil, wherein the nitrogen content of the hydrogenated oil is greater than 20 ppm by mass and 80 ppm by mass or less.

6. The manufacturing method according to claim 5, wherein the hydrogenation treatment temperature in the high-temperature hydrogenation step is 280°C or higher and 450°C or lower.

7. The manufacturing method according to claim 5, wherein the nitrogen content of the hydrogenated oil contains aniline.

8. The manufacturing method according to claim 7, wherein the aniline content of the pyrolysis hydrogenation oil is 10 ppm by mass or more and 50 ppm by mass or less.

9. The manufacturing method according to claim 5, wherein the nitrogen content of the pyrolysis oil is 1,000 ppm by mass or more and 10,000 ppm by mass or less.

10. The manufacturing method according to claim 5, wherein recycled oil containing at least a portion of the hydrogenated oil is used as part of the raw material oil for the low-temperature hydrogenation step.

11. The manufacturing method according to claim 10, wherein the amount of recycled oil in the raw material oil used in the low-temperature hydrogenation step is 20% by mass or more and 90% by mass or less relative to the total amount of recycled oil and pyrolysis oil.

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