Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
  • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
  • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours

Definitions

• Patent Document 1 In recent years, conversion of waste materials such as waste tires, waste rubber, and waste plastics into chemical products through pyrolysis or other methods has been considered as a method of recycling such materials (for example, Patent Document 1).
• the inventors have investigated a series of processes for producing chemical products using waste tires in particular, including a pyrolysis step in which pyrolysis oil is obtained by pyrolysis of waste tires, a hydrocracking step in which at least light fractions are obtained by hydrotreating the pyrolysis oil, and a steam cracking step in which the light fractions are steam cracked to obtain chemical products.
• a pyrolysis step in which pyrolysis oil is obtained by pyrolysis of waste tires
• a hydrocracking step in which at least light fractions are obtained by hydrotreating the pyrolysis oil
• a steam cracking step in which the light fractions are steam cracked to obtain chemical products.
• the present invention aims to provide a method for efficiently producing chemical products from waste tires by improving each step in a series of processes, and for efficiently obtaining carbonized materials at the same time.
• the present invention also aims to provide a method for managing chemical products, which is carried out using a management device used when producing chemical products from waste tires.
• One aspect of the present invention relates, for example, to the following: [1] A pyrolysis step of obtaining a first gas fraction, a pyrolysis oil, and a residue fraction by pyrolysis of crushed waste tires; a carbonized matter recovery step of recovering a carbonized matter from the residue; a low-temperature hydrogenation step of subjecting a feedstock oil containing at least a portion of the pyrolysis oil to low-temperature hydrogenation treatment at a temperature of 180° C. or more and 350° C.
• a method for producing a tire comprising: a vulcanization step of obtaining a tire by a vulcanization reaction using the synthetic rubber obtained by the production method according to [18] as at least a part of a raw material for the tire.
• a method for managing chemical products which is carried out using a management device used in producing chemical products using waste tires, comprising:
• the management method is a method of allocating a value as a renewable product to the chemical product using the management device in accordance with a content ratio of renewable raw materials contained in the scrap tires, using a mass balance method;
• the management method includes a step (V) of confirming that the chemical product is obtained,
• the step (V) includes the following steps (V-1), (V-2), (V-3), (V-4), and (V-5):
• the step (V-1) is a step of confirming that the pyrolysis oil is produced from the waste tires that have been input into a pyrolysis unit in which the waste tires are subjected to a pyrolysis treatment at 350° C.
• the step (V-2) is a step of confirming that the low-temperature hydrogenated oil is produced from the pyrolysis oil input into a low-temperature hydrogenation unit in which a feedstock oil containing at least a part of the pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180° C. or more and 350° C.
• the step (V-4) is a step of confirming that the chemical product is obtained from the light fraction input into a steam cracker that subjects a steam cracking feedstock oil containing at least a portion of the light fraction to a steam cracking treatment
• the step (V-5) is a step of confirming that the chemical products can be obtained from the scrap tires by treating them in the order of the thermal cracking unit, the low-temperature hydrogenation unit, the hydrocracking unit, and the steam cracker,
• the method includes a step (Z) of identifying the proportion of products to be assigned a value as a renewable product;
• the step (Z) includes the following steps (Z-1), (Z-2), (Z-3), and (Z-4):
• the step (Z-1) is a step of selecting a product to be allocated as a renewable product from among the products obtained by the steam cracker
• the step (Z-2) is a step of determining a value of a proportion (P) to be allocated as a renewable product among the proportion of the product selected in the
• the management device includes a computer-readable storage medium storing a management program, A management device that executes the management method described in [21] by executing the management program.
• the management device according to [22] which, after executing the management method, outputs a result of allocating a value as a renewable product to a product selected according to the content ratio of renewable raw materials contained in scrap tires, obtained by the management method.
• a computer-readable storage medium storing a computer program comprising: A storage medium storing a management program that causes a computer to execute the management method according to [21].
• the present invention provides a method for efficiently producing chemical products from waste tires and efficiently obtaining carbonized materials by improving each step in a series of processes.
• the present invention also provides a method for managing chemical products, which is carried out using a management device used when producing chemical products from waste tires.
• FIG. 1 is a schematic diagram showing an example of a pyrolysis device.
• FIG. 1 is a schematic diagram showing an example of a system for implementing a method for producing chemical products and carbides.
• FIG. 2 is a schematic diagram illustrating a functional configuration of a management device.
• FIG. 2 is a block diagram illustrating an example of a hardware configuration of a management device.
• 10 is a flowchart showing an example of a processing procedure of a management program in a control unit of the management device.
• FIG. 1 is a schematic diagram of a stain evaluation test device (HLPS) used in the examples.
• HLPS stain evaluation test device
• the method for producing chemical products and charcoal in this embodiment includes a pyrolysis process for obtaining a first gas fraction, a pyrolysis oil, and a residue by pyrolysis of crushed waste tires, a char recovery process for recovering charcoal from the residue, a low-temperature hydrogenation process for subjecting a feedstock oil containing at least a portion of the pyrolysis oil to low-temperature hydrogenation treatment at 180°C or higher and 350°C or lower to obtain low-temperature hydrogenated oil, a hydrocracking process for subjecting a feedstock oil containing at least a portion of the low-temperature hydrogenated oil to hydrocracking treatment at a temperature higher than the low-temperature hydrogenation treatment to obtain a second gas fraction, a light fraction having a boiling point of 350°C or lower, and a heavy fraction having a boiling point of more than 350°C, and a steam cracking process for steam cracking a steam cracking feedstock oil containing at least a portion of the light fraction to obtain a chemical product and a charcoal
• the pyrolysis temperature is 350°C or higher and 750°C or lower.
• the pyrolysis step is a step of obtaining a first gas fraction, a pyrolysis oil, and a residue fraction by pyrolysis of crushed waste tires (hereinafter, also simply referred to as waste material).
• Waste tires may contain metals.
• scrap tires may contain metals from the steel cords and wires that are the aggregates of tires.
• the manufacturing method of this embodiment may further include a removal step of removing the metals from the waste tires or their crushed products.
• a removal step of removing the metals from the waste tires or their crushed products There are no particular limitations on the method of removing the metals from the waste tires or their crushed products, and examples of the method include removal methods using magnets, sieves, etc.
• the manufacturing method of this embodiment may further include a removal step of removing metals from the mixture.
• a removal step of removing metals from the mixture There are no particular limitations on the method of removing metals from the mixture, and examples include removal methods using magnets, sieves, etc.
• the method for crushing the waste tires is not particularly limited, and may be, for example, mechanical crushing using a single-shaft or twin-shaft crusher, crushing using a water jet, freezing crushing, laser crushing, or the like.
• the pyrolysis of crushed waste tires can be carried out, for example, by placing the crushed waste tires in a pyrolysis furnace, supplying high-temperature gas to the pyrolysis furnace, and bringing the crushed waste tires into contact with the high-temperature gas.
• the high-temperature gas is preferably an oxygen-free gas that contains substantially no oxygen (for example, a gas with an oxygen content of 1% by volume or less).
• the high-temperature gas may be any gas other than oxygen and oxides, and may be, for example, an inert gas such as nitrogen, argon, or helium, hydrogen, or a hydrocarbon with 1 to 4 carbon atoms.
• the pyrolysis furnace is not particularly limited, and may be, for example, a kettle-type pyrolysis furnace, a fluidized bed-type pyrolysis furnace, or a kiln-type pyrolysis furnace.
• the pyrolysis temperature (temperature of the high-temperature gas) in the pyrolysis step is 350° C. or higher, and from the viewpoints of further improving the yield of chemical products, of making it easier to obtain a powdered charcoal from the residue, of further improving the dispersibility of the obtained powdered charcoal when added to a resin, elastomer, or the like, and of making the heavy fraction obtained in the steam cracking step more suitable as a raw material for producing charcoal (particularly a raw material for producing carbon black), the pyrolysis temperature is preferably 370° C. or higher, more preferably 390° C. or higher.
• the pyrolysis temperature (temperature of the high-temperature gas) in the pyrolysis step may be, for example, 750° C.
• the pyrolysis temperature is preferably 730° C. or lower, more preferably 710° C. or lower.
• such a temperature range tends to make it easier to obtain the amounts of the preferred products (first gas fraction, pyrolysis oil, and residue fraction) described below, and also tends to make it easier to obtain a feedstock oil with a high-boiling point oil content within a preferred range.
• the pyrolysis temperature (temperature of the high-temperature gas) in the pyrolysis step may be, for example, 350 to 750°C, 350 to 730°C, 350 to 710°C, 370 to 750°C, 370 to 730°C, 370 to 710°C, 390 to 750°C, 390 to 730°C, or 390 to 710°C.
• the pyrolysis may be carried out in the presence of a pyrolysis catalyst or in the absence of a pyrolysis catalyst.
• a pyrolysis catalyst any catalyst used in ordinary petrochemical pyrolysis may be used without any particular restrictions.
• the pyrolysis catalyst it may be an acidic catalyst or a basic catalyst.
• an acidic catalyst for example, a catalyst containing an aluminosilicate may be mentioned.
• a smectite group such as zeolite and montmorillonite may be mentioned.
• a catalyst containing montmorillonite for example, clays or minerals such as activated clay, acid clay, and bentonite may be mentioned.
• a basic catalyst for example, a carbonate such as sodium carbonate may be used.
• the pyrolysis conditions may be adjusted as appropriate, for example, so that the resulting component ratios and the properties of the resulting pyrolysis oil are within the preferred ranges described below.
• a first gas fraction, a pyrolysis oil, and a residue fraction are obtained.
• the residue fraction may be obtained as a mixture with a metal fraction, as described above.
• a pyrolysis gas is generated in a pyrolysis furnace, and the pyrolysis gas can be cooled to recover pyrolysis oil as an oil fraction.
• the first gas fraction can be recovered as the residual gas after cooling the pyrolysis gas to recover the oil fraction.
• the residue fraction can be recovered as the solid fraction remaining in the pyrolysis furnace after pyrolysis.
• the amount of the thermal decomposition oil relative to the total amount of the first gas fraction, the thermal decomposition oil and the residue may be, for example, 40% by mass or more.
• the amount of the thermal decomposition oil relative to the total amount of the first gas fraction, the thermal decomposition oil and the residue may be preferably 45% by mass or more, more preferably 48% by mass or more, even more preferably 50% by mass or more, and may be 51% by mass or more or 52% by mass or more.
• the amount of the thermal decomposition oil relative to the total amount of the first gas fraction, the thermal decomposition oil and the residue may be, for example, 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, even more preferably 65% by mass or less, and may be 60% by mass or less.
• the amount of pyrolysis oil relative to the total amount of the first gas component, the pyrolysis oil, and the residue component is, for example, 40 to 80 mass%, 40 to 75 mass%, 40 to 70 mass%, 40 to 65 mass%, 40 to 60 mass%, 45 to 80 mass%, 45 to 75 mass%, 45 to 70 mass%, 45 to 65 mass%, 45 to 60 mass%, 48 to 80 mass%, 48 to 75 mass%, 48 to 70 mass%, Mass%, 48-65 mass%, 48-60 mass%, 50-80 mass%, 50-75 mass%, 50-70 mass%, 50-65 mass%, 50-60 mass%, 51-80 mass%, 51-75 quality %, 51-70% by weight, 51-65% by weight, 51-60% by weight, 52-80% by weight, 52-75% by weight, 52-70% by weight, 52-65% by weight, or 52-60% by weight.
• the amount of the first gas component relative to the total amount of the first gas component, the thermal decomposition oil, and the residue is, for example, 25% by mass or less.
• the amount of the first gas component relative to the total amount of the first gas component, the thermal decomposition oil, and the residue is preferably 20% by mass or less, more preferably 15% by mass or less, and may be 13% by mass or less or 10% by mass or less.
• the amount of the first gas component is 25% by mass or less under the thermal decomposition conditions, the decrease in the yield of the thermal decomposition oil due to the excessive progress of the thermal decomposition of the crushed material can be suppressed.
• the thermal decomposition oil generated by the thermal decomposition of the crushed material can be suppressed from being further thermally decomposed into a gas component, and the yield of the thermal decomposition oil that can be made into a chemical product through the low-temperature hydrogenation step, the hydrocracking step, and the steam cracking step can be further improved, and thus the yield of the chemical product can be further improved.
• the amount of the first gas component relative to the total amount of the first gas component, the pyrolysis oil, and the residue may be, for example, 0.1% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 1% by mass or more, 1.3% by mass or more, or 1.5% by mass or more.
• the crushed material contains, for example, chlorine
• a part of the chlorine content in the crushed material is gasified as chlorine gas or the like by pyrolysis. That is, a part of the chlorine content contained in the crushed material is removed as a part of the first gas component.
• the chlorine content contained in the pyrolysis oil can be reduced compared to when the first gas component is not generated in the pyrolysis process. Therefore, by setting the pyrolysis conditions under which a predetermined amount of the first gas component is generated, the purity of the chemical product obtained through the low-temperature hydrogenation process for the pyrolysis oil, the hydrocracking process for the low-temperature hydrogenation oil, and the steam cracking process for the steam cracking feedstock oil is further improved. In addition, when a catalyst is used in the hydrocracking process, poisoning of the catalyst caused by chlorine can be suppressed, and deterioration of the catalyst can be suppressed.
• the amount of the first gas component relative to the total amount of the first gas component, the pyrolysis oil, and the residue is, for example, 0.1 to 25 mass%, 0.1 to 20 mass%, 0.1 to 15 mass%, 0.1 to 13 mass%, 0.1 to 10 mass%, 0.5 to 25 mass%, 0.5 to 20 mass%, 0.5 to 15 mass%, 0.5 to 13 mass%, 0.5 to 10 mass%, 0.7 to 25 mass%, 0.7 to 20 mass%, 0.7 to 15 mass%, 0.7 to 25 mass%, 0.7 to 25 mass%, 0.7 to 25 mass%, 0.7 to 15 mass%, 0.7 to 15 mass%, 0.7 to 25 mass%, 0.7 to 15 mass%, 0.7 to 15 mass%, 0.7 to 25 mass%, 0.7 to 15 mass%, 0.7 to 25 mass%, 0.7 to 15 mass%, 0.7 to 25 mass%, 0.7 to 15 mass%, 0.7 to 25 mass%, 0.7 to 15 mass%, 0.7 to 25 mass%, 0.7 to 15 mass%, 0.7 to 25
• % by mass 0.7-13% by mass, 0.7-10% by mass, 1-25% by mass, 1-20% by mass, 1-15% by mass, 1-13% by mass, 1-10% by mass, 1.3-25% by mass, 1.3-20% by mass, 1. It may be 3-15% by weight, 1.3-13% by weight, 1.3-10% by weight, 1.5-25% by weight, 1.5-20% by weight, 1.5-15% by weight, 1.5-13% by weight or 1.5-10% by weight.
• the amount of the residue relative to the total amount of the first gas fraction, the pyrolysis oil, and the residue may be, for example, 10% by mass or more, and is preferably 15% by mass or more, more preferably 20% by mass or more, from the viewpoint of improving the yield of the chemical product obtained through the low-temperature hydrogenation step, the hydrocracking step, and the steam cracking step, and from the viewpoint of improving the yield of the carbonized material recovered as the residue. If the thermal decomposition conditions are such that the amount of the residue is 10% by mass or more, the decrease in the yield of the pyrolysis oil due to the excessive progress of the pyrolysis of the crushed material can be suppressed.
• the pyrolysis oil generated by the pyrolysis of the crushed material can be suppressed from being further pyrolyzed into a gaseous material, and the yield of the pyrolysis oil that can become a chemical product through the low-temperature hydrogenation step, the hydrocracking step, and the steam cracking step can be further improved, and thus the yield of the chemical product can be further improved.
• the above range is preferable from the viewpoint of recovering more carbonized material.
• the amount of the residue with respect to the total amount of the first gas fraction, the pyrolysis oil, and the residue may be, for example, 60% by mass or less.
• it is preferably 55% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, and may be 40% by mass or less.
• the amount of the residue with respect to the total amount of the first gas fraction, the pyrolysis oil, and the residue increases, the amount of the first gas fraction and the pyrolysis oil with respect to the total amount of the first gas fraction, the pyrolysis oil, and the residue becomes smaller. Therefore, under pyrolysis conditions where the amount of the residue is 60% by mass or less, it is possible to suppress the crushed material that should become the pyrolysis oil from remaining as the residue, and the yield of the pyrolysis oil that can become a chemical product through the low-temperature hydrogenation step, the hydrocracking step, and the steam cracking step can be improved, and thus the yield of the chemical product is further improved.
• the amount of the residue relative to the total amount of the first gas fraction, the pyrolysis oil, and the residue fraction may be, for example, 10 to 60 mass%, 10 to 55 mass%, 10 to 50 mass%, 10 to 45 mass%, 10 to 40 mass%, 15 to 60 mass%, 15 to 55 mass%, 15 to 50 mass%, 15 to 45 mass%, 15 to 40 mass%, 20 to 60 mass%, 20 to 55 mass%, 20 to 50 mass%, 20 to 45 mass%, or 20 to 40 mass%.
• the first gas component may be, for example, a component of the product produced by pyrolysis that is gaseous at normal pressure and 20°C.
• the first gas component may contain, for example, hydrogen, a hydrocarbon having 1 to 4 carbon atoms, etc.
• the method for recovering the first gas component is not particularly limited.
• the first gas component can be recovered as the residual gas remaining after cooling the pyrolysis gas produced by pyrolysis and recovering the oil component (pyrolysis oil).
• the first gas portion can be reused, for example, as high-temperature gas (oxygen-free gas) in pyrolysis. That is, the first gas portion can be heated and supplied to the pyrolysis furnace as part (or all) of the high-temperature gas (oxygen-free gas).
• the first gas portion can be used, for example, as a combustion gas for heating the pyrolysis section in the pyrolysis process or as a combustion gas for a heating furnace in other processes.
• the pyrolysis oil may be, for example, a component of the product produced by pyrolysis that is liquid at normal pressure and 20°C.
• the method for recovering the pyrolysis oil is not particularly limited.
• the pyrolysis oil can be recovered, for example, as an oil fraction distilled from a pyrolysis furnace. That is, the pyrolysis oil can be recovered, for example, as an oil fraction condensed by cooling the pyrolysis gas produced by pyrolysis.
• the distillation properties of the pyrolysis oil are not particularly limited, and it is sufficient if the properties allow it to be used as a feedstock oil in, for example, a low-temperature hydrogenation process or a hydrocracking process.
• the 10% distillation temperature (T10) of the pyrolysis oil may be, for example, 90° C. or higher, preferably 140° C. or higher, more preferably 150° C. or higher, and even more preferably 155° C. or higher.
• the 10% distillation temperature of the pyrolysis oil may be, for example, 200° C. or lower, 190° C. or lower, or 180° C. or lower.
• the 10% distillation temperature (T10) of the pyrolysis oil may be, for example, 90 to 200°C, 90 to 190°C, 90 to 180°C, 140 to 200°C, 140 to 190°C, 140 to 180°C, 150 to 200°C, 150 to 190°C, 150 to 180°C, 155 to 200°C, 155 to 190°C, or 155 to 180°C.
• the 90% distillation temperature (T90) of the pyrolysis oil may be, for example, 350° C. or higher, preferably 370° C. or higher, more preferably 390° C. or higher, and even more preferably 400° C. or higher, and may be 410° C. or higher, 420° C. or higher, 430° C. or higher, 440° C. or higher, or 450° C. or higher.
• the 90% distillation temperature (T90) of the pyrolysis oil may be, for example, 650° C. or lower, preferably 600° C. or lower, and more preferably 550° C. or lower.
• the 90% distillation temperature (T90) of the pyrolysis oil is, for example, 350 to 650 ° C., 350 to 600 ° C., 350 to 550 ° C., 370 to 650 ° C., 370 to 600 ° C., 370 to 550 ° C., 390 to 650 ° C., 390 to 600 ° C., 390 to 550 ° C., 400 to 650 ° C., 400 to 600 ° C., 400 to 550 ° C., 410 to 650 ° C., 410 to 600 ° C., 410 to 550 ° C., 420 to 650 ° C., °C, 420 to 600 °C, 420 to 550 °C, 430 to 650 °C, 430 to 600 °C, 430 to 550 °C, 440 to 650 °C, 440 to 600 °C, 440 to 550 °C, 450 to 650 °C,
• the pyrolysis oil contains low-boiling oils with a boiling point of 350°C or less, and may also contain high-boiling oils with a boiling point of more than 350°C.
• the content of the high boiling point oil in the pyrolysis oil is not particularly limited, but is preferably 50 mass% or less, more preferably 45 mass% or less, even more preferably 40 mass% or less, and even more preferably 35 mass% or less, based on the total amount of the pyrolysis oil.
• the content of high boiling point oil in the pyrolysis oil may be, for example, 5 mass% or more, 8 mass% or more, or 10 mass% or more, based on the total amount of the pyrolysis oil. That is, the content of high boiling point oil in the pyrolysis oil may be, for example, 5 to 50 mass%, 5 to 45 mass%, 5 to 40 mass%, 5 to 35 mass%, 8 to 50 mass%, 8 to 45 mass%, 8 to 40 mass%, 8 to 35 mass%, 10 to 50 mass%, 10 to 45 mass%, 10 to 40 mass%, or 10 to 35 mass%, based on the total amount of the pyrolysis oil.
• the pyrolysis oil may contain nitrogen, sulfur, chlorine, halogen elements, etc.
• the nitrogen content of the pyrolysis oil may be, for example, 100 ppm by mass or more, 2000 ppm by mass or more, 2500 ppm by mass or more, or 3000 ppm by mass or more.
• the nitrogen content is converted into gas components such as ammonia by hydrogenation in the hydrocracking process, and can be easily separated from the liquid product. Then, by supplying the liquid product with a significantly reduced nitrogen content to the steam cracking process, a high-purity chemical product (a chemical product with little nitrogen content) can be easily obtained.
• the nitrogen content of the pyrolysis oil may be, for example, 20,000 ppm by mass or less, 15,000 ppm by mass or less, or 10,000 ppm by mass or less. If the nitrogen content is 20,000 ppm by mass or less, the nitrogen content of the liquid product after the hydrocracking process can be more significantly reduced.
• the nitrogen content of the pyrolysis oil may be, for example, 100 to 20,000 ppm by mass, 100 to 15,000 ppm by mass, 100 to 10,000 ppm by mass, 2000 to 20,000 ppm by mass, 2000 to 15,000 ppm by mass, 2000 to 10,000 ppm by mass, 2500 to 20,000 ppm by mass, 2500 to 15,000 ppm by mass, 2500 to 10,000 ppm by mass, 3000 to 20,000 ppm by mass, 3000 to 15,000 ppm by mass, or 3000 to 10,000 ppm by mass.
• the sulfur content of the pyrolysis oil may be, for example, 10 ppm by mass or more, 100 ppm by mass or more, 500 ppm by mass or more, or 1000 ppm by mass or more.
• the sulfur content is converted into gas components such as hydrogen sulfide by hydrogenation in the hydrocracking process, and can be easily separated from the liquid product. Then, by supplying the liquid product with a significantly reduced sulfur content to the steam cracking process, a high-purity chemical product (a chemical product with little sulfur content) can be easily obtained.
• the sulfur content of the pyrolysis oil may be, for example, 30,000 ppm by mass or less, 20,000 ppm by mass or less, or 10,000 ppm by mass or less. This makes it possible to more significantly reduce the sulfur content of the liquid product after the hydrocracking process.
• the sulfur content of the pyrolysis oil may be, for example, 10 to 30,000 ppm by mass, 10 to 20,000 ppm by mass, 10 to 10,000 ppm by mass, 100 to 30,000 ppm by mass, 100 to 20,000 ppm by mass, 100 to 10,000 ppm by mass, 500 to 30,000 ppm by mass, 500 to 20,000 ppm by mass, 500 to 10,000 ppm by mass, 1000 to 30,000 ppm by mass, 1000 to 20,000 ppm by mass, or 1000 to 10,000 ppm by mass.
• the chlorine content of the pyrolysis oil may be, for example, 10 ppm by mass or more, 30 ppm by mass or more, 50 ppm by mass or more, or 100 ppm by mass or more.
• the chlorine content is converted into gas components such as hydrogen chloride by hydrogenation in the hydrocracking process, and can be easily separated from the liquid product. Then, by supplying the liquid product with a significantly reduced chlorine content to the steam cracking process, a high-purity chemical product (a chemical product with little chlorine content) can be easily obtained.
• the chlorine content of the pyrolysis oil may be, for example, 2000 ppm by mass or less, 1500 ppm by mass or less, or 1000 ppm by mass or less. If the chlorine content is 1000 ppm by mass or less, the chlorine content of the liquid product after the hydrocracking process can be more significantly reduced. In addition, it is preferable that not only the chlorine content but also the other halogen element content is in the same range.
• the chlorine content of the pyrolysis oil may be, for example, 10 to 2000 ppm by mass, 10 to 1500 ppm by mass, 10 to 1000 ppm by mass, 30 to 2000 ppm by mass, 30 to 1500 ppm by mass, 30 to 1000 ppm by mass, 50 to 2000 ppm by mass, 50 to 1500 ppm by mass, 50 to 1000 ppm by mass, 100 to 2000 ppm by mass, 100 to 1500 ppm by mass, or 100 to 1000 ppm by mass.
• the residue may be, for example, solids that are not recovered as pyrolysis gas from the products produced by pyrolysis. There are no particular limitations on the method for recovering the residue.
• the residue can be recovered, for example, as solids remaining in the pyrolysis furnace (solids that are not discharged outside the reaction system as pyrolysis gas).
• the residue may be a carbonized material formed by thermal decomposition of crushed waste tires.
• the residue may be recovered as a carbonized material (carbonized material recovery process).
• Carbide is a component in which carbon is the majority.
• the carbide may be a carbon concentrate whose main component is carbon black.
• the carbide may have clumps that have aggregated during the pyrolysis process.
• the aggregated carbide can be pulverized using a crusher or the like to obtain powdered carbide.
• the carbonized material recovery process in the manufacturing method of this embodiment may be a process in which the residue is pulverized to obtain a powdered carbonized material.
• Powdered carbonized materials can be used effectively as additives for rubber, resins, colorants, etc.
• the residue may contain, for example, rubber components of waste materials that were not completely pyrolyzed.
• the rubber components are sticky, the carbonized material is recovered as a mass of a mixture of carbon black and rubber components.
• Such carbonized material is difficult to pulverize using a grinder or the like because the stickiness of the rubber components inhibits the powderization of the carbonized material.
• the lump-shaped carbonized material leads to poor dispersion in the base material, it is difficult to use it as an additive for rubber, an additive for resin, a colorant, or the like.
• the pyrolysis process may be carried out, for example, by a pyrolysis apparatus equipped with a pyrolysis furnace.
• Figure 1 is a schematic diagram showing an example of a pyrolysis apparatus.
• the pyrolysis apparatus in FIG. 1 includes a heat exchanger 1 for heating the oxygen-free gas, a decomposition device 7 having a pyrolysis furnace 2 that contains waste material 6 inside and an external heating means 8 for heating the pyrolysis furnace 2 from the outside, an oil recovery device 5 for cooling the pyrolysis gas generated in the decomposition device 7 and recovering the condensed oil (pyrolysis oil), a circulation path 4 for supplying the remaining gas after the oil has been recovered in the oil recovery device 5 to the heat exchanger 1 as oxygen-free gas, and an oxygen-free gas supply source 3 for supplying the oxygen-free gas to the heat exchanger 1.
• a heat exchanger 1 for heating the oxygen-free gas
• a decomposition device 7 having a pyrolysis furnace 2 that contains waste material 6 inside and an external heating means 8 for heating the pyrolysis furnace 2 from the outside
• an oil recovery device 5 for cooling the pyrolysis gas generated in the decomposition device 7 and recovering the condensed oil (pyrolysis oil)
• the pyrolysis apparatus of FIG. 1 also includes a flowmeter 9, a damper 10, and a blower 11 in the piping that connects the oxygen-free gas source 3 to the heat exchanger 1 in order to supply oxygen-free gas from the oxygen-free gas source 3, and a flowmeter 9, a damper 10, a blower 11, and a hot air stove 14 in the circulation path 4 in order to circulate the remaining gas after recovery in the oil recovery device 5 to the heat exchanger 1 as oxygen-free gas.
• the oil recovery device 5 may also include multiple dry distillation towers 12a and 12b to separate the recovered oil according to its boiling point. Each dry distillation tower 12 may be connected to a recovery tank 13 through piping at its lower part, allowing the recovered oil to be stored.
• the thermal cracking device in FIG. 1 includes multiple dry distillation towers 12a and 12b, but in this embodiment, the thermal cracking oil can be used as is as feed oil for the hydrocracking process, so there may only be one dry distillation tower. In the thermal cracking device in FIG. 1, each dry distillation tower 12 is connected to a separate recovery tank 13, but each dry distillation tower 12 may be connected to the same recovery tank 13.
• By removing at least a portion of the high boiling point oil from the pyrolysis oil it is possible to suppress the generation of fouling in the heat exchanger or heating furnace in the low-temperature hydrogenation step or hydrocracking step, and to make it possible to realize long-term operation of the process.
• it is more preferable to remove at least a portion of the high boiling point oil for example, with a boiling point exceeding 450°C.
• the method for removing the high boiling point oils is to cool the pyrolysis gas immediately after it is produced in the pyrolysis process, separate it into a pyrolysis oil containing a large amount of high boiling point oils and a gas fraction containing a large amount of low boiling point oils, and then further cool the gas fraction containing a large amount of low boiling point oils to separate it into a first gas fraction and a pyrolysis oil containing a large amount of low boiling point oils.
• the pyrolysis oil can be heated and separated into low boiling point oils and high boiling point oils in a distillation tower, but this is not limited to the methods described above.
• the content of high boiling point oil in the pyrolysis oil from which a portion of the high boiling point oil has been removed before the low-temperature hydrogenation step is not particularly limited, but is 40 mass% or less, more preferably 35 mass% or less, even more preferably 30 mass% or less, and even more preferably 25 mass% or less, based on the total amount of the pyrolysis oil fractionated before the low-temperature hydrogenation step. If the content of high boiling point oil in the pyrolysis oil fractionated before the low-temperature hydrogenation step is 40 mass% or less, the effects of easily heavy components such as heavy olefins and dienes can be suppressed.
• the content of high boiling point oil in the pyrolysis oil fractionated before the low-temperature hydrogenation step may be, for example, 1 mass% or more, 3 mass% or more, or 5 mass% or more, based on the total amount of the pyrolysis oil fractionated before the low-temperature hydrogenation step.
• the removed high boiling oil may be recycled as a raw material for the pyrolysis process, may be used as a raw material for carbon black production, or may be used as a fuel.
• the low-temperature hydrogenation step is a step in which a feedstock oil containing at least a portion of the pyrolysis oil is subjected to low-temperature hydrotreatment at 180° C. or higher and 350° C. or lower to obtain a low-temperature hydrogenated oil.
• the feedstock oil in the low-temperature hydrogenation process may contain pyrolysis oil, or may contain a portion of the fraction obtained by fractional distillation of pyrolysis oil.
• the feedstock oil in the low-temperature hydrogenation process may further contain components other than pyrolysis oil, or pyrolysis oil may be used as it is as the feedstock oil.
• Recycled oil containing at least a portion of the light and heavy fractions obtained in the hydrocracking process described below or any diluting hydrocarbon oil may be used as part of the feedstock oil in the low-temperature hydrogenation process.
• recycled oil or any diluting hydrocarbon oil dienes and olefins that tend to polymerize and generate dirt can be diluted, which has the effect of preventing the generation of dirt.
• the heat generation effect in the reactor in the low-temperature hydrogenation process and hydrocracking process can be reduced, improving the stability of process operation.
• diluting hydrocarbons include kerosene fraction, diesel fraction, and vacuum diesel fraction obtained from an atmospheric distillation unit derived from crude oil, LCO obtained from an FCC unit, and even product kerosene and product diesel.
• the amount of recycled oil relative to the total amount of recycled oil and pyrolysis oil in the feed oil is preferably 10% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 97% by mass or less, even more preferably 30% by mass or more and 95% by mass or less, particularly preferably 40% by mass or more and 93% by mass or less, and most preferably 50% by mass or more and 90% by mass or less.
• the low-temperature hydrogenation process may be a process of hydrogenating a feedstock in the presence of a hydrogenation catalyst.
• Hydrogenation can be carried out, for example, by supplying the feedstock to a reactor in which a hydrogenation catalyst is disposed and contacting the feedstock with the hydrogenation catalyst in the reactor.
• the hydrogenation catalyst for example, a known hydrogenation catalyst used in the hydrogenation of hydrocarbon oils can be used. From the viewpoint of hydrogenation ability, it is preferable that the hydrogenation catalyst contains, for example, a Ni-based or Co-based catalyst.
• a Ni-based catalyst is a catalyst having Ni as an active metal.
• a Co-based catalyst is a catalyst having Co as an active metal.
• the hydrogenation catalyst one type of hydrogenation catalyst may be used, or multiple types of hydrogenation catalysts may be used.
• the reaction temperature in the low-temperature hydrogenation step is from 180°C to 350°C, preferably from 190°C to 340°C, more preferably from 200°C to 330°C, even more preferably from 2102°C to 320°C, particularly preferably from 220°C to 310°C, and most preferably from 240°C to 305°C.
• the reaction pressure in the low-temperature hydrogenation step is not particularly limited and may be, for example, 1 MPaG or more, preferably 3 MPaG or more, more preferably 5 MPaG or more.
• the reaction pressure in the low-temperature hydrogenation step is not particularly limited and may be, for example, 20 MPaG or less, preferably 19 MPaG or less, more preferably 18 MPaG or less. That is, the reaction pressure in the low-temperature hydrogenation step may be, for example, 1 to 20 MPaG, 1 to 19 MPaG, 1 to 18 MPaG, 3 to 20 MPaG, 3 to 19 MPaG, 3 to 18 MPaG, 5 to 20 MPaG, 5 to 19 MPaG, or 5 to 18 MPaG.
• the weight hourly space velocity (WHSV) of the feed oil may be, for example, 0.1 h ⁇ 1 or more, preferably 0.15 h ⁇ 1 or more, more preferably 0.2 h ⁇ 1 or more.
• the weight hourly space velocity (WHSV) of the feed oil may be, for example, 5 h ⁇ 1 or less, preferably 4 h ⁇ 1 or less, more preferably 3 h ⁇ 1 or less.
• the weight hourly space velocity (WHSV) of the feed oil may be 0.1 to 5 h ⁇ 1 , 0.1 to 4 h ⁇ 1 , 0.1 to 3 h ⁇ 1 , 0.15 to 5 h ⁇ 1 , 0.15 to 4 h ⁇ 1 , 0.15 to 3 h ⁇ 1 , 0.2 to 5 h ⁇ 1 , 0.2 to 4 h ⁇ 1 or 0.2 to 3 h ⁇ 1 .
• the low-temperature hydrogenation step is carried out in the presence of hydrogen.
• the hydrogen/oil ratio may be, for example, 100 NL/L or more, preferably 150 NL/L or more, more preferably 200 NL/L or more.
• the hydrogen/oil ratio may be, for example, 1500 NL/L or less, preferably 1400 NL/L or less, more preferably 1300 NL/L or less.
• the hydrogen/oil ratio may be, for example, 100 to 1500 NL/L, 100 to 1400 NL/L, 100 to 1300 NL/L, 150 to 1500 NL/L, 150 to 1400 NL/L, 150 to 1300 NL/L, 200 to 1500 NL/L, 200 to 1400 NL/L, or 200 to 1300 NL/L.
• the low-temperature hydrogenated oil obtained in the low-temperature hydrogenation step preferably has the following properties:
• the diene value of the low-temperature hydrogenated oil is preferably less than 14.0 gI 2 /100g, more preferably 13.0 gI 2 /100g or less, further preferably 12.0 gI 2 /100g or less, and particularly preferably 11.0 gI 2 /100g or less.
• the iodine value of the low-temperature hydrogenated oil is preferably less than 160 gI 2 /100 g, more preferably 155 gI 2 /100 g or less, further preferably 150 gI 2 /100 g or less, and particularly preferably 145 gI 2 /100 g or less.
• the total acid value of the low-temperature hydrogenated oil is less than 5.0 mgKOH/g, more preferably 4.8 mgKOH/g or less, further preferably 4.7 mgKOH/g or less, particularly preferably 4.5 mgKOH/g or
• the present invention by reducing in advance the olefins, dienes, higher fatty acids, and other substances that polymerize and cause fouling in the pyrolysis oil treated in the low-temperature hydrogenation process, it is possible to suppress the occurrence of fouling in heat exchangers and heating furnaces even when the oil is heated to the high temperatures required in the subsequent hydrocracking process, making it possible to realize long-term operation of the process.
• the hydrocracking step is a step in which a feedstock oil containing at least a portion of low-temperature hydrogenated oil is hydrocracked to obtain a second gas fraction, a light fraction having a boiling point of 350°C or less, and a heavy fraction having a boiling point of more than 350°C.
• the feedstock oil in the hydrocracking process contains low-temperature hydrogenated oil, but may also contain a portion of pyrolysis oil, a portion of the fraction obtained by fractional distillation of pyrolysis oil, and may further contain other components.
• the feedstock oil in the hydrocracking process contains low-boiling oil with a boiling point of 350°C or less and high-boiling oil with a boiling point of more than 350°C, and the content of high-boiling oil is, for example, 50 mass% or less based on the total amount of feedstock oil.
• the content of high boiling point oil in the feedstock in the hydrocracking step is preferably 50 mass% or less, based on the total amount of the feedstock, more preferably 40 mass% or less, even more preferably 30 mass% or less, still more preferably 20 mass% or less, particularly preferably 10 mass% or less, and most preferably 5 mass% or less.
• the content of high boiling point oil in the feedstock oil in the hydrocracking step may be 1.0 mass% or more, 2.0 mass% or more, or 3.0 mass% or more, based on the total amount of the feedstock oil.
• the 10% distillation temperature of the feedstock oil in the hydrocracking step may be, for example, 90° C. or higher, preferably 140° C. or higher, more preferably 150° C. or higher, and even more preferably 155° C. or higher.
• the 10% distillation temperature of the feedstock oil in the hydrocracking step may be, for example, 200° C. or lower, 190° C. or lower, or 180° C. or lower.
• the 10% distillation temperature of the feedstock oil in the hydrocracking step may be, for example, 90 to 200 ° C., 90 to 190 ° C., 90 to 180 ° C., 140 to 200 ° C., 140 to 190 ° C., 140 to 180 ° C., 150 to 200 ° C., 150 to 190 ° C., 150 to 180 ° C., 155 to 200 ° C., 155 to 190 ° C., or 155 to 180 ° C.
• the 90% distillation temperature of the feedstock oil in the hydrocracking step may be, for example, 350° C. or higher, preferably 370° C. or higher, more preferably 390° C. or higher, and even more preferably 400° C. or higher, and may be 410° C. or higher, 420° C. or higher, 430° C. or higher, 440° C. or higher, or 450° C. or higher.
• the 90% distillation temperature of the feedstock oil in the hydrocracking step may be, for example, 650° C. or lower, preferably 600° C. or lower, and more preferably 550° C. or lower.
• the 90% distillation temperature of the feedstock oil in the hydrocracking step is, for example, 350 to 650°C, 350 to 600°C, 350 to 550°C, 370 to 650°C, 370 to 600°C, 370 to 550°C, 390 to 650°C, 390 to 600°C, 390 to 550°C.
• the feedstock oil used in the hydrocracking process may contain nitrogen, sulfur, chlorine, other halogen elements, etc.
• the nitrogen content of the feedstock oil in the hydrocracking step may be, for example, 100 ppm by mass or more, 2000 ppm by mass or more, 2500 ppm by mass or more, or 3000 ppm by mass or more.
• the nitrogen content of the feedstock oil may be, for example, 20,000 ppm by mass or less, 15,000 ppm by mass or less, or 10,000 ppm by mass or less.
• the nitrogen content of the feedstock oil in the hydrocracking step may be, for example, 100 to 20,000 ppm by mass, 100 to 15,000 ppm by mass, 100 to 10,000 ppm by mass, 2000 to 20,000 ppm by mass, 2000 to 15,000 ppm by mass, 2000 to 10,000 ppm by mass, 2500 to 20,000 ppm by mass, 2500 to 15,000 ppm by mass, 2500 to 10,000 ppm by mass, 3000 to 20,000 ppm by mass, 3000 to 15,000 ppm by mass, or 3000 to 10,000 ppm by mass.
• the sulfur content of the feedstock oil in the hydrocracking step may be, for example, 10 ppm by mass or more, 100 ppm by mass or more, 500 ppm by mass or more, or 1000 ppm by mass or more.
• the sulfur content of the feedstock oil may be, for example, 30,000 ppm by mass or less, 20,000 ppm by mass or less, or 10,000 ppm by mass or less.
• the sulfur content of the feedstock oil in the hydrocracking step may be, for example, 10 to 30,000 ppm by mass, 10 to 20,000 ppm by mass, 10 to 10,000 ppm by mass, 100 to 30,000 ppm by mass, 100 to 20,000 ppm by mass, 100 to 10,000 ppm by mass, 500 to 30,000 ppm by mass, 500 to 20,000 ppm by mass, 500 to 10,000 ppm by mass, 1000 to 30,000 ppm by mass, 1000 to 20,000 ppm by mass, or 1000 to 10,000 ppm by mass.
• the chlorine content of the feedstock oil in the hydrocracking step may be, for example, 10 ppm by mass or more, 30 ppm by mass or more, 50 ppm by mass or more, or 100 ppm by mass or more.
• the chlorine content of the feedstock oil may be, for example, 2000 ppm by mass or less, 1500 ppm by mass or less, or 1000 ppm by mass or less.
• other halogen element contents may be in the same range.
• the chlorine content of the feedstock oil in the hydrocracking step may be, for example, 10 to 2000 ppm by mass, 10 to 1500 ppm by mass, 10 to 1000 ppm by mass, 30 to 2000 ppm by mass, 30 to 1500 ppm by mass, 30 to 1000 ppm by mass, 50 to 2000 ppm by mass, 50 to 1500 ppm by mass, 50 to 1000 ppm by mass, 100 to 2000 ppm by mass, 100 to 1500 ppm by mass, or 100 to 1000 ppm by mass.
• the hydrocracking process may be a process of hydrocracking a feedstock in the presence of a hydrocracking catalyst.
• Hydrocracking can be carried out, for example, by supplying the feedstock to a reactor in which a hydrocracking catalyst is disposed and contacting the feedstock with the hydrocracking catalyst in the reactor.
• hydrocracking catalyst for example, a known hydrocracking catalyst used for hydrocracking of hydrocarbon oils can be used.
• the hydrocracking catalyst when the feedstock oil in the hydrocracking process contains high-boiling-point oil, the hydrocracking catalyst is preferably a catalyst that has excellent hydrogenation ability and can efficiently hydrocrack the high-boiling-point oil. From the viewpoint of hydrogenation ability, the hydrocracking catalyst preferably contains, for example, a Ni-based catalyst.
• a Ni-based catalyst is a catalyst that has Ni as an active metal.
• the hydrocracking process may be carried out using one type of hydrocracking catalyst, or may be carried out using multiple types of hydrocracking catalysts.
• an appropriate combination of desulfurization/denitrification catalysts, high-resolution catalysts, low-resolution catalysts, etc., described below, may be used as the hydrocracking catalyst.
• the desulfurization/denitrification catalyst may be a hydrocracking catalyst that has excellent desulfurization and denitrification performance.
• An example of a desulfurization/denitrification catalyst is a hydrocracking catalyst in which an active metal is supported on a support containing alumina. Such hydrocracking catalysts tend to have excellent desulfurization and denitrification performance.
• the support for the desulfurization/denitrification catalyst may be an alumina-containing support, and preferably has an alumina content of 50% by mass or more.
• the alumina content in the support for the desulfurization/denitrification catalyst may be, for example, 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more, based on the total amount of the support.
• the carrier of the desulfurization/denitrogenation catalyst may contain a component other than alumina.
• the carrier of the desulfurization/denitrogenation catalyst may contain, for example, an oxide of an element of Group 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the carrier of the desulfurization/denitrogenation catalyst may contain, for example, at least one oxide of silica, phosphorus, magnesia, zirconia, boria, titania, calcia, zinc, etc.
• the carrier of the desulfurization/denitrogenation catalyst contains silica, silica-alumina, silica-alumina-phosphorus, silica-magnesia, alumina-silica-magnesia, alumina-silica-zirconia, etc.
• the carrier of the desulfurization/denitrogenation catalyst may be crystalline or amorphous.
• the shape of the support for the desulfurization/denitrification catalyst is not particularly limited, and may be, for example, spherical, cylindrical, trilobe, or quadrilobe.
• Examples of active metals contained in the desulfurization/denitrification catalyst include Ni, Mo, Co, W, and P.
• the desulfurization/denitrification catalyst may contain one type of active metal, or may contain two or more types. From the viewpoint of easily realizing excellent hydrogenation ability and enabling more efficient desulfurization/denitrification, the desulfurization/denitrification catalyst preferably contains at least Ni, and more preferably contains Ni and Mo or W.
• the active metal may be activated by a sulfurization treatment. By containing sulfides of Ni, among the above metals, in particular, the desulfurization/denitrification catalyst is more likely to realize excellent hydrogenation ability.
• An example of a high-resolution catalyst is a hydrocracking catalyst that is made by supporting an active metal on a carrier containing zeolite.
• Such hydrocracking catalysts have small pores and tend to have excellent hydrocracking ability.
• the carrier of the high resolution catalyst may be a carrier containing zeolite, and preferably the zeolite content is 1 mass% or more.
• the zeolite content in the carrier of the high resolution catalyst may be, for example, 2 mass% or more, preferably 3 mass% or more, and more preferably 5 mass% or more, based on the total amount of the carrier.
• the carrier of the high-resolution catalyst may contain a component other than zeolite.
• the carrier of the high-resolution catalyst may contain, for example, an oxide of an element of Groups 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the carrier of the high-resolution catalyst may contain at least one oxide of, for example, silica, alumina, phosphorus, magnesia, zirconia, boria, titania, calcia, zinc, etc.
• the carrier of the high-resolution catalyst contains alumina, silica, silica-alumina, silica-alumina-phosphorus, silica-magnesia, alumina-silica-magnesia, alumina-silica-zirconia, etc.
• the carrier of the high-resolution catalyst may be crystalline or amorphous.
• the shape of the carrier of the high-resolution catalyst is not particularly limited, and may be, for example, spherical, cylindrical, trilobal, or quadrolobal.
• Examples of active metals contained in the high-resolution catalyst include Ni, Mo, Co, W, and P.
• the high-resolution catalyst may contain one type of active metal, or may contain two or more types. From the viewpoint of easily realizing excellent hydrogenation ability and being able to hydrocrack high boiling point oils more efficiently, the high-resolution catalyst preferably contains at least Ni, and more preferably contains Ni and Mo or W.
• the active metal may be activated by a sulfurization treatment. By containing sulfides of Ni, particularly of the above metals, the desulfurization/denitrogenation catalyst is more likely to realize excellent hydrogenation ability.
• a low-resolution catalyst is a hydrocracking catalyst that has an active metal supported on a support containing alumina.
• Such hydrocracking catalysts have many large pores compared to high-resolution catalysts, and tend to have milder hydrocracking properties compared to high-resolution catalysts.
• the support of the low-resolution catalyst may be a support containing alumina.
• the alumina content in the support of the low-resolution catalyst may be, for example, 20 mass% or more, preferably 25 mass% or more, and more preferably 30 mass% or more, based on the total amount of the support.
• the support of the low-resolution catalyst may contain a component other than alumina.
• the support of the low-resolution catalyst may contain, for example, an oxide of an element of Group 2, 3, 4, 13, 14, or 15 of the periodic table. More specifically, the support of the low-resolution catalyst may contain at least one oxide of, for example, silica, phosphorus, magnesia, zirconia, boria, titania, calcia, zinc, etc.
• Examples of active metals contained in the low-resolution catalyst include Ni, Mo, Co, W, and P.
• the low-resolution catalyst may contain one type of active metal, or may contain two or more types. From the viewpoint of more efficient hydrocracking of high boiling point oils, the low-resolution catalyst preferably contains at least Ni, and more preferably contains Ni and Mo or W.
• the active metal may be activated by a sulfurization treatment. By containing sulfides of Ni, particularly of the above metals, the desulfurization/denitrogenation catalyst is more likely to achieve excellent hydrogenation ability.
• the nitrogen in the feedstock oil may adhere to the active sites of the high-resolution catalyst or low-resolution catalyst, thereby reducing the cracking performance of the high-resolution catalyst or low-resolution catalyst.
• the nitrogen in the feedstock oil is converted to ammonia, etc., and the nitrogen content in the feedstock oil is reduced. Therefore, in the hydrocracking process, it is preferable to place the desulfurization/denitrification catalyst in a stage before the high-resolution catalyst or low-resolution catalyst. In other words, it is preferable to place the desulfurization/denitrification catalyst in a stage before the hydrocracking unit described below. With this arrangement, even if the feedstock oil contains nitrogen, it is possible to prevent the cracking performance of the high-resolution catalyst or low-resolution catalyst from decreasing.
• the hydrocracking step may be carried out, for example, using a flow reactor.
• a flow reactor it is preferable to arrange, in the flow reactor from the inlet side, a first catalyst layer containing a desulfurization/denitrification catalyst and a second catalyst layer containing a decomposition catalyst in this order.
• a third catalyst layer containing a type of decomposition catalyst with a different decomposition ability and a fourth catalyst layer containing a desulfurization/denitrification catalyst may be further arranged downstream of the second catalyst layer.
• the reaction temperature in the hydrocracking step is not particularly limited, and may be, for example, 300°C or higher, preferably 320°C or higher, and more preferably 340°C or higher.
• the reaction temperature in the hydrocracking step may be, for example, 480°C or lower, preferably 460°C or lower, and more preferably 440°C or lower. That is, the reaction temperature in the hydrocracking step may be, for example, 300 to 480°C, 300 to 460°C, 300 to 440°C, 320 to 480°C, 320 to 460°C, 320 to 440°C, 340 to 480°C, 340 to 460°C, or 340 to 440°C.
• the weight hourly space velocity (WHSV) of the feed oil may be, for example, 0.1 h ⁇ 1 or more, preferably 0.15 h ⁇ 1 or more, more preferably 0.2 h ⁇ 1 or more.
• the weight hourly space velocity (WHSV) of the feed oil may be, for example, 5 h ⁇ 1 or less, preferably 4 h ⁇ 1 or less, more preferably 3 h ⁇ 1 or less.
• the weight hourly space velocity (WHSV) of the feed oil may be 0.1 to 5 h ⁇ 1 , 0.1 to 4 h ⁇ 1 , 0.1 to 3 h ⁇ 1 , 0.15 to 5 h ⁇ 1 , 0.15 to 4 h ⁇ 1 , 0.15 to 3 h ⁇ 1 , 0.2 to 5 h ⁇ 1 , 0.2 to 4 h ⁇ 1 or 0.2 to 3 h ⁇ 1 .
• the hydrocracking step is carried out in the presence of hydrogen.
• the hydrogen/oil ratio may be, for example, 100 NL/L or more, preferably 150 NL/L or more, more preferably 200 NL/L or more.
• the hydrogen/oil ratio may be, for example, 1500 NL/L or less, preferably 1400 NL/L or less, more preferably 1300 NL/L or less.
• the hydrogen/oil ratio may be, for example, 100 to 1500 NL/L, 100 to 1400 NL/L, 100 to 1300 NL/L, 150 to 1500 NL/L, 150 to 1400 NL/L, 150 to 1300 NL/L, 200 to 1500 NL/L, 200 to 1400 NL/L, or 200 to 1300 NL/L.
• the feedstock oil is hydrocracking to produce a second gas fraction, a light fraction with a boiling point of 350°C or less, and a heavy fraction with a boiling point of more than 350°C.
• the second gas component may be, for example, a component of the product produced by hydrocracking that is gaseous at room temperature, 20°C.
• the second gas component may contain, for example, hydrogen, hydrocarbons with 1 to 4 carbon atoms, etc.
• the light fraction may be, for example, a hydrocarbon oil having a boiling point of 350°C or less, among the products produced by hydrocracking.
• the light fraction is subjected to a steam cracking process.
• the sulfur content in the light fraction is, for example, 1500 ppm by mass or less, and from the viewpoints of reducing the amount of impurities in the chemical products obtained in the cracking process, preventing catalyst poisoning in the later stages of the cracking process, and preventing equipment corrosion, it is preferably 1000 ppm by mass or less, and more preferably 900 ppm by mass or less.
• the nitrogen content in the light fraction is, for example, 25 ppm by mass or less, and from the viewpoint of reducing the amount of impurities in the chemical products obtained in the cracking process and preventing catalyst poisoning and equipment corrosion in the later stages of the cracking process, it is preferably 20 ppm by mass or less, and more preferably 15 ppm by mass or less.
• the chlorine content in the light fraction is, for example, 20 ppm by mass or less, and from the viewpoint of reducing the amount of impurities in the chemical products obtained in the cracking process and preventing catalyst poisoning and equipment corrosion in the later stages of the cracking process, it is preferably 15 ppm by mass or less, and more preferably 10 ppm by mass or less.
• the contents of other halogen elements are in the same range.
• the heavy fraction may be, for example, a hydrocarbon oil having a boiling point exceeding 350°C, which is a product produced by hydrocracking.
• the heavy fraction may be reused, for example, as part or all of the feedstock oil for the low-temperature hydrogenation process or hydrocracking process.
• the heavy fraction may also be used, for example, as fuel oil for heating the thermal cracking section in the thermal cracking process or as fuel oil for heating furnaces in other processes, or may be processed in FCC units in oil refineries.
• the steam cracking step is a step in which a steam cracking feedstock oil containing a part of the light fraction obtained in the hydrocracking step is subjected to a steam cracking treatment to obtain a chemical product and a raw material for carbonization comprising a heavy fraction having a 10% distillation temperature of 190° C. or more.
• the steam cracking feedstock oil is heat treated with steam to decompose the light fraction and generate components useful as chemical products.
• the heavy fraction obtained in the steam cracking step and having a 10% distillation temperature of 190° C. or more can be suitably used as a raw material for carbonization.
• the steam cracking feedstock oil in the steam cracking process may further contain, in addition to the light fraction, ethane, naphtha, kerosene, diesel fractions, etc. derived from petroleum, etc.
• the light fraction may be used as it is as the steam cracking feedstock oil.
• the conditions for the steam cracking process are not particularly limited and may be appropriately selected from known conditions used in the steam cracking processes of ethane, naphtha, kerosene, etc.
• the reaction temperature of the steam cracking process may be, for example, 650°C or higher, preferably 700°C or higher, and more preferably 750°C or higher.
• the reaction temperature of the steam cracking process may be, for example, 1000°C or lower, preferably 950°C or lower, and more preferably 900°C or lower. That is, the reaction temperature of the steam cracking process may be, for example, 650 to 1000°C, 650 to 950°C, 650 to 900°C, 700 to 1000°C, 700 to 950°C, 700 to 900°C, 750 to 1000°C, 750 to 950°C, or 750 to 900°C.
• the reaction time (residence time) of the steam cracking treatment may be, for example, 0.05 seconds or more, preferably 0.06 seconds or more, more preferably 0.08 seconds or more, and may be, for example, 2.0 seconds or less, preferably 1.9 seconds or less, more preferably 1.8 seconds or less. That is, the reaction time of the steam cracking treatment may be, for example, 0.05 to 2.0 seconds, 0.05 to 1.9 seconds, 0.05 to 1.8 seconds, 0.06 to 2.0 seconds, 0.06 to 1.9 seconds, 0.06 to 1.8 seconds, 0.08 to 2.0 seconds, 0.08 to 1.9 seconds, or 0.08 to 1.8 seconds.
• the steam/steam cracking feedstock oil ratio (mass ratio) in the steam cracking treatment may be, for example, 0.2 or more, preferably 0.25 or more, more preferably 0.3 or more, and may be, for example, 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less. That is, the ratio (mass ratio) of steam to steam cracking feed oil may be, for example, 0.2 to 1.0, 0.2 to 0.9, 0.2 to 0.8, 0.25 to 1.0, 0.25 to 0.9, 0.25 to 0.8, 0.3 to 1.0, 0.3 to 0.9, or 0.3 to 0.8.
• the outlet reaction pressure of the steam cracking treatment may be, for example, 0.1 MPaA or more, preferably 0.15 MPaA or more, more preferably 0.2 MPaA or more.
• the reaction pressure of the steam cracking treatment may be, for example, 1.0 MPaA or less, preferably 0.8 MPaA or less, more preferably 0.6 MPaA or less. That is, the outlet reaction pressure of the steam cracking treatment may be, for example, 0.1 to 1.0 MPaA, 0.1 to 0.8 MPaA, 0.1 to 0.6 MPaA, 0.15 to 1.0 MPaA, 0.15 to 0.8 MPaA, 0.15 to 0.6 MPaA, 0.2 to 1.0 MPaA, 0.2 to 0.8 MPaA, or 0.2 to 0.6 MPaA.
• Chemical products obtained from the steam cracking process include, for example, ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, indene, methylstyrene, and other olefin-containing C9 aromatics for resin conversion.
• light fractions may be obtained in addition to chemical products.
• light fractions include methane, ethane, propane, butane, pentane, hexane, etc.
• heavy fractions may be obtained in addition to chemical products.
• the heavy fractions obtained in the steam cracking process of this embodiment tend to have a high aromatic content and can be suitably used as raw materials for producing charcoal (particularly carbon black).
• the 10% distillation temperature of the heavy fraction may be, for example, 190° C. or higher, and may be 200° C. or higher.
• the 10% distillation temperature of the heavy fraction may be, for example, 250° C. or lower, and may be 240° C. or lower.
• the 90% distillation temperature of the heavy fraction may be, for example, 450° C. or higher, and may be 500° C. or higher.
• the 90% distillation temperature of the heavy fraction may be, for example, 750° C. or lower, and may be 700° C. or lower. That is, the 10% distillation temperature of the heavy fraction may be, for example, 190 to 250° C., 190 to 240° C., 200 to 250° C., or 200 to 240° C.
• the 90% distillation temperature of the heavy fraction may be, for example, 450 to 750° C., 450 to 700° C., 500 to 750° C., or 500 to 700° C.
• the aromatic content of the heavy fraction may be, for example, 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and may be, for example, 90% by mass or less. That is, the aromatic content of the heavy fraction may be, for example, 30 to 90 mass %, 35 to 90 mass %, or 40 to 90 mass %.
• the steam cracking process may be carried out, for example, using a steam cracking apparatus equipped with a reactor.
• the manufacturing method of this embodiment may further include a char production step of obtaining a char by pyrolysis or incomplete combustion of a char production raw material.
• the raw materials for charcoal production obtained through the steam cracking process tend to have a high aromatic content, making it easier to produce charcoal (especially carbon black) with high production yields.
• the pyrolysis or incomplete combustion in the charcoal production process can be carried out, for example, using the soft carbon black production apparatus disclosed in JP Patent Publication 61-34071 (applicant: Asahi Carbon Co., Ltd.) by spraying the heavy fraction obtained in the steam cracking process into a combustion reaction chamber containing high-temperature oxygen, and then quenching with water or the like.
• incomplete combustion can be said to be combustion in an atmosphere with a low oxygen concentration.
• a low oxygen concentration is a concentration lower than the oxygen concentration in the atmosphere (approximately 21% by volume).
• the temperature of pyrolysis or incomplete combustion in the carbide production process is not particularly limited, and may be, for example, 1200° C. or higher, 1300° C. or higher, 1400° C. or higher, or 1500° C. or higher.
• the temperature of pyrolysis or incomplete combustion in the carbide production process may be, for example, 1900° C. or lower, 1800° C. or lower, 1700° C. or lower, or 1600° C. or lower.
• the temperature of pyrolysis or incomplete combustion in the carbide production process may be, for example, 1200 to 1900°C, 1200 to 1800°C, 1200 to 1700°C, 1200 to 1600°C, 1300 to 1900°C, 1300 to 1800°C, 1300 to 1700°C, 1300 to 1600°C, 1400 to 1900°C, 1400 to 1800°C, 1400 to 1700°C, 1400 to 1600°C, 1500 to 1900°C, 1500 to 1800°C, 1500 to 1700°C, or 1500 to 1600°C.
• the carbonized material obtained in the carbonization process is, for example, carbon black.
• FIG. 2 is a schematic diagram showing an example of a system for carrying out the manufacturing method of this embodiment.
• the system 100 shown in FIG. 2 includes a pyrolysis unit 110, a first separation unit 111, a pulverization unit 112, a low-temperature hydrogenation unit 115, a hydrocracking unit 120, a second separation unit 121, a steam cracker 130, and a carbide production unit 140.
• the waste material S1 is supplied to the pyrolysis unit 110, where the waste material S1 is pyrolyzed.
• a mixture S4 of a first gas component S2, pyrolysis oil S3, a residue component, and a metal component is generated.
• the first gas component S2 may be discharged outside the system, or may be reused as an oxygen-free gas in the pyrolysis unit 110.
• the pyrolysis oil S3 is supplied to the hydrocracking unit 120.
• the mixture S4 is supplied to the first separation unit 111, where it is separated into a residue component S5 and a metal component S6.
• the residue component S5 is pulverized in the pulverization unit 112 and collected as powdered charcoal S7.
• low-temperature hydrogenation unit 115 low-temperature hydrogenation of the pyrolysis oil S3 produces low-temperature hydrogenated oil S8.
• the low-temperature hydrogenated oil S8 is supplied to the hydrocracking unit 120.
• the pyrolysis oil S3 is hydrocracking to produce a second gas fraction S9 and a hydrocracked oil S10.
• the second gas fraction S9 may be discharged from the system, or may be used as a combustion gas for heating the pyrolysis section in the pyrolysis process or as a combustion gas for a heating furnace in other processes.
• the hydrocracked oil S10 is supplied to the second separation unit 121, where it is fractionated into a light fraction S11 and a heavy fraction S12.
• the light fraction S11 is supplied to the steam cracker 130.
• the heavy fraction S12 may be recovered as a heavy oil fraction, may be reused in the hydrocracking unit 120, or may be used as a combustion oil for heating the pyrolysis section in the pyrolysis process or as a combustion oil for a heating furnace in other processes.
• the recycled oil S17 containing the light fraction S11 and the heavy fraction S12 may be reused in the low-temperature hydrogenation unit 115.
• the light fraction S11 is subjected to steam cracking treatment to produce a product gas S13, a product oil S14, and a heavy fraction S15.
• the product gas S13 and the product oil S14 contain ethylene, propylene, butadiene, butenes, isoprene, benzene, toluene, xylene, ethylbenzene, styrene, cyclopentadiene, dicyclopentadiene, olefin-containing C9 aromatics for resin conversion such as indene and methylstyrene, which are useful as chemical products, and the product gas S13 and the product oil S14 are appropriately separated and recovered to obtain chemical products.
• the heavy fraction S15 is supplied to the char production unit 140. In the char production unit 140, the heavy fraction S15 is thermally decomposed to produce a char S16.
• the method for producing butadiene according to the present embodiment includes a polymerization step of obtaining synthetic rubber by a polymerization reaction using the butadiene obtained by the above-described production method as at least a part of the raw material of the synthetic rubber.
• a polymerization composition containing at least butadiene as a monomer is polymerized by a conventionally known method 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.
• the monomer may be butadiene alone, or in addition to butadiene, other conventionally known monomers for synthetic rubber may be used depending on the composition and properties of the desired synthetic rubber.
• Other monomers for synthetic rubber include conjugated diene compounds other than butadiene and aromatic vinyl compounds.
• Conjugated diene compounds other than butadiene include, for example, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, etc.
• Conjugated diene compounds other than butadiene may be used alone or in combination of two or more kinds.
• Aromatic vinyl compounds include, for example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethylether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-buty
• the polymerization composition may contain, in addition to the monomer, additives and solvents that are conventionally known.
• additives include polymerization initiators, emulsifiers, and surfactants.
• an alkali metal compound is used as the polymerization initiator.
• alkali metal compounds include alkyl lithium such as methyl lithium, ethyl lithium, n-propyl lithium, n-butyl lithium, sec-butyl lithium, and t-butyl lithium; 1,4-dilithiobutane, phenyl lithium, stilbene lithium, naphthyl lithium, 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentylidene)dilithium, naphthyl sodium, naphthyl potassium, and ethoxy potassium.
• the tire of the present embodiment contains synthetic rubber obtained by the above-described method for producing synthetic rubber.
• the method for producing a tire according to the present embodiment includes a vulcanization step of obtaining a tire by a vulcanization reaction using the synthetic rubber obtained by the above-described method for producing synthetic rubber as at least a part of the raw materials for the tire.
• a tire in the vulcanization process, can be obtained by vulcanizing a vulcanization composition containing at least synthetic rubber using a conventionally known method.
• the vulcanization conditions are not particularly limited and can be adjusted as appropriate depending on the composition of the vulcanization composition and the shape and structure of the desired tire.
• the vulcanization composition may contain, in addition to synthetic rubber, additives that are conventionally known.
• additives include vulcanizing agents, vulcanization accelerators, vulcanization accelerator assistants, antioxidants, softeners, antioxidants, and colorants. These additives may be used alone or in combination of two or more.
• vulcanizing agents include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, and alkylphenol disulfide, as well as zinc oxide, magnesium oxide, litharge, p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylene dianiline, phenolic resin, brominated alkylphenol resin, and chlorinated alkylphenol resin.
• sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, and alkylphenol disulfide, as well as zinc oxide, magnesium oxide, litharge, p-quinone dioxime, p-dibenzoylquinone dioxime, te
• vulcanization accelerators include thiuram-based agents such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM); aldehyde/ammonia-based agents such as hexamethylenetetramine; guanidine-based agents such as diphenylguanidine (DPG); thiazole-based agents such as 2-mercaptobenzothiazole (MBT) and dibenzothiazyl disulfide (DM); sulfenamide-based agents such as N-cyclohexyl-2-benzothiazylsulfenamide (CBS) and N-t-butyl-2-benzothiazylsulfenamide (BBS); and dithiocarbamate-based agents such as zinc dimethyldithiocarbamate (ZnPDC).
• TMTD tetramethylthiuram disul
• vulcanization accelerators include fatty acids, zinc fatty acids, zinc salts of fatty acids, and zinc oxide.
• fatty acids that can be used include acetic acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid.
• zinc fatty acids that can be used include zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc acrylate, and zinc maleate.
• antioxidants include aliphatic and aromatic hindered amine and hindered phenol compounds.
• antioxidants examples include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
• Colorants include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate, azo pigments, and copper phthalocyanine pigments.
• the mass balance method has been attracting attention in various industries, including the chemical, steel, and aluminum industries, in order to sell environmentally friendly products that use plant-based raw materials and recycled materials in a more attractive manner. It is desirable to be able to assign a value as a renewable product to each product produced by the above-mentioned manufacturing method of the present invention using waste tires in a simple and reliable manner using the mass balance method. Therefore, the present invention provides a management method that, when producing chemical products using the above-mentioned production method of the present invention, can simply and reliably assign a value as a renewable product to each product depending on the content of renewable raw materials contained in scrap tires.
• renewable raw materials refers to renewable organic resource raw materials.
• Renewable raw materials are not intended to be limited to products derived from biological resources, but are broadly interpreted as anything that falls under the category of renewable organic resources. For example, even if the product is derived from petroleum, it is intended to include those derived from recycled products that use petroleum-derived products as raw materials, such as waste tires.
• the mass balance method refers to a method in which, for example, when raw materials with specific characteristics, such as biomass raw materials, are mixed with raw materials without those characteristics during the distribution and processing process from raw materials to products, the characteristics are assigned as credits to part of the product in accordance with the content ratio of the raw materials with those characteristics. Since the mass balance method is a method in which biomass fractions are used as credits and allocated arbitrarily by the producer, it is common for the legitimacy of the method to be verified by a third-party certification body, such as ISCC (International Sustainable Carbon) or RSB (Roundtable on Sustainable Biofuels).
• ISCC International Sustainable Carbon
• RSB Raundtable on Sustainable Biofuels
• the method for managing chemical products of the present invention can be used when producing chemical products using waste tires.
• the management method of the present invention is a method of using a management device to assign a value as a renewable product to a chemical product based on the content ratio of renewable raw materials contained in scrap tires, using a mass balance method.
• the management method of the present invention includes, for example, a step (V) in which a management device described below confirms that chemical products can be obtained (the management device acquires information indicating that chemical products can be obtained using the scrap tires), and a step (Z) in which the management device confirms the proportion of products to which a value as a renewable product is assigned (the management device acquires information indicating the proportion of products to which a value as a renewable product is assigned).
• the step (V) of confirming that a chemical product is obtained includes the following steps (V-1), (V-2), (V-3), (V-4), and (V-5).
• the step (V-1) is a step in which the management device confirms that the pyrolysis oil is produced from the waste tires that have been input into a pyrolysis unit in which the waste tires are subjected to a pyrolysis treatment at 350° C. or higher and 750° C. or lower to obtain pyrolysis oil.
• the step (V-2) is a step in which the management device confirms that the low-temperature hydrogenated oil is produced from the pyrolysis oil input into a low-temperature hydrogenation unit in which a feedstock oil containing at least a portion of the pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180°C or higher and 350°C or lower to obtain low-temperature hydrogenated oil.
• the step (V-3) is a step in which the management device confirms that the light fractions are produced from the low-temperature hydrogenated oil input into a hydrocracking unit in which a feedstock oil containing at least a portion of the low-temperature hydrogenated oil is subjected to hydrocracking at a temperature higher than that of the low-temperature hydrogenation treatment to obtain light fractions having a boiling point of 350°C or lower.
• Step (V-4) is a step in which the management device confirms that the chemical product is obtained from the light fraction fed into a steam cracker that subjects a steam cracking feedstock oil containing at least a portion of the light fraction to a steam cracking treatment.
• the step (V-5) is a step in which the management device confirms that the chemical products can be obtained from the scrap tires by processing the scrap tires in the order of the pyrolysis unit, the hydrocracking unit, the hydrocracking unit, and the steam cracker.
• Step (Z) of identifying the proportion of a product to be assigned a value as a renewable product includes the following steps (Z-1), (Z-2), (Z-3), and (Z-4).
• the step (Z-1) is a step in which the management device selects a product to be allocated as a renewable product from among the products obtained by the steam cracker.
• the step (Z-2) is a step in which the management device determines the value of the proportion (P) to be allocated as a renewable product among the proportion of the product selected in the step (Z-1) to the products obtained by the steam cracker.
• the step (Z-3) is a step in which the management device grasps the content ratio (Q) of renewable raw materials contained in the waste tires.
• Step (Z-4) is a step in which the management device compares the value of the ratio (P) with the value of the content ratio (Q) and confirms that the value of the ratio (P) is equal to or less than the value of the content ratio (Q).
• Step (Z-1) If the products obtained by the steam cracker are ethylene, propylene, butadiene, and other products, select butadiene.
• Step (Z-3) When the renewable raw materials in the waste tires are 5% by mass and the non-renewable raw materials are 95% by mass, the content ratio (Q) of the renewable raw materials is determined (obtained) to be 5% by mass.
• the content ratio (Q) of the renewable raw material is 5 mass%
• the ratio (P) allocated to the butadiene as a renewable product is 5 mass% or less.
• the butadiene product from the steam cracker can be assigned a value as a renewable product according to the percentage of renewable raw materials contained in the scrap tires.
• the butadiene product excluding (P) mass% out of 10 mass% butadiene product (10-(P) mass% butadiene product) actually contains renewable components.
• the (P) mass% butadiene is assigned a credit for 100% renewable butadiene, it is not treated as renewable butadiene.
• the value of 5 mass% of the content ratio (Q) of the renewable raw material and the value of 10 mass% of the butadiene product are set for the sake of convenience in order to facilitate understanding of the present invention, and are not limited to these values.
• the management method of the present invention can be executed by using a management device as described above. Furthermore, the processes in the steps of the management method executed by the management device are executed by a computer having a control unit constituting the management device.
• a management device for executing the management method of the present invention and a management program (computer program) executed by a computer of the management device will be described below.
• the management device is a device that assigns a value as a renewable product to the chemical product using a mass balance method in accordance with a content ratio of renewable raw materials contained in the scrap tires,
• the management device has a confirmation unit (I) for confirming that the chemical product is obtained,
• the confirmation unit (I) includes the following means (V-1), (V-2), (V-3), (V-4), and (V-5):
• the means (V-1) is a means for confirming that the pyrolysis oil is produced from the waste tires that have been input into a pyrolysis unit that subjects the waste tires to a pyrolysis treatment at 350° C.
• the means (V-2) is a means for confirming that the low-temperature hydrogenated oil is produced from the pyrolysis oil input into a low-temperature hydrogenation unit in which a feedstock oil containing at least a part of the pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180° C. or more and 350° C.
• the means (V-3) is a means for confirming that the light fraction is produced from the low-temperature hydrogenated oil input into a hydrocracking unit in which a feedstock oil containing at least a part of the low-temperature hydrogenated oil is subjected to hydrocracking at a temperature higher than that of the low-temperature hydrogenation treatment to obtain light fractions having a boiling point of 350° C.
• the means (V-4) is a means for confirming that the chemical product is obtained from the light fraction input into a steam cracker that subjects a steam cracking feedstock oil containing at least a part of the light fraction to a steam cracking treatment
• the means (V-5) is a means for confirming that the chemical products can be obtained from the waste tires by treating them in the order of the thermal cracking unit, the low-temperature hydrogenation unit, the hydrocracking unit, and the steam cracker
• the management device has a confirmation unit (I) for confirming the proportion of the product that is assigned a value as a renewable product
• the confirmation unit (I) includes the following means (Z-1), the following means (Z-2), the following means (Z-3), and the following means (Z-4),
• the means (Z-1) is a means for selecting a product to be allocated as a renewable product from among the products obtained by the steam cracker
• the means (Z-2) is a means for determining a value of a proportion (P) to be allocated as a renewable
• the management program executed by a management device used when manufacturing chemical products using waste tires
• the management program is a program for allocating values as renewable products to the chemical products using a mass balance method in accordance with a content ratio of renewable raw materials contained in the scrap tires, by using the management device;
• the management program includes: (V-1): Confirming that the pyrolysis oil is produced from the waste tires that are fed into a pyrolysis unit in which the waste tires are subjected to a pyrolysis treatment at 350°C or higher and 750°C or lower to obtain pyrolysis oil; (V-2): A step of confirming that the low-temperature hydrogenated oil is produced from the pyrolysis oil introduced into a low-temperature hydrogenation unit in which a feedstock oil containing at least a portion of the pyrolysis oil is subjected to low-temperature hydrogenation treatment at 180° C.
• V-3 A step of confirming that the light fraction is produced from the low-temperature hydrogenated oil input into a hydrocracking unit in which a feedstock oil containing at least a portion of the low-temperature hydrogenated oil is subjected to hydrocracking at a temperature higher than that of the low-temperature hydrogenation treatment to obtain light fractions having a boiling point of 350° C.
• (V-4) A step of subjecting a steam cracking feedstock oil containing at least a portion of the light fraction to a steam cracking treatment, and confirming that the chemical product can be obtained from the light fraction fed into a steam cracker; (V-5): A step of confirming that the chemical products can be obtained from the waste tires by treating them in the order of the thermal cracking unit, the low-temperature hydrogenation unit, the hydrocracking unit, and the steam cracker,
• the management program includes: The method includes a step (Z) of identifying the proportion of products to be assigned a value as a renewable product; (Z-1): Select a product to be allocated as a renewable product from among the products obtained by the steam cracker; (Z-2): Determine the value of the proportion (P) to be allocated as a renewable product among the proportion of the product selected in the step (Z-1) to the product obtained by the steam cracker; (Z-3): Determine the content ratio (Q) of renewable raw materials contained in the waste tires, (Z-4): The value of the
• the management device is a device that executes the management method of the present invention.
• a preferred embodiment of the management device will be described with reference to FIG.
• the management device 100 includes a control unit 110 and a storage unit 120 .
• the control unit 110 has a confirmation unit (I) 130 , a comparison unit 140 , and a notification unit (output unit) 150
• the storage unit 120 has a reaction database 160 .
• the hardware configuration and the functional configuration of the management device 100 will be described.
• FIG. 4 is a block diagram showing an example of the hardware configuration of the management device 100.
• the management device 100 includes the following components, which are connected to each other via a bus 207.
• the CPU 201 is a processing device (computer) that performs various controls and calculations.
• the CPU 201 realizes various functions by executing an OS and computer programs stored in the main memory device 202, etc. That is, in this embodiment, the CPU 201 executes a management program to function as the control unit 110 of the management device and execute the management method.
• the CPU 201 controls the overall operation of the management device 100.
• the device that controls the overall operation of the management device 100 is the CPU 201, but this is not limited thereto, and may be, for example, an FPGA (Field Programmable Gate Array).
• the management program and various databases do not necessarily have to be stored in the main storage device 202, the auxiliary storage device 203, etc.
• the management program and various databases may be stored in other information processing devices connected to the management device 100 via the Internet, a local area network (LAN), a wide area network (WAN), etc.
• the management device 100 may acquire the management program and various databases from these other information processing devices and execute them.
• the main memory device 202 is a computer-readable storage medium that stores various programs and stores data necessary to execute the various programs.
• the main memory device 202 includes a ROM and a RAM, both of which are not shown.
• the ROM stores various programs such as the BIOS.
• the RAM functions as a working area in which various programs stored in the ROM are deployed when the CPU 201 executes them.
• the RAM there are no limitations on the RAM, and it can be appropriately selected according to the purpose. Examples of the RAM include DRAM and SRAM.
• the auxiliary storage device 203 is not particularly limited as long as it can store various information, and can be appropriately selected depending on the purpose, and examples of the auxiliary storage device 203 include a solid state drive, a hard disk drive, etc.
• the auxiliary storage device 203 may also be a portable storage device such as a CD drive, a DVD drive, or a BD drive.
• a display, a speaker, etc. can be used as the output device 204.
• the input device 205 is not particularly limited as long as it can accept various requests to the management device 100, and any known device may be used as appropriate, such as a keyboard, a mouse, or a touch panel.
• the communication interface (communication I/F) 206 is not particularly limited and may be any known interface as appropriate, such as a wireless or wired communication device.
• the processing functions of the management device 100 can be realized by the above hardware configuration.
• the management device 100 includes a control unit 110 and a storage unit 120.
• the control unit 110 controls the entire management device 100.
• the control unit 110 has a confirmation unit (I) 130 , a comparison unit 140 , and a notification unit (output unit) 150 .
• the confirmation unit (I) of the control unit 110 performs the confirmation operations described in the above means (V-1) to (V-5).
• the confirmation unit (I) of the control unit 110 performs a confirmation operation in the above means (Z-1), which selects a product to be allocated as a renewable product from among the products obtained by the steam cracker, in the above means (Z-2), which determines the value of the proportion (P) to be allocated as a renewable product from the proportion of the product selected in the above means (Z-1) to the product obtained by the steam cracker, in the above means (Z-3), which grasps the value of the content proportion (Q) of renewable raw materials contained in the scrap tires, and in the above means (Z-4), which compares the value of the proportion (P) with the value of the content proportion (Q) and confirms that the value of the proportion (P) is equal to or less than the value of the content proportion (Q) (obtains information indicating that the value of the proportion (P) is equal to or less than the value of the content proportion (Q)).
• the comparison unit 140 of the control unit 110 performs a comparison operation to compare the value of the ratio (P) with the value of the content ratio (Q) in order to have the confirmation unit (I) confirm the value in the above-mentioned means (Z-4).
• the notification section 150 of the control section 110 notifies (outputs) that the selected product in an amount of (P) mass% can be allocated as a renewable product in the product, and when the value of the proportion (P) exceeds the content proportion (Q), the notification section 150 notifies (outputs) that the value has been exceeded.
• the management device 100 outputs the result in which a value as a renewable product is assigned to the selected product according to the content ratio of renewable raw materials contained in the scrap tires obtained by the management method.
• Information about the apparatus used in the management method of the present invention and information about the reactions carried out in the apparatus are stored in the reaction database 160 in the storage unit 120.
• the storage unit 120 is a computer-readable storage medium that stores a computer program, and includes a storage medium that stores the management program that causes the control unit 110, which includes a computer, to execute the management method.
• the amount and yield of the product produced from each device can be determined by measurement. However, in addition to obtaining yield results by actual measurement, by using the reaction database 160, it is possible to obtain the yield theoretically by calculation or to predict the yield based on accumulated data from the past.
• Figure 5 is a flowchart showing an example of the processing procedure of the management program in the control unit 110 of the management device 100. The following description will be given with reference to Figure 5.
• step S101 the confirmation unit 130 of the control unit 110 of the management device 100 acquires information about the pyrolysis unit, and the process proceeds to step S102.
• step S102 the confirmation unit 130 of the control unit 110 of the management device 100 confirms, for example, based on information output from the pyrolysis unit, that pyrolysis oil (OUT) is being produced from the waste tires (IN) in the pyrolysis unit, and if it is confirmed that pyrolysis oil (OUT) has been produced, transitions to step S103.
• step S103 the confirmation unit 130 of the control unit 110 of the management device 100 acquires information related to the low-temperature hydrogenation unit, and the process proceeds to step S104.
• step S104 the confirmation unit 130 of the control unit 110 of the management device 100 confirms, for example, based on information output from the low-temperature hydrogenation unit, that low-temperature hydrogenated oil (OUT) is produced from the pyrolysis oil (IN) in the low-temperature hydrogenation unit, and confirms that the low-temperature hydrogenated oil (OUT) has been produced. In the same manner, it confirms that light fractions are produced from the low-temperature hydrogenated oil fed to the hydrocracking unit, and if it confirms that chemical products can be obtained from the light fractions fed to the steam cracker, the process proceeds to step S105.
• OUT low-temperature hydrogenated oil
• the process proceeds to step S105.
• step S105 the confirmation unit 130 of the control unit 110 of the management device 100 confirms that the processing is carried out in the order of the pyrolysis unit, the low-temperature hydrogenation unit, the hydrocracking unit, and the steam cracker, for example, based on information output from the pyrolysis unit, the low-temperature hydrogenation unit, the hydrocracking unit, and the steam cracker, and confirms that chemical products (OUT) are produced from the scrap tires (IN) as a result of these processes. If it is confirmed that chemical products (OUT) have been produced, the confirmation unit 130 transitions to step S106.
• step S106 the confirmation unit 130 of the control unit 110 of the management device 100 receives information from the input device (input device 205 in FIG.
• a value as a renewable product can be assigned to the desired selected product according to the content ratio of renewable raw materials contained in the waste tires.
• the result of the assignment is notified to the user through the notification unit 150 of the control unit 110 of the chemical product management device 100. That is, as described above, after executing the chemical product management method, the chemical product management device 100 outputs the result of the assignment of a value as a renewable product to the selected product according to the content ratio of renewable raw materials contained in the waste tires obtained by the chemical product management method. If the conditions are not met during this process, the user is notified of this fact, for example, through the notification unit 150 of the control unit 110 of the chemical product management device 100. In this case, the operator can review the type of product selected, review the value of the allocation ratio (P) of the selected product, review the value of the content ratio (Q) of the renewable raw material, and further review various conditions such as reaction conditions, and try the process again.
• Iodine value JIS K 0070 (Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value, and unsaponifiable matter of chemical products)
• Total acid number JIS K 2501 (Petroleum products and lubricants - Neutralization test method)
• Heat exchange fouling evaluation for low-temperature hydrogenated oil after the low-temperature hydrogenation process The temperature drop (°C) due to fouling attached to a test piece 61 of a fouling evaluation test device (HLPS) 60 for evaluating heat exchange fouling shown in Figure 6 is measured in the following order. 1. Low-temperature hydrogenated oil at 25° C.
• HLPS soiling evaluation test device
• the difference between the initial measured temperature at the outlet 63 and the measured temperature after a certain time has elapsed is defined as the "temperature decrease caused by the electric heat decrease due to fouling.”
• a "heat exchanger fouling evaluation” is performed according to the following criteria. (Evaluation Criteria) Good: The temperature drop during evaluation for a certain period of time (200 minutes) was less than 10°C, and it was determined that fouling of the heat exchanger was suppressed.
• ⁇ The temperature drop during evaluation for a certain period of time (200 minutes) was 10° C. or more, and it was determined that the heat exchanger was significantly fouled.
• Example 1 Pyrolysis Step The pyrolysis step is carried out using the pyrolysis apparatus shown in FIG. Specifically, about 100 kg of cut-up waste truck tires (waste tires 6) are put into the pyrolysis furnace 2 (volume 0.5 m 3 ), the atmosphere inside the pyrolysis furnace 2 is replaced with nitrogen gas, and the gas temperature is raised to 500°C by the heat exchanger 1 while circulating the nitrogen gas in the pyrolysis device, and this temperature is maintained.
• the flow rate of the nitrogen gas introduced into the pyrolysis furnace 2 is set to 0.005 m 3 /s [ntp] and controlled in the range of 0.0045 m 3 /s [ntp] to 0.0055 m 3 /s [ntp].
• the impregnated solution is impregnated into the support by incipient wetness 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.
• the obtained impregnated product (catalyst precursor) is dried at 120°C for 3 hours, and then calcined at 500°C for 1 hour under air flow to obtain hydrogenation catalyst A-1.
• This impregnated solution is impregnated into the support by incipient wetness 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.
• the obtained impregnated product (catalyst precursor) is dried at 120°C for 3 hours, and then calcined at 500°C for 1 hour under air flow to obtain hydrogenation catalyst B-1.
• Example 2 A chemical product is produced in the same manner as in Example 1, except that the thermal decomposition temperature in the thermal decomposition step is changed to 400°C.
• Example 3 A chemical product was produced in the same manner as in Example 1, except that the pyrolysis temperature in the pyrolysis step was changed to 700°C.
• Example 4 Chemical products are produced in the same manner as in Example 1, except that the low-temperature hydrogenation step is carried out using a feed oil (75% by mass of low boiling oil, 25% by mass of high boiling oil) obtained by distilling the pyrolysis oil to remove 18% by mass of high boiling oil.
• the properties of the feed oil used in the low-temperature hydrogenation step are shown in Table 3.
• Example 5 Chemical products are produced in the same manner as in Example 1, except that the low-temperature hydrogenation step is carried out using a feed oil (67% by mass of low boiling oil, 33% by mass of high boiling oil) obtained by distilling the pyrolysis oil to remove 10% by mass of high boiling oil.
• the properties of the feed oil used in the low-temperature hydrogenation step are shown in Table 3.
• Example 6 A chemical product is produced in the same manner as in Example 1, except that the thermal decomposition step is carried out in the presence of a catalyst and the thermal decomposition temperature in the thermal decomposition step is changed to 350° C.
• the catalyst used in the thermal decomposition step acid clay is used.
• Example 1 A chemical product is produced in the same manner as in Example 1, except that the thermal decomposition temperature in the thermal decomposition step is changed to 300°C.
• Example 2 A chemical product was produced in the same manner as in Example 1, except that the pyrolysis temperature in the pyrolysis step was changed to 800°C.
• Examples 1 to 6 and Comparative Example 2 a powdered carbonized material suitable for use as a rubber additive, resin additive, colorant, etc. is obtained from the residue of the pyrolysis process.
• Comparative Example 1 rubber components remain in the residue, making powderization difficult and resulting in no powdered carbonized material being obtained.
• the results of the thermal decomposition step, low-temperature hydrogenation step, hydrocracking step, and steam cracking step in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Tables 1 to 9.
• the chemical product yield (mass%) relative to the total amount of thermal decomposition products excluding metals refers to the ratio of the total amount of chemical products (ethylene, propylene, butadiene, butenes, isoprene, cyclopentadiene, benzene, toluene, xylene, ethylbenzene, styrene, indene, methylstyrene) to the total amount of the first gas component, thermal decomposition oil, and residue obtained in the thermal decomposition step.
• Example 3 Chemical products are produced in the same manner as in Example 1, except that the pyrolysis oil obtained in the pyrolysis step is used as feedstock oil and hydrocracking is carried out in the hydrocracking step without going through the low-temperature hydrogenation step.
• Example 7 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 190°C.
• Example 8 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 200°C.
• Example 9 A chemical product is produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step is changed to 210°C.
• Example 10 A chemical product was produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step was changed to 250°C.
• Example 11 A chemical product was produced in the same manner as in Example 1, except that the low-temperature hydrogenation temperature in the low-temperature hydrogenation step was changed to 300°C.
• Example 12 Chemical products are produced in the same manner as in Example 1, except that a feedstock oil containing 50 mass% of pyrolysis oil obtained in the pyrolysis step and 50 mass% of recycled oil consisting of hydrocracked oil (light and heavy fractions) obtained in the hydrocracking step is used and low-temperature hydrogenation is performed in the low-temperature hydrogenation step.
• Example 13 Chemical products are produced in the same manner as in Example 1, except that a feedstock oil containing 20 mass% of pyrolysis oil obtained in the pyrolysis step and 80 mass% of recycled oil consisting of hydrocracked oil (light and heavy fractions) obtained in the hydrocracking step is used and low-temperature hydrogenation treatment is performed in the low-temperature hydrogenation step.
• Example 14 Chemical products are produced in the same manner as in Example 4, except that a low-temperature hydrogenation process is carried out in the low-temperature hydrogenation step using a feedstock oil containing 50 mass% of a feedstock oil obtained by distilling a thermal cracking oil to remove 18 mass% of high-boiling point oil and 50 mass% of a recycled oil consisting of a hydrocracked oil (light and heavy fractions) obtained in the hydrocracking step.
• Example 15 Chemical products are produced in the same manner as in Example 5, except that a low-temperature hydrogenation process is carried out in the low-temperature hydrogenation step using a feedstock oil containing 20 mass% of a feedstock oil obtained by distilling a thermal cracking oil to remove 10 mass% of high-boiling point oil and 80 mass% of a recycled oil consisting of hydrocracked oil (light and heavy fractions) obtained in the hydrocracking step.

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