[go: up one dir, main page]

WO2025178122A1 - Composition d'hydrocarbures, son procédé de production, procédé de production de composition d'oléfine inférieure, procédé de production de polymère à base de polyoléfine et procédé d'évaluation de composition d'hydrocarbures - Google Patents

Composition d'hydrocarbures, son procédé de production, procédé de production de composition d'oléfine inférieure, procédé de production de polymère à base de polyoléfine et procédé d'évaluation de composition d'hydrocarbures

Info

Publication number
WO2025178122A1
WO2025178122A1 PCT/JP2025/006023 JP2025006023W WO2025178122A1 WO 2025178122 A1 WO2025178122 A1 WO 2025178122A1 JP 2025006023 W JP2025006023 W JP 2025006023W WO 2025178122 A1 WO2025178122 A1 WO 2025178122A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrocarbon composition
mass
oxygen
ppm
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/006023
Other languages
English (en)
Japanese (ja)
Inventor
拓馬 成松
成康 嘉糠
竜郎 田中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Publication of WO2025178122A1 publication Critical patent/WO2025178122A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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

Definitions

  • the present invention relates to a hydrocarbon composition and a method for producing the same. Furthermore, the present invention relates to a method for producing a lower olefin composition from the hydrocarbon composition. Furthermore, the present invention relates to a polyolefin polymer obtained by polymerizing the above-mentioned lower olefin composition. Furthermore, the present invention relates to a method for determining a hydrocarbon composition.
  • Plastics are widely used in a variety of products, including beverage containers, food packaging, household goods, and automobile parts.
  • plastic decomposition oil is obtained from waste plastic using known thermal decomposition methods such as thermal recycling and chemical recycling, and the resulting decomposition oil is then further distilled to obtain purified decomposition oil.
  • pyrolysis oils such as plastic cracking oil obtained from chemically recycled raw materials such as waste plastics contain oxygen-containing compounds, and that when this pyrolysis oil is thermally cracked to produce various lower olefins, the amount of carbon monoxide (CO) produced by decomposition of the oxygen-containing compounds in the cracker equipment increases significantly, and this can poison the catalyst in the downstream hydrogenation tank, and when the oxygen-containing compound is an organic acid, can cause corrosion of the equipment, and that methanol derived from the pyrolysis product of the oxygen-containing compounds is produced in the obtained lower olefin product.
  • CO carbon monoxide
  • Patent Document 1 discloses a method of subjecting waste plastic decomposition oil to hydrorefining treatment as is. Furthermore, Patent Documents 2 and 3 disclose a method for reducing catalyst coking by diluting waste plastic cracking oil with diesel and hydrorefining the diluted oil. Furthermore, Patent Document 4 discloses a method for producing high-quality jet fuel using a hydrogenation catalyst and an isomerization catalyst in a hydrorefining step. Furthermore, Non-Patent Document 1 discloses a method for removing sulfur-containing compounds, nitrogen-containing compounds, and the like from petroleum-derived naphtha by hydrorefining the petroleum-derived naphtha.
  • Patent Documents 1 to 4 were unable to sufficiently reduce the oxygen-containing compounds in the plastic decomposition oil.
  • the methods described in Patent Documents 2 and 3 were not economically viable because they required a step of diluting the waste plastic decomposition oil with diesel.
  • the method described in Non-Patent Document 1 was unable to sufficiently reduce not only the oxygen-containing compounds in petroleum-derived naphtha but also the oxygen-containing compounds in plastic cracking oil.
  • an object of the present invention is to provide a hydrocarbon composition containing decomposition products of waste plastics and having a reduced concentration of oxygen-containing compounds, a method for producing the hydrocarbon composition, and a method for determining the quality of the hydrocarbon composition.
  • Another object of the present invention is to provide a method for producing a lower olefin composition using the hydrocarbon composition, and a polyolefin polymer obtained by polymerizing the lower olefin composition.
  • the inventors discovered that when the pyrolysis oil produced by the thermal decomposition of waste plastics is purified, the content of oxygen-containing compounds can be significantly reduced by subjecting it to hydrogenation and dehydration reactions in the presence of two types of catalysts that exist independently, thereby solving the above-mentioned problems and completing the present invention.
  • a method for producing a hydrocarbon composition comprising purifying a pyrolysis oil produced by pyrolysis of a chemical recycling raw material to obtain a hydrocarbon composition, the chemically recycled raw material contains a polyolefin polymer and an oxygen-containing compound, the pyrolysis oil contains oxygenates,
  • the method for producing a hydrocarbon composition includes subjecting oxygen-containing compounds in the pyrolysis oil to a hydrogenation reaction and a dehydration reaction in the presence of a hydrogenation catalyst and a dehydration catalyst (excluding the hydrogenation catalyst) under a hydrogen atmosphere in the refining treatment.
  • [2] The method for producing the hydrocarbon composition according to [1], comprising reducing the amount of oxygen-containing compounds in the pyrolysis oil by the hydrogenation reaction and the dehydration reaction.
  • [3] The method for producing a hydrocarbon composition according to [1] or [2], which comprises converting at least a portion of the oxygen-containing compounds in the pyrolysis oil into paraffins by the hydrogenation reaction and the dehydration reaction.
  • [4] A method for producing a hydrocarbon composition according to any one of [1] to [3], comprising: subjecting the chemically recycled raw material to thermal decomposition without a catalyst to obtain a thermal decomposition product.
  • the hydrocarbon composition determination method according to [25] or [26], wherein the hydrocarbon composition is a hydrocarbon composition obtained by purifying a pyrolysis oil produced by pyrolysis of a chemical recycling feedstock.
  • the hydrocarbon composition is a mixture containing a decomposition product of a chemical recycling feedstock and another naphtha prepared in advance.
  • the hydrocarbon composition determination method according to any one of [25] to [28].
  • [X8] A hydrocarbon composition according to any one of [X1] to [X7], in which the content of ether compounds as the oxygen-containing compounds, as measured using gas chromatography, is 5 ppm by mass or less in terms of oxygen atoms.
  • hydrocarbon composition according to any one of [X1] to [X8], wherein the hydrocarbon composition is a mixture containing decomposition products of waste plastics and other naphtha that has been prepared in advance.
  • [X10] A method for producing a lower olefin composition, comprising a hydrocarbon composition cracking step of cracking a hydrocarbon composition described in any one of [X1] to [X9].
  • a method for producing a hydrocarbon composition comprising purifying a cracked oil (i.e., a pyrolysis oil, preferably a plastic cracked oil) produced by the thermal decomposition of waste plastics to obtain a hydrocarbon composition
  • the method for producing a hydrocarbon composition includes subjecting oxygen-containing compounds in the cracked oil (i.e., thermal cracking oil, preferably plastic cracking oil) to a hydrogenation reaction and a dehydration reaction in the presence of a hydrogenation catalyst and a dehydration catalyst (excluding the hydrogenation catalyst) under a hydrogen atmosphere in the refining treatment.
  • [X15] A method for producing a hydrocarbon composition according to [X13] or [X14], comprising controlling the reaction conditions for the hydrogenation reaction or the dehydration reaction in the purification process so that the content of oxygen-containing compounds in the obtained hydrocarbon composition, as measured using elemental analysis, is 900 mass ppm or less in terms of oxygen atoms.
  • [X16] A method for producing a hydrocarbon composition according to any one of [X13] to [X15], comprising controlling the reaction conditions for the hydrogenation reaction or the dehydration reaction in the purification process so that the content of oxygen-containing compounds in the obtained hydrocarbon composition, as measured using gas chromatography, is 260 ppm by mass or less (preferably 160 ppm by mass or less) in terms of oxygen atoms.
  • [X17] A method for producing a hydrocarbon composition according to any one of [X13] to [X16], wherein the mass ratio of the hydrogenation catalyst to the dehydration catalyst used in the purification process is 0.5 (preferably 10 or more) to 90 or less.
  • [X18] A method for producing a hydrocarbon composition according to any one of [X13] to [X17], wherein the total mass of the dehydration catalyst and hydrogenation catalyst used in the refining treatment is 300% by mass or more and 2000% by mass or less, relative to the oxygen atom equivalent amount of oxygen-containing compounds in the cracked oil (i.e., thermal cracked oil, preferably plastic cracked oil).
  • the cracked oil i.e., thermal cracked oil, preferably plastic cracked oil.
  • [X19] A method for producing a hydrocarbon composition according to any one of [X13] to [X18], wherein the oxygen-containing compound is at least one selected from the group consisting of alcohol compounds, ketone compounds, carboxylic acid compounds, aldehyde compounds, and ether compounds.
  • [X20] A method for producing a hydrocarbon composition according to any one of [X13] to [X19], wherein the content of alcohol compounds as oxygen-containing compounds in the obtained hydrocarbon composition, as measured using gas chromatography, is 40 mass ppm or less in terms of oxygen atoms.
  • [X22] A method for producing a hydrocarbon composition according to any one of [X13] to [X21], wherein the content of carboxylic acid compounds as oxygen-containing compounds in the obtained hydrocarbon composition, as measured using gas chromatography, is 30 mass ppm or less in terms of oxygen atoms.
  • [X23] A method for producing a hydrocarbon composition according to any one of [X13] to [X22], wherein the content of aldehyde compounds as oxygen-containing compounds in the obtained hydrocarbon composition, as measured using gas chromatography, is 15 mass ppm or less in terms of oxygen atoms.
  • [X25] A method for producing a hydrocarbon composition according to any one of [X13] to [X24], wherein the hydrogenation catalyst contains at least one metal selected from transition metals belonging to groups 8 to 10 of the periodic table.
  • a method for determining a hydrocarbon composition to be used in the production of lower olefins the hydrocarbon composition being a hydrocarbon composition containing decomposition products of waste plastics, the method comprising determining that the hydrocarbon composition is acceptable for use in the production of lower olefins when the measured content of oxygen-containing compounds in the hydrocarbon composition is equal to or less than a predetermined threshold, and subjecting the hydrocarbon composition to a thermal cracking treatment.
  • [X28] A method for determining a hydrocarbon composition according to [X27], wherein the hydrocarbon composition is a hydrocarbon composition obtained by purifying cracked oil (i.e., pyrolysis oil, preferably plastic cracked oil) produced by the thermal decomposition of waste plastic.
  • cracked oil i.e., pyrolysis oil, preferably plastic cracked oil
  • [X30] A method for determining a hydrocarbon composition according to any one of [X27] to [X29], comprising determining that the hydrocarbon composition is acceptable for use in the production of lower olefins when the content of the oxygen-containing compounds in the hydrocarbon composition, measured using elemental analysis, is 900 mass ppm or less in terms of oxygen atoms.
  • [X31] A method for determining a hydrocarbon composition according to any one of [X27] to [X30], comprising determining that the hydrocarbon composition is acceptable for use in the production of lower olefins when the content of the oxygen-containing compounds in the hydrocarbon composition, measured using gas chromatography, is 160 mass ppm or less in terms of oxygen atoms.
  • pyrolysis oils such as plastic cracking oils produced by thermal decomposition can be refined to provide hydrocarbon compositions with a reduced content of oxygen-containing compounds.
  • the hydrocarbon composition provided by the present invention has a low content of oxygen-containing compounds. This prevents a significant increase in the amount of carbon monoxide (CO) produced by the decomposition of oxygen-containing compounds in a cracker facility when the hydrocarbon composition is thermally cracked to produce various lower olefins, which can poison the catalyst in the downstream hydrogenation tank. Furthermore, if the oxygen-containing compounds contain organic acids, this can prevent corrosion of the equipment.
  • CO carbon monoxide
  • the hydrocarbon composition evaluation method of the present invention makes it possible to accurately determine whether a hydrocarbon composition containing decomposition products of waste plastics is suitable as a hydrocarbon composition for use in the production of lower olefins.
  • a person skilled in the art can appropriately optimize the pyrolysis reaction temperature in a pyrolysis reactor, the residence time in the pyrolysis reactor, the type of the pyrolysis reactor, the pressure in the pyrolysis reactor, the type of pyrolysis catalyst, and the like to perform the pyrolysis treatment.
  • the term "decomposition treatment using a supercritical fluid or subcritical fluid” refers to a thermochemical decomposition treatment of organic substances by adjusting the temperature and pressure to utilize the high reactivity of supercritical fluids or subcritical fluids close to a supercritical state, in which solvents such as methanol or water, or gases such as CO2, are in a state that is neither liquid nor gas.
  • waste plastics are melted and pyrolyzed using a known heating means such as an extruder, and the resulting melt, vapor, or both are brought into contact with a pyrolysis catalyst to lighten the waste.
  • a pyrolysis catalyst include inorganic solid acid oxide particles such as silica-alumina, silica-titania, silica-zirconia, alumina-magnesia, alumina-zirconia, alumina-titania, bentonite, kaolinite, and ceolite.
  • lower olefin refers to an unsaturated hydrocarbon having 2 to 4 carbon atoms and containing one or two unsaturated bonds per molecule.
  • Specific examples of lower olefins include ethylene, propylene, butenes (1-butene, 2-butene, isobutene), and butadienes (1,2-butadiene and 1,3-butadiene).
  • the hydrocarbons having 5 to 12 carbon atoms are mainly aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and styrene; aliphatic hydrocarbons such as normal pentane, 1-hexene, normal octane, 1-nonene, normal decane, and normal dodecane; and naphthenes such as methylcyclohexane and ethylcyclohexane.
  • the content of hydrocarbons contained in the hydrocarbon composition can be measured using a known analytical method such as gas chromatography.
  • the content of the oxygen-containing compound is 900 ppm by mass or less in terms of oxygen atoms relative to the total mass of the hydrocarbon composition, when the hydrocarbon composition is thermally cracked to produce various lower olefins, a significant increase in the amount of carbon monoxide (CO) produced by decomposition of the oxygen-containing compound in a cracker facility, which would otherwise poison the catalyst in a downstream hydrogenation tank, can be suppressed. Furthermore, if the oxygen-containing compound contains an organic acid, corrosion of the equipment can be suppressed.
  • CO carbon monoxide
  • the content of the oxygen-containing compound is 900 mass ppm or less in terms of oxygen atoms relative to the total mass of the hydrocarbon composition, the amount of methanol produced during thermal decomposition is small, and therefore a lower olefin composition having a low methanol content can be produced with a high olefin yield.
  • hydrocarbon composition of the present invention is a hydrocarbon-containing composition containing 14.0 mass % or more of hydrocarbons having 7 or more carbon atoms, relative to 100% of the total mass of the hydrocarbon composition.
  • the hydrocarbons having 7 or more carbon atoms are mainly aromatic hydrocarbons such as ethylbenzene and styrene; aliphatic hydrocarbons such as normal heptane, normal octane and normal decane; and naphthenes such as methylcyclohexane and ethylcyclohexane.
  • the upper limit of the carbon number of these hydrocarbons is usually 15 or less.
  • the composition may contain only one or two or more of these hydrocarbons having 7 or more carbon atoms.
  • the content of these hydrocarbons having 7 or more carbon atoms is 14.0% by mass or more, relative to 100% by total mass of the hydrocarbon composition.
  • the content of hydrocarbons having 7 or more carbon atoms is 14.0% by mass or more, lower olefins can be efficiently obtained when the hydrocarbon composition is thermally cracked in a naphtha cracker, and specifically, the lower olefin composition can be produced with a higher olefin yield.
  • a hydrocarbon composition having an olefinic compound content of 180 mass ppm or less, as measured using the PONA analytical method, can be obtained by the hydrocarbon composition production method of the present invention described below. In particular, this can be obtained by carrying out a hydrogenation reaction and/or a dehydration reaction in the refining process in the hydrocarbon composition production method of the present invention.
  • hydrocarbon composition of the present invention is a hydrocarbon composition obtained by the method for producing a hydrocarbon composition of the present invention described below.
  • another embodiment of the hydrocarbon composition of the present invention is a mixture obtained by mixing a decomposition product of waste plastics and at least one of other naphtha or crude oil that has been prepared in advance.
  • the mixture is subjected to distillation purification to recover a fraction corresponding to so-called naphtha, and this recovered fraction is fed into a naphtha cracker to obtain lower olefin products.
  • Non-fossil fuel refers to, for example, hydrogen or organic matter derived from plants or animals that is not derived from fossil fuels or non-edible biomass. Specific examples include methane and sugar ethanol obtained from firewood, charcoal, dried livestock manure, etc., but are not limited to these.
  • the chemically recycled raw material in the present invention is a raw material used to produce the hydrocarbon composition of the present invention, and the hydrocarbon composition of the present invention contains a decomposition product obtained by thermally decomposing the chemically recycled raw material. Furthermore, the hydrocarbon composition of the present invention can also be obtained by purifying decomposition products such as plastic decomposition oils that are produced when chemically recycled raw materials such as waste plastics are thermally decomposed using the method for producing a hydrocarbon composition of the present invention described below.
  • the chemically recycled raw material in the present invention can contain, as waste plastic, a polyolefin polymer, which will be described later.
  • the lower limit of the content of the polyolefin polymer in the chemically recycled raw material in the present invention is not particularly limited, and can usually be set to 60% by mass or more, preferably 70% by mass or more, more preferably 75% by mass or more, even more preferably 80% by mass or more, and particularly preferably 85% by mass or more, relative to 100% by total mass of the chemically recycled raw material.
  • the upper limit of the content of the polyolefin-based polymer is not particularly limited, and from the viewpoint of economic efficiency such as the production cost required to highly purify the chemically recycled raw material, it can usually be set to 99% by mass or less, preferably 98% by mass or less, more preferably 97% by mass or less, even more preferably 96% by mass or less, and particularly preferably 94% by mass or less, relative to 100% by total mass of the chemically recycled raw material.
  • the upper and lower limits can be combined arbitrarily.
  • the content of the polyolefin polymer contained in the chemically recycled raw material in the present invention is not particularly limited, and can be 60% by mass or more and 99% by mass or less, preferably 70% by mass or more and 98% by mass or less, more preferably 75% by mass or more and 97% by mass or less, still more preferably 80% by mass or more and 96% by mass or less, and particularly preferably 85% by mass or more and 94% by mass or less, relative to 100% by total mass of the chemically recycled raw material.
  • the chemically recycled raw material used in the present invention contains an oxygen-containing compound in addition to the polyolefin polymer.
  • the lower limit of the content of the oxygen-containing compound in the chemically recycled raw material is not particularly limited, and is usually 200 ppm by mass or more, preferably 500 ppm by mass or more, more preferably 1000 ppm by mass or more, even more preferably 2000 ppm by mass or more, and particularly preferably 5000 ppm by mass or more, relative to 100% by total mass of the chemically recycled raw material.
  • the upper limit of the content of the oxygen-containing compound is not particularly limited, and is usually 200,000 mass ppm or less, preferably 100,000 mass ppm or less, more preferably 50,000 mass ppm or less, even more preferably 20,000 mass ppm or less, and particularly preferably 10,000 mass ppm or less, relative to 100% of the total mass of the chemically recycled raw material.
  • the upper and lower limits can be combined arbitrarily.
  • the content ratio of the oxygen-containing compound contained in the chemically recycled raw material in the present invention is not particularly limited, and can be 200 ppm by mass or more and 200,000 ppm by mass or less, preferably 500 ppm by mass or more and 100,000 ppm by mass or less, more preferably 1,000 ppm by mass or more and 50,000 ppm by mass or less, still more preferably 2,000 ppm by mass or more and 20,000 ppm by mass or less, and particularly preferably 5,000 ppm by mass or more and 10,000 ppm by mass or less, relative to 100% by total mass of the chemically recycled raw material.
  • the oxygen-containing compound in the present invention is one of the components of the chemically recycled raw material in the present invention, particularly when the chemically recycled raw material contains waste plastics.
  • the oxygen-containing compound in the present invention is not particularly limited as long as it is a compound containing an oxygen atom in the molecule of the compound, and examples thereof include polyamide resins, polyurethane resins, polyester resins, ethylene-vinyl acetate copolymer resins (EVA), ethylene-vinyl alcohol copolymer resins (EVOH), polyvinyl alcohol copolymers (PVA), paper, wood chips, and resin additives containing oxygen atoms.
  • the pyrolysis oil of the present invention or the hydrocarbon composition of the present invention may contain an olefinic compound.
  • the olefin-based compound in the present invention is an unsaturated hydrocarbon having 5 to 12 carbon atoms and containing one or two unsaturated bonds per molecule, and specific examples thereof include cyclopentadiene, 2-methylcyclopentadiene, 2-methyl-1-pentene, 2,3-dimethyl-1-pentene, 1-hexene, 2-hexene, 2-methyl-2-hexene, cyclopentene, methylcyclopentene, ethylcyclopentene, dimethylcyclopentene, 1-heptene, 2-heptene, 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene, 2-decene, 1-undecene, 2-undecene, 1-dodecene, and 2-dodecene.
  • the hydrocarbon composition of the present invention has a content of oxygen-containing compounds of 900 mass ppm or less in terms of oxygen atoms relative to the total mass of the hydrocarbon composition, as measured by elemental analysis.
  • the oxygen-containing compound in the present invention is an oxygen-containing component contained in a pyrolysis oil obtained by pyrolyzing a chemically recycled raw material containing the oxygen-containing compound, and is derived from the oxygen-containing compound.
  • the oxygen-containing compound used in the present invention is not particularly limited, and examples thereof include oxygen-containing organic compounds having at least one oxygen atom selected from a hydroxyl group, a ketone group, a carboxyl group, an aldehyde group, and an ether group. Specific examples include at least one compound selected from the group consisting of alcohol-based compounds (described below), ketone-based compounds (described below), carboxylic acid-based compounds (described below), aldehyde-based compounds (described below), and ether-based compounds (described below).
  • the upper limit of the content of oxygen-containing compounds contained in the hydrocarbon composition of the present invention, as measured using elemental analysis, is 900 ppm by mass or less, in terms of oxygen atoms, relative to the total mass of the hydrocarbon composition, from the viewpoints of suppressing catalyst poisoning and equipment corrosion when a lower olefin composition is produced by further pyrolyzing the hydrocarbon composition obtained by pyrolyzing waste plastics and refining the resulting plastic cracked oil, and of suppressing the amount of methanol produced in the resulting lower olefin composition.
  • the lower limit of the content of oxygen-containing compounds contained in the hydrocarbon composition of the present invention as measured using elemental analysis is not particularly limited, and it is acceptable for the composition to contain substantially no oxygen-containing compounds (0 ppm by mass).
  • the content can usually be 0.1 ppm by mass or more, preferably 0.2 ppm by mass or more, more preferably 1.0 ppm by mass or more, even more preferably 5.0 ppm by mass or more, even more preferably 10.0 ppm by mass or more, even more preferably 200 ppm by mass or more, and particularly preferably 250 ppm by mass or more, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition.
  • the content of oxygen-containing compounds in the hydrocarbon composition of the present invention as measured using elemental analysis is not particularly limited, and may be substantially free of oxygen-containing compounds (0 ppm by mass), or may be 0.1 ppm by mass to 900 ppm by mass, relative to the total mass of the hydrocarbon composition.
  • 0.2 ppm by mass to 800 ppm by mass is preferred, 1.0 ppm by mass to 700 ppm by mass is more preferred, 5.0 ppm by mass to 600 ppm by mass is even more preferred, 10.0 ppm by mass to 500 ppm by mass is even more preferred, 200 ppm by mass to 400 ppm by mass is even more preferred, and 250 ppm by mass to 300 ppm by mass is particularly preferred.
  • the hydrocarbon composition of the present invention can have an oxygen-containing compound content, measured using gas chromatography, of 260 mass ppm or less in terms of oxygen atoms relative to the total mass of the hydrocarbon composition.
  • the upper limit of the content of oxygen-containing compounds contained in the hydrocarbon composition of the present invention can be set to 260 ppm by mass or less, in terms of oxygen atoms, relative to the total mass of the hydrocarbon composition, preferably 230 ppm by mass or less, more preferably 200 ppm by mass or less, even more preferably 150 ppm by mass or less, particularly preferably 120 ppm by mass or less, and even optionally 100 ppm by mass or less, 80 ppm by mass or less, 50 ppm by mass or less, or 20 ppm by mass or less, from the viewpoints of suppressing catalyst poisoning and equipment corrosion when a lower olefin composition is produced by further thermally cracking a hydrocarbon composition obtained by thermally cracking waste plastics and refining the resulting plastic cracked oil, and of suppressing the amount of methanol produced in the resulting lower olefin composition.
  • the lower limit of the content of oxygen-containing compounds contained in the hydrocarbon composition of the present invention as measured using gas chromatography is not particularly limited, and it is acceptable for the composition to contain substantially no oxygen-containing compounds (0 ppm by mass).
  • the content can usually be 0.1 ppm by mass or more, preferably 0.2 ppm by mass or more, more preferably 0.5 ppm by mass or more, even more preferably 1 ppm by mass or more, particularly preferably 2 ppm by mass or more, and may even be 5 ppm by mass or more, or 10 ppm by mass or more, calculated as oxygen atoms relative to the total mass of the hydrocarbon composition.
  • the content of oxygen-containing compounds in the hydrocarbon composition of the present invention is not particularly limited, and may be substantially free of oxygen-containing compounds (0 ppm by mass).
  • the content can be typically from 0.1 ppm by mass to 260 ppm by mass, in terms of oxygen atoms, relative to the total mass of the hydrocarbon composition. It is preferably from 0.2 ppm by mass to 230 ppm by mass, more preferably from 0.5 ppm by mass to 200 ppm by mass, even more preferably from 1 ppm by mass to 150 ppm by mass, and particularly preferably from 2 ppm by mass to 120 ppm by mass.
  • the method for controlling the content ratio of oxygen-containing compounds in a hydrocarbon composition is not particularly limited, and examples include the manufacturing method for the hydrocarbon composition of the present invention described below, known extraction methods, known purification methods, and methods combining these, as well as a method of mixing two or more hydrocarbon compositions with different oxygen-containing compound content ratios, and a method of diluting the hydrocarbon composition by blending it with diesel or the like.
  • the hydrocarbon composition of the present invention may contain an alcohol-based compound as a constituent of the oxygen-containing compound.
  • the alcohol-based compound in the present invention is not particularly limited, and is an alcohol having one or more hydroxyl groups in the molecule.
  • Specific examples include primary alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, propyl alcohol, butanol, pentanol, and hexanol; secondary alcohols having 3 to 8 carbon atoms, such as phenol, 2-butanol, 2-hexanol, and 1-phenylethanol; and tertiary alcohols having 4 to 9 carbon atoms, such as tert-butyl alcohol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 1-methylcyclohexanol, and 2-phenyl-2-propanol.
  • primary alcohols having 1 to 6 carbon atoms such as methanol, ethanol, propyl alcohol, butanol, pentanol, and hexanol
  • secondary alcohols having 3 to 8 carbon atoms such as phenol, 2-butanol, 2-hexanol, and 1-phenylethanol
  • tertiary alcohols having 4 to 9 carbon atoms such
  • the upper limit of the content of alcohol-based compounds contained in the hydrocarbon composition of the present invention is not particularly limited, but from the viewpoints of suppressing catalyst poisoning and equipment corrosion when a lower olefin composition is produced by further pyrolyzing a hydrocarbon composition obtained by pyrolyzing waste plastics and refining the resulting plastic cracked oil, and suppressing the amount of methanol produced in the resulting lower olefin composition, the content of oxygen-containing organic compounds measured using gas chromatography, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition, is preferably 160 ppm by mass or less, more preferably 80 ppm by mass or less, even more preferably 40 ppm by mass or less, even more preferably 30 ppm by mass or less, even more preferably 20 ppm by mass or less, and even more preferably 10 ppm by mass or less.
  • the lower limit of the content of alcohol-based compounds contained in the hydrocarbon composition of the present invention is not particularly limited, and it is acceptable for the composition to contain substantially no alcohol-based compounds (0 ppm by mass).
  • the content of oxygen-containing organic compounds measured using gas chromatography is typically 0.1 ppm by mass or more, preferably 0.2 ppm by mass or more, more preferably 0.4 ppm by mass or more, even more preferably 0.8 ppm by mass or more, and particularly preferably 1.6 ppm by mass or more, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition.
  • the upper limit of the content of ketone compounds contained in the hydrocarbon composition of the present invention is not particularly limited.
  • the content of oxygen-containing organic compounds measured using gas chromatography, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition is preferably 70 ppm by mass or less, more preferably 40 ppm by mass or less, even more preferably 20 ppm by mass or less, even more preferably 18 ppm by mass or less, even more preferably 15 ppm by mass or less, even more preferably 12 ppm by mass or less, and particularly preferably 10 ppm by mass or less.
  • the lower limit of the content of ketone compounds contained in the hydrocarbon composition of the present invention is not particularly limited, and it is acceptable for the composition to contain substantially no ketone compounds (0 ppm by mass).
  • the content of oxygen-containing organic compounds measured using gas chromatography is typically 0.1 ppm by mass or more, preferably 0.2 ppm by mass or more, more preferably 0.4 ppm by mass or more, even more preferably 0.8 ppm by mass or more, and particularly preferably 1.6 ppm by mass or more, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition.
  • the hydrocarbon composition of the present invention may contain a carboxylic acid compound as a constituent of the oxygen-containing compound.
  • the carboxylic acid compound in the present invention is not particularly limited, and is a carboxylic acid having one or more carboxyl groups in the molecule, such as acetic acid, propionic acid, butyric acid, isobutyric acid, enanthic acid, and benzoic acid.
  • the upper limit of the content of carboxylic acid compounds contained in the hydrocarbon composition of the present invention is not particularly limited.
  • the content of oxygen-containing organic compounds measured using gas chromatography, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition is preferably 30 ppm by mass or less, more preferably 20 ppm by mass or less, even more preferably 15 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5 ppm by mass or less, and even preferably 3.0 ppm by mass or less, 2.5 ppm by mass or less, 2.0 ppm by mass or less, 1.5 ppm by mass or less, or 1.1 ppm by mass or less.
  • the hydrocarbon composition of the present invention may contain an ether compound as a constituent of the oxygen-containing compound.
  • the ether-based compound in the present invention is not particularly limited, and specific examples include asymmetric ethers having an asymmetric structure with respect to the oxygen atom constituting the ether bond (hereinafter, may be referred to as "ether oxygen atom"), and symmetric ethers having a symmetric structure, preferably asymmetric ethers.
  • asymmetric ethers having an asymmetric structure with respect to the ether oxygen atom include 2-methoxybutane (CH 3 CH 2 CH(CH 3 )-O-CH 3 ), methoxycyclopentane (C 5 H 9 -O-CH 3 ), 1-methoxypropane (CH 3 CH 2 CH 2 -O-CH 3 ), t-amyl methyl ether (C(CH 3 ) 2 (CH 2 CH 3 )-O-CH 3 ), sec-butyl methyl ether (CH(OCH 3 )(CH 2 CH 3 )-O-CH 3 ), cyclopentyl methyl ether (C 5 H 9 -O-CH 3 ), etc.
  • symmetric ethers examples include dimethyl ether (CH 3 -O-CH 3 ), diethyl ether (CH 3 -CH 2 -O-CH 2 -CH 3 ), diisopropyl ether ((CH 3 ) 2 CH-O-CH(CH 3 ) 2 ), and dipropyl ether (CH 3 -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 3 ).
  • the asymmetric ethers are preferred from the viewpoint of being able to effectively reduce the content of methanol produced in the lower olefin composition obtained in the thermal cracking process of a hydrocarbon composition obtained from waste plastics.
  • ether compounds in which one of the two carbon atoms bonded to the oxygen atom constituting the ether bond of the ether compound is a carbon atom of a methyl group, or monoethers having only one ether oxygen atom in the molecule are preferred.
  • the lower limit of the content of ether compounds contained in the hydrocarbon composition of the present invention is not particularly limited, and it is acceptable for the composition to contain substantially no ether compounds (0 ppm by mass).
  • the content of oxygen-containing organic compounds measured using gas chromatography can typically be 0.1 ppm by mass or more, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition. 0.2 ppm by mass or more is preferred, 0.4 ppm by mass or more is more preferred, 0.5 ppm by mass or more is even more preferred, 0.6 ppm by mass or more is even more preferred, and 0.8 ppm by mass or more is even more preferred. 1.0 ppm by mass or more is even more preferred, and 2.0 ppm by mass or more is particularly preferred.
  • the upper limit of the total content of the alcohol compounds, ketone compounds, carboxylic acid compounds, aldehyde compounds, and ether compounds contained in the hydrocarbon composition of the present invention is not particularly limited.
  • the content of oxygen-containing organic compounds measured using gas chromatography, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition can be 260 ppm by mass or less, preferably 230 ppm by mass or less, more preferably 200 ppm by mass or less, even more preferably 160 ppm by mass or less, even more preferably 150 ppm by mass or less, even more preferably 120 ppm by mass or less, even more preferably 100 ppm by mass or less, or even 50 ppm by
  • the lower limit of the total content of the alcohol compounds, ketone compounds, carboxylic acid compounds, aldehyde compounds, and ether compounds contained in the hydrocarbon composition of the present invention is not particularly limited, and may be substantially absent (0 ppm by mass).
  • the content of oxygen-containing organic compounds measured using gas chromatography, calculated as oxygen atoms, relative to the total mass of the hydrocarbon composition is typically 0.1 ppm by mass or more, preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, even more preferably 0.5 ppm by mass or more, still more preferably 1.0 ppm by mass or more, even more preferably 2.0 ppm by mass or more, even more preferably 3.0 ppm by mass or more, and particularly preferably 5.0 ppm by mass or more.
  • the process for producing the hydrocarbon composition of the present invention comprises purifying a pyrolysis oil, such as a plastic cracking oil, produced by the thermal decomposition of a chemically recycled feedstock such as waste plastics, to obtain a hydrocarbon composition, wherein the chemically recycled feedstock comprises a polyolefin polymer and an oxygen-containing compound, and the purification comprises subjecting the oxygen-containing compound in the pyrolysis oil to a hydrogenation reaction and a dehydration reaction in a hydrogen atmosphere in the presence of a hydrogenation catalyst and a dehydration catalyst (excluding the hydrogenation catalyst).
  • a pyrolysis oil such as a plastic cracking oil
  • a chemically recycled feedstock such as waste plastics
  • the purification comprises subjecting the oxygen-containing compound in the pyrolysis oil to a hydrogenation reaction and a dehydration reaction in a hydrogen atmosphere in the presence of a hydrogenation catalyst and a dehydration catalyst (excluding the hydrogenation catalyst).
  • the hydrogenation reaction or the dehydration reaction is carried out in the purification treatment so that the content of oxygen-containing compounds in the obtained hydrocarbon composition, as measured by elemental analysis, is 900 ppm by mass or less in terms of oxygen atoms.
  • the hydrogenation reaction or the dehydration reaction can be carried out in the purification treatment so that the content of oxygen-containing compounds in the obtained hydrocarbon composition, measured by gas chromatography, is 260 ppm by mass or less, preferably 160 ppm by mass or less, calculated as oxygen atoms.
  • the oxygen-containing compound in the method for producing a hydrocarbon composition of the present invention has the same meaning as the oxygen-containing compound in the hydrocarbon composition of the present invention, and the preferred range is also the same.
  • the oxygen-containing compound in the method for producing a hydrocarbon composition of the present invention has the same meaning as the oxygen-containing compound in the hydrocarbon composition of the present invention, and the preferred range is also the same.
  • the oxygen-containing compound can specifically include at least one compound selected from the group consisting of alcohol-based compounds, ketone-based compounds, carboxylic acid-based compounds, aldehyde-based compounds, and ether-based compounds.
  • the alcohol-based compound, the ketone-based compound, the carboxylic acid-based compound, the aldehyde-based compound, and the ether-based compound are respectively synonymous with the alcohol-based compound, the ketone-based compound, the carboxylic acid-based compound, the aldehyde-based compound, and the ether-based compound in the hydrocarbon composition of the present invention.
  • waste plastic raw material (hereinafter referred to as "waste plastic raw material") applicable to the method for producing a hydrocarbon composition of the present invention is not particularly limited, and examples include known thermoplastic resins, known thermosetting resins, and known synthetic rubbers.
  • thermosetting resins examples include phenolic resin, melamine resin, urea resin, alkyd resin, and polyurethane (PU).
  • waste plastic raw materials may be one type alone or a mixture of two or more types.
  • the biomass feedstock applicable to the method for producing a hydrocarbon composition of the present invention is not particularly limited, and is a compound derived from known non-edible biomass and/or a compound derived from known non-fossil fuel.
  • the use of biomass raw materials can contribute to the achievement of the Sustainable Development Goals (SDGs).
  • SDGs Sustainable Development Goals
  • a single biomass-derived compound or a mixture containing a biomass-derived compound and a fossil fuel-derived compound can be used.
  • a compound derived from a fossil fuel refers to at least one compound selected from petroleum-derived compounds, coal-derived compounds, and natural gas-derived compounds.
  • the plastic cracked oil is required to have specific distillation properties, and the 95% distillation temperature is preferably 100 to 600°C, particularly preferably above 300°C, and even more preferably above 400°C, and the initial boiling point is preferably 200°C or lower, particularly preferably 100°C or lower. Furthermore, with regard to the distillate of the naphtha-equivalent fraction obtained by distilling and refining the plastic cracked oil produced by the thermal cracking of the waste plastic, the 95% distillation temperature is preferably 100 to 400°C, particularly 150 to 250°C, and the initial boiling point is preferably 200°C or lower, particularly 100°C or lower.
  • the pyrolysis oil in the present invention contains oxygen-containing compounds.
  • the lower limit of the content of oxygen-containing compounds in the pyrolysis oil is typically 1500 mass ppm or more in terms of oxygen atoms, relative to 100% of the total mass of the pyrolysis oil, and may further be 2000 mass ppm or more, 3000 mass ppm or more, 3500 mass ppm or more, or 4000 mass ppm or more.
  • the upper limit of the content of the oxygen-containing compound is usually 30,000 mass ppm or less, or even 10,000 mass ppm or less, in terms of oxygen atoms, relative to 100% by total mass of the pyrolysis oil. It may be 7000 mass ppm or less, 6000 mass ppm or less, or 5000 mass ppm or less. The upper and lower limits can be arbitrarily combined. That is, the content ratio of the oxygen-containing compound contained in the pyrolysis oil in the present invention is not particularly limited, and is, for example, 1500 mass ppm or more and 30000 mass ppm or less in terms of oxygen atoms relative to 100% of the total mass of the pyrolysis oil.
  • It may be 2000 mass ppm or more and 10000 mass ppm or less, 3000 mass ppm or more and 7000 mass ppm or less, 3500 mass ppm or more and 6000 mass ppm or less, or 4000 mass ppm or more and 5000 mass ppm or less.
  • the dehydration catalyst (excluding the hydrogenation catalyst) is a catalyst used in the dehydration reaction of thermal cracking oil such as plastic cracking oil during the refining treatment, and specifically, a catalyst used in the reaction (3) below.
  • the lower limit of the mass ratio of the hydrogenation catalyst to the dehydration catalyst used in the purification treatment is not particularly limited, and from the viewpoint of reducing olefinic compounds in the pyrolysis oil, it is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more.
  • the upper limit of the mass ratio is not particularly limited, and from the viewpoint of reducing oxygen-containing compounds in the pyrolysis oil, it is preferably 90 or less, more preferably 30 or less, even more preferably 10 or less, and particularly preferably 3.0 or less.
  • the above upper and lower limits can be combined in any desired manner.
  • the mass ratio of the hydrogenation catalyst to the dehydration catalyst is preferably 0.5 to 90, more preferably 0.6 to 30, even more preferably 0.7 to 10, and particularly preferably 0.8 to 3.0.
  • the method for producing a lower olefin composition of the present invention includes purifying a pyrolysis oil produced by thermal decomposition of a chemically recycled feedstock to obtain a hydrocarbon composition, wherein the chemically recycled feedstock contains a polyolefin polymer and an oxygen-containing compound, and the purification process includes subjecting the oxygen-containing compounds in the pyrolysis oil to a hydrogenation reaction and a dehydration reaction in a hydrogen atmosphere in the presence of a hydrogenation catalyst and a dehydration catalyst (excluding the hydrogenation catalyst) to obtain the hydrocarbon composition, and the method includes introducing the hydrocarbon composition into a naphtha cracker for thermal decomposition to obtain the lower olefin composition.
  • hydrocarbon composition of the present invention and the “hydrocarbon composition obtained by the production method of the present invention” will be collectively referred to as the "hydrocarbon composition of the present invention.”
  • a lower olefin composition containing lower olefins and methanol is produced.
  • this method for producing a lower olefin composition by using the hydrocarbon composition of the present invention as a cracker feedstock to be subjected to thermal cracking, as described above, it is possible to significantly reduce the amount of methanol produced and also to suppress catalyst poisoning in the hydrogenation tank and corrosion of the equipment.
  • the method for producing the lower olefin composition of the present invention can be carried out in accordance with a conventional method, except that the hydrocarbon composition of the present invention is used. That is, the hydrocarbon composition of the present invention (hereinafter may be simply referred to as the "hydrocarbon composition") is thermally decomposed (steam cracked) in the presence of steam at a temperature of 700 to 1000°C to obtain a lower olefin composition.
  • the hydrocarbon composition of the present invention hereinafter may be simply referred to as the "hydrocarbon composition” is thermally decomposed (steam cracked) in the presence of steam at a temperature of 700 to 1000°C to obtain a lower olefin composition.
  • the reaction temperature for thermal cracking is usually 700 to 1000°C, preferably 750 to 950°C. If the reaction temperature is below 700°C, the thermal cracking of the hydrocarbon composition will not proceed sufficiently, resulting in a lower yield of the desired lower olefins. If the reaction temperature exceeds 1000°C, the thermal cracking of the hydrocarbon composition will be excessive, resulting in increased generation of undesirable by-products such as methane, and a lower yield of the desired lower olefins.
  • the thermal cracking reaction time is preferably 0.01 to 1 second, more preferably 0.04 to 0.7 seconds. If the reaction time is less than 0.01 second, the thermal cracking of the hydrocarbon composition will not proceed sufficiently, and the yield of the desired lower olefins will tend to decrease. If the reaction time exceeds 1 second, the thermal cracking of the hydrocarbon composition will be excessive, increasing the generation of undesirable by-products such as methane and tending to decrease the yield of the desired lower olefins.
  • the reaction pressure for pyrolysis is preferably 0.01 to 1.5 MPa (gauge pressure), more preferably 0.05 to 0.5 MPa (gauge pressure), and even more preferably 0.07 to 0.2 MPa (gauge pressure).
  • the reaction products that have left the pyrolysis reaction zone can be rapidly cooled to prevent excessive decomposition.
  • the cooling temperature is not particularly limited, but when carried out on an industrial scale, it is preferably 200 to 700°C, more preferably 250 to 650°C. When carried out on a small scale, such as in a pilot or laboratory, it is preferably 0 to 100°C, more preferably 3 to 40°C.
  • the reaction product containing the lower olefin thus obtained can be subjected to treatments such as purification and fractionation according to conventional methods, thereby obtaining lower olefins such as ethylene, propylene, butene, and butadiene, aromatic hydrocarbons, and other hydrocarbons, respectively. Saturated hydrocarbons such as ethane and propane can be recovered and subjected to thermal cracking again.
  • lower olefins butene and butadiene are usually obtained as a mixture with butane. Therefore, butadiene is isolated by solvent extraction in a separate process.
  • the butene and butane mixture remaining after extraction is preferably utilized or fractionated by polymerization, rectification, or the like in a separate process.
  • the method for producing a lower olefin composition using the hydrocarbon composition of the present invention makes it possible to produce a lower olefin composition that contains lower olefins and in which methanol production is suppressed, i.e., a lower olefin composition with a low methanol content.
  • a propylene composition containing propylene and methanol can be produced. More specifically, by using the method for producing a lower olefin composition of the present invention, it is possible to produce a propylene composition which contains propylene and in which the production of methanol is suppressed, i.e., a propylene composition with a low methanol content.
  • the method for producing a lower olefin composition of the present invention is effective when producing lower olefins such as propylene.
  • the lower olefin composition of the present invention is a composition containing lower olefins and/or derivatives thereof, which are cracking products of the hydrocarbon composition of the present invention.
  • the "lower olefin” is an unsaturated hydrocarbon having 2 to 4 carbon atoms and containing one or two unsaturated bonds per molecule.
  • Specific examples include ethylene, propylene, butene (1-butene, 2-butene, isobutene), and butadiene (1,2-butadiene and 1,3-butadiene). Of these, at least one selected from the group consisting of ethylene, propylene, 1-butene, and 2-butene is preferred.
  • the "derivative thereof”, i.e., the “derivative of a lower olefin” may be a compound produced when the hydrocarbon composition of the present invention is cracked, or may be a compound obtained using a lower olefin that is a cracking product of the hydrocarbon composition of the present invention.
  • the “derivative of a lower olefin” is not particularly limited, and examples thereof include the following ethylene derivatives, propylene derivatives, and butene derivatives.
  • ethylene Ethylene oxide, ethylene glycol, ethanolamine, glycol ether, etc., obtained by the oxidation reaction of ethylene Vinyl chloride monomer, 1,1,1-trichloroethane, vinylidene chloride, polyvinyl chloride, etc., obtained by the chlorination of ethylene ⁇ -olefins obtained by the polymerization of ethylene, and higher alcohols obtained by the oxo reaction and subsequent hydrogenation reaction using the ⁇ -olefins as raw materials
  • Low-density to high-density polyethylene, etc. obtained by the polymerization of ethylene Vinyl acetate, etc., obtained by the reaction of ethylene with acetic acid Acetaldehyde, obtained by the Wacker reaction of ethylene, and its derivative, ethyl acetate, etc.
  • butadiene obtained by oxidative dehydrogenation of butene.
  • 1,4-butanediol obtained through acetoxylation, hydrogenation, and hydrolysis of butadiene, and pyrrolidones such as ⁇ -butyl lactone and N-methylpyrrolidone obtained from this as a raw material.
  • Tetrahydrofuran and polytetramethylene glycol obtained by dehydration of pyrrolidones.
  • Various synthetic rubbers obtained using butadiene.
  • the polyolefin polymer of the present invention is a polyolefin polymer obtained by polymerizing the lower olefin and/or its derivative contained in the lower olefin composition of the present invention by a known polymerization method.
  • the polyolefin polymer of the present invention contains repeating units derived from an olefin (hereinafter referred to as "lower olefin units”) or repeating units derived from a derivative thereof (hereinafter referred to as "lower olefin derivative units").
  • reproducing unit refers to a unit formed directly by the polymerization reaction of a lower olefin and/or its derivative, and may be a unit in which some of the units have been converted into a different structure by processing the polymer.
  • the polyolefin polymer of the present invention may be a polyolefin polymer obtained by polymerizing a lower olefin composition of the present invention from which methanol has been removed by a known methanol separation method such as distillation.
  • the polyolefin polymer of the present invention may be a polyolefin polymer obtained by polymerizing the lower olefin composition of the present invention as it is.
  • the methanol content in the lower olefin composition is low for the reasons described above, the performance of the catalyst used in polymerizing the lower olefin is not substantially impaired by methanol, and the obtained polyolefin polymer is excellent in quality from the viewpoints of molecular weight distribution, impurities, etc.
  • One example of the method for producing a polyolefin-based polymer of the present invention is a method for producing a polyolefin-based polymer, which includes obtaining a lower olefin composition by the above-mentioned method for producing a lower olefin composition of the present invention, and polymerizing the lower olefin contained in the lower olefin composition to obtain a polyolefin-based polymer.
  • the method for determining a hydrocarbon composition of the present invention is a method for determining a hydrocarbon composition to be used in the production of lower olefins, wherein the hydrocarbon composition is a hydrocarbon composition containing decomposition products of chemically recycled raw materials such as waste plastics, and the method comprises determining that the hydrocarbon composition is acceptable as a hydrocarbon composition to be used in the production of lower olefins when a measured value of the content of oxygen-containing compounds in the hydrocarbon composition is equal to or less than a predetermined threshold value, and subjecting the determined hydrocarbon composition to a thermal cracking treatment.
  • the "oxygen-containing compound” has the same meaning as the oxygen-containing compound in the hydrocarbon composition of the present invention, and the preferred range is also the same.
  • the "oxygen-containing compound” has the same meaning as the oxygen-containing compound in the hydrocarbon composition of the present invention, and the preferred range is also the same.
  • the "chemically recycled raw material” has the same meaning as the "chemically recycled raw material” in the above-mentioned method for producing a hydrocarbon composition of the present invention, and the preferred range is also the same.
  • composition products of waste plastics is more specifically synonymous with the “decomposition products of waste plastics” described in the section on the hydrocarbon composition production method of the present invention, and is a hydrocarbon composition obtained by purifying pyrolysis oil, such as plastic decomposition oil, produced by the thermal decomposition of waste plastics.
  • the hydrocarbon composition to be determined can be a mixture containing a decomposition product of a chemically recycled raw material such as waste plastics and another naphtha that has been prepared in advance.
  • the "other naphtha prepared in advance” in the method for determining a hydrocarbon composition of the present invention has the same meaning as the “other naphtha prepared in advance” in the hydrocarbon composition of the present invention.
  • the term “mixture” in the method for determining a hydrocarbon composition of the present invention has the same meaning as the term “mixture” in the hydrocarbon composition of the present invention.
  • the method for determining a hydrocarbon composition of the present invention is a method for determining a hydrocarbon composition, which comprises, for the reasons described above, determining that the hydrocarbon composition is acceptable as a hydrocarbon composition to be used for producing lower olefins when the content of oxygen-containing compounds in the hydrocarbon composition, measured using elemental analysis, is 900 mass ppm or less in terms of oxygen atoms relative to the total mass of the hydrocarbon composition, and subjecting the hydrocarbon composition to a thermal cracking treatment.
  • the method for determining a hydrocarbon composition of the present invention is a method for determining a hydrocarbon composition, which comprises, for the reasons described above, determining that the hydrocarbon composition is acceptable as a hydrocarbon composition to be used for producing lower olefins when the content of oxygen-containing compounds in the hydrocarbon composition, as measured by gas chromatography, is 260 ppm by mass or less (preferably 160 ppm by mass or less) in terms of oxygen atoms relative to the total mass of the hydrocarbon composition, and subjecting the hydrocarbon composition to a thermal cracking treatment.
  • the method for determining a hydrocarbon composition of the present invention comprises, for the reasons described above, determining that the hydrocarbon composition is acceptable as a hydrocarbon composition to be used for producing lower olefins when the measured content of oxygen-containing compounds in the hydrocarbon composition using elemental analysis is 900 mass ppm or less, in terms of oxygen atoms, relative to the total mass of the hydrocarbon composition, and the measured content of oxygen-containing compounds in the hydrocarbon composition using gas chromatography is 260 mass ppm or less, in terms of oxygen atoms, relative to the total mass of the hydrocarbon composition, and subjecting the hydrocarbon composition to a thermal cracking treatment.
  • the determination is preferably made immediately before the hydrocarbon composition is charged into the naphtha cracker.
  • the oxygen-containing compound can specifically include at least one compound selected from the group consisting of alcohol-based compounds, ketone-based compounds, carboxylic acid-based compounds, aldehyde-based compounds, and ether-based compounds.
  • the alcohol-based compounds, ketone-based compounds, carboxylic acid-based compounds, aldehyde-based compounds, and ether-based compounds are synonymous with the alcohol-based compounds, ketone-based compounds, carboxylic acid-based compounds, aldehyde-based compounds, and ether-based compounds in the hydrocarbon composition of the present invention, respectively.
  • ⁇ Evaluation method> Measurement of Oxygen-Containing Compound Content by Elemental Analysis
  • the hydrocarbon compositions obtained in the Experimental Examples and Comparative Experimental Examples were measured for the oxygen-containing compound content in terms of oxygen atoms by elemental analysis according to the following procedure.
  • the hydrocarbon composition was subjected to oxygen analysis using an elemental analyzer (device name: Vario EL cube, manufactured by Elemental GmbH) to calculate the oxygen atom content (unit: mass ppm). This value was used as the oxygen atom-equivalent content (unit: mass ppm) of the oxygen-containing compound contained in the hydrocarbon composition.
  • SIM60 mass spectrometer
  • a model hydrocarbon composition was prepared by blending petroleum-derived naphtha manufactured by our company as a hydrocarbon solvent with oxygen-containing compounds such as alcohol-based compounds, ketone-based compounds, aldehyde-based compounds, carboxylic acid-based compounds, and ether-based compounds listed in Table 1 so as to obtain the oxygen atom-equivalent contents listed in Table 2.
  • oxygen-containing compounds such as alcohol-based compounds, ketone-based compounds, aldehyde-based compounds, carboxylic acid-based compounds, and ether-based compounds listed in Table 1 so as to obtain the oxygen atom-equivalent contents listed in Table 2.
  • the analytical results of the content of oxygen-containing compounds in terms of oxygen atoms measured using the above-mentioned measurement method and the content of olefinic compounds measured using the PONA analysis method for the model hydrocarbon composition are shown in Table 3.
  • Table 3 The analytical results of the plastic cracked oil obtained after the purification process are shown in Table 3.
  • Example 1 a hydrogenation catalyst and a dehydration catalyst were used in combination during the purification treatment, and as a result, the content of oxygen-containing compounds and the content of olefinic compounds measured using the PONA analysis method in the hydrocarbon composition after the purification treatment were reduced compared to Reference Example 1.
  • Comparative Example 1 a dehydration catalyst was not used during the purification treatment, and only a hydrogenation catalyst was used. Therefore, in the hydrocarbon composition after the purification treatment, the content of oxygen-containing compounds and the content of olefinic compounds measured using the PONA analysis method were both reduced compared to Reference Example 1, but were higher than Example 1.
  • Example 2 The same procedure as in Example 1 was carried out, except that the amount of dehydration catalyst X added was 0.28 g and the mass ratio of hydrogenation catalyst/dehydration catalyst was 2.0. A decrease in oxygen-containing compounds was observed in the resulting hydrocarbon composition.
  • Example 4 The procedure of Example 1 was repeated except that the hydrogenation catalyst A was replaced with an equivalent amount of hydrogenation catalyst B. A decrease in the amount of oxygen-containing compounds was observed in the resulting hydrocarbon composition.
  • Example 2 The procedure of Example 1 was repeated except that the hydrogenation catalyst A was not used. The resulting hydrocarbon composition had a higher content of oxygen-containing compounds than that of Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne : une composition d'hydrocarbures ; son procédé de production ; un procédé de production d'une composition d'oléfine inférieure ; un procédé de production d'un polymère à base de polyoléfine ; et un procédé d'évaluation d'une composition d'hydrocarbures. La composition d'hydrocarbures comprend un produit de décomposition d'une charge d'alimentation recyclée chimiquement, et présente une teneur en composé contenant de l'oxygène telle que déterminée par analyse élémentaire de 900 ppm en masse ou moins en termes de quantité d'atomes d'oxygène. La charge d'alimentation recyclée chimiquement comprend un polymère à base de polyoléfine et un composé contenant de l'oxygène.
PCT/JP2025/006023 2024-02-22 2025-02-21 Composition d'hydrocarbures, son procédé de production, procédé de production de composition d'oléfine inférieure, procédé de production de polymère à base de polyoléfine et procédé d'évaluation de composition d'hydrocarbures Pending WO2025178122A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024025199 2024-02-22
JP2024-025199 2024-02-22

Publications (1)

Publication Number Publication Date
WO2025178122A1 true WO2025178122A1 (fr) 2025-08-28

Family

ID=96847290

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/006023 Pending WO2025178122A1 (fr) 2024-02-22 2025-02-21 Composition d'hydrocarbures, son procédé de production, procédé de production de composition d'oléfine inférieure, procédé de production de polymère à base de polyoléfine et procédé d'évaluation de composition d'hydrocarbures

Country Status (1)

Country Link
WO (1) WO2025178122A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023073019A1 (fr) * 2021-10-26 2023-05-04 Topsoe A/S Procédé pour la production d'un hydrocarbure à faible teneur en composés aromatiques à partir d'huile de pyrolyse
WO2023073018A1 (fr) * 2021-10-26 2023-05-04 Topsoe A/S Procédé d'hydrotraitement de composés azotés aromatiques
WO2023078983A1 (fr) * 2021-11-03 2023-05-11 Topsoe A/S Procédé pour la stabilisation d'une charge de départ liquide réactive
WO2023126567A1 (fr) * 2021-12-27 2023-07-06 Neste Oyj Charge d'hydrocarbures de gamme naphta stabilisée renouvelable, procédé de craquage thermique et produits associés
JP2023537380A (ja) * 2020-08-13 2023-08-31 トプソー・アクチエゼルスカベット 再生可能な供給物からガソリンを製造するための方法およびプラント

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023537380A (ja) * 2020-08-13 2023-08-31 トプソー・アクチエゼルスカベット 再生可能な供給物からガソリンを製造するための方法およびプラント
WO2023073019A1 (fr) * 2021-10-26 2023-05-04 Topsoe A/S Procédé pour la production d'un hydrocarbure à faible teneur en composés aromatiques à partir d'huile de pyrolyse
WO2023073018A1 (fr) * 2021-10-26 2023-05-04 Topsoe A/S Procédé d'hydrotraitement de composés azotés aromatiques
WO2023078983A1 (fr) * 2021-11-03 2023-05-11 Topsoe A/S Procédé pour la stabilisation d'une charge de départ liquide réactive
WO2023126567A1 (fr) * 2021-12-27 2023-07-06 Neste Oyj Charge d'hydrocarbures de gamme naphta stabilisée renouvelable, procédé de craquage thermique et produits associés

Similar Documents

Publication Publication Date Title
Praveen Kumar et al. Catalytic co-pyrolysis of biomass and plastics (polypropylene and polystyrene) using spent FCC catalyst
Lin et al. Catalytic fast pyrolysis of a wood-plastic composite with metal oxides as catalysts
Shylesh et al. Novel strategies for the production of fuels, lubricants, and chemicals from biomass
US20230012831A1 (en) Two-step process for converting liquefied waste plastics into steam cracker feed
Gayubo et al. Transformation of oxygenate components of biomass pyrolysis oil on a HZSM-5 zeolite. II. Aldehydes, ketones, and acids
EP3898895B1 (fr) Procédé de production de composants de qualité supérieure à partir de matière première renouvelable
KR101695057B1 (ko) 혼합 알코올을 생성하기 위한 혼합 부텐의 수산화 공정
US9080109B2 (en) Methods for deoxygenating biomass-derived pyrolysis oil
CA2853907A1 (fr) Procedes de desoxygenation d'huile de pyrolyse derivee de biomasse
EP3775104B1 (fr) Procédé de production d'un mélange d'hydrocarbures
EA028987B1 (ru) Способ превращения фенольных соединений в ароматические углеводороды
FI130443B (en) Renewable isomeric paraffin composition and use thereof
CN104870406A (zh) 由缩合的含氧化合物的加氢处理料流生成可再生生物燃料的方法
WO2025178122A1 (fr) Composition d'hydrocarbures, son procédé de production, procédé de production de composition d'oléfine inférieure, procédé de production de polymère à base de polyoléfine et procédé d'évaluation de composition d'hydrocarbures
US20250011655A1 (en) Renewable jet production from catalytic pyrolysis feedstock
FI129351B (en) Process for the production of bio - based hydrocarbons
JP7529164B2 (ja) 低級オレフィン製造用ナフサ及びその製造方法、低級オレフィン製造用ナフサの判定方法、低級オレフィン組成物及びその製造方法、並びに、ポリオレフィン系重合体
Gong et al. Biobased Paraxylene
EP3187570B1 (fr) Procédé de production d'un mélange de carburant
WO2025078359A1 (fr) Fabrication de produits chimiques dérivés d'éthylène ayant une teneur en carbone d'origine biologique à partir de bio-naphta
WO2025078353A1 (fr) Fabrication de produits chimiques dérivés d'éthylène ayant une teneur en carbone d'origine biologique à partir d'huile de pyrolyse
WO2013170280A1 (fr) Conversion d'alcools en distillats

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25758361

Country of ref document: EP

Kind code of ref document: A1