WO2007126120A1 - Procédé et dispositif servant à traiter du plastique - Google Patents

Procédé et dispositif servant à traiter du plastique Download PDF

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Publication number
WO2007126120A1
WO2007126120A1 PCT/JP2007/059403 JP2007059403W WO2007126120A1 WO 2007126120 A1 WO2007126120 A1 WO 2007126120A1 JP 2007059403 W JP2007059403 W JP 2007059403W WO 2007126120 A1 WO2007126120 A1 WO 2007126120A1
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WO
WIPO (PCT)
Prior art keywords
plastic
water
coal
heavy fraction
hydrocracking
Prior art date
Application number
PCT/JP2007/059403
Other languages
English (en)
Japanese (ja)
Inventor
Joichi Takenaka
Kunio Miyazawa
Original Assignee
Jfe Chemical Corporation
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
Priority claimed from JP2006123188A external-priority patent/JP2007291290A/ja
Priority claimed from JP2006122988A external-priority patent/JP2007291281A/ja
Priority claimed from JP2006123187A external-priority patent/JP2007291289A/ja
Priority claimed from JP2006130127A external-priority patent/JP2007302732A/ja
Priority claimed from JP2006131543A external-priority patent/JP2007302766A/ja
Application filed by Jfe Chemical Corporation filed Critical Jfe Chemical Corporation
Publication of WO2007126120A1 publication Critical patent/WO2007126120A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • 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
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a plastic processing method and apparatus.
  • the present invention relates to a method and apparatus for treating plastic waste, and relates to the recovery or effective use of useful components such as benzenes.
  • Japanese Patent Application Laid-Open No. 2 0 3-3 2 1 6 8 2 discloses a technique for obtaining benzene or a benzene derivative (hereinafter also referred to as benzene) by hydrocracking a plastic.
  • benzenes can be obtained as a reaction product of hydrocracking.
  • waste plastic contains polyvinyl chloride, etc. or salt, that is, chlorine such as seasonings containing chlorine.
  • Aromatic chlorine compounds are by-produced during the chemical decomposition reaction, and it is difficult to remove them.
  • cracked oil can be obtained as a product of this technology, but there are also problems such as an increase in the chlorine concentration in the cracked oil.
  • light fractions with a boiling point of 20 ° C or higher, which are hydrocracking reaction products tend to contain a large amount of chlorine in heavy fractions. It cannot be used as black oil.
  • the object of the present invention has been made in view of the above points, and is a method for treating plastics, in which benzenes are obtained from plastics, particularly plastics containing chlorine, and at the same time, cracked oil having a low chlorine concentration can be obtained. It is to provide such a device. Disclosure of the invention
  • This effort has a step of dissolving a plastic in a water-insoluble solvent, a step of washing the obtained plastic solution with water, and a step of hydrolyzing the plastic solution after the washing.
  • This is a plastic processing method.
  • This treatment method preferably further includes a step of fractionating the product of the hydrocracking step and a step of thermally decomposing at least a part of the heavy fraction of the fraction. At this time, it is more preferable that the thermal decomposition is performed in the hydrocracking step by returning at least a part of the heavy fraction to the hydrocracking step.
  • the thermal decomposition is at least partial coating of the heavy fraction.
  • the pyrolysis is carried out together with the coking of coal by charging at least a part of the heavy fraction into the coke oven. More preferably, at least a part of the heavy fraction is mixed with the coal. More preferably, the temperature at which at least a part of the heavy fraction is mixed with the coal is 20 to 100 ° C. Further, it is more preferable to use a mixture of at least a part of the heavy fraction and the coal shown in this paragraph.
  • the thermal decomposition is performed in a step of reforming the coal by mixing at least a part of the heavy fraction with the coal and heating.
  • the thermal decomposition is performed at 400 to 600 ° C.
  • the boiling point of the heavy fraction is preferably at least 30 ° C.
  • the plastic force is preferably a plastic containing at least polystyrene.
  • the solvent is preferably at least one selected from the group consisting of coal tar and coal tar distillation fraction.
  • the product of the hydrocracking step is preferably a benzene.
  • the present invention also includes a step of dissolving polystyrene in a water-insoluble solvent, a step of washing the obtained polystyrene solution with water, and a step of hydrocracking the plastic solution after the washing. It is also a manufacturing method of the kind.
  • the polystyrene is preferably waste polystyrene.
  • the present invention also relates to a dissolution tank equipped with a stirrer and a heating device up to 250 ° C., a separator equipped with a heating device up to 250 ° C. and a water injection device, and 500 ° C. It is also a plastic processing device equipped with a pressure reaction vessel that can withstand 120 kg / cm 2 G in C.
  • the apparatus further comprises a fractionator after the pressure reaction vessel.
  • the present invention includes a dissolving step in which a plastic and a solvent are mixed and heated to dissolve the plastic, water is added to the solution obtained in the dissolving step, and water-soluble chlorine content in the solution is removed by water.
  • the water-soluble chlorine extraction / removal step to remove the water, and the solution from which the water-soluble chlorine content has been removed by the water-soluble chlorine extraction / removal step and hydrogen are reacted in the presence of a catalyst.
  • a hydrocracking process for performing a hydrocracking reaction.
  • FIG. 1 is an explanatory diagram schematically showing the configuration of a benzene production apparatus according to the present invention.
  • FIG. 2 is an explanatory diagram schematically showing the configuration of another benzene production apparatus according to the present invention.
  • FIG. 3 is an explanatory view schematically showing the configuration of another benzene production apparatus according to the present invention.
  • FIG. 4 is an explanatory diagram schematically showing the configuration of another benzene production apparatus according to the present invention.
  • the present inventors have conducted intensive studies. As a result, when plastics are dissolved in a solvent and then washed with water, most of the chlorine, including water-soluble impurities, migrates to the water. Therefore, the plastic solution is hydrolyzed at a later stage. Also found that useful components such as benzene can be obtained while suppressing the by-production of organochlorine compounds.
  • the present invention relates to a plastic having a step of dissolving a plastic in a solvent hardly soluble in water, a step of washing the obtained plastic solution with water, and a step of hydrocracking the plastic solution after the water washing. It is a processing method.
  • a processing method As a preferred embodiment of the present invention, there is a chemical recycling of waste plastic that can significantly reduce the by-product of organochlorine compounds.
  • the plastic is dissolved in a solvent.
  • the plastic applicable to the present invention may be an unused plastic or a plastic after it has been used for some purpose.
  • plastic that has been used and discarded (hereinafter also referred to as waste plastic).
  • waste plastic including chlorine-containing plastics, such as polysalts, which are well known as city waste.
  • waste plastics including chlorine-containing plastics, such as polysalts, which are well known as city waste.
  • waste plastics including chlorine-containing plastics, such as polysalts, which are well known as city waste.
  • polyethylene, polypropylene, polystyrene, etc. or industrial waste mixed with a large amount thereof may be used.
  • the typical composition weight.
  • waste plastics is: polyethylene: 20 to 40%, polypropylene: 10 to 20%, polystyrene: 10 to 40%, polyethylene terephthalate: 5 ⁇ 10%, polyvinyl resin 'polyvinylidene chloride resin: 1 to 10%, and other impurities: 1 to 10%.
  • waste plastics containing aromatic plastics such as polystyrene are preferred.
  • There is no particular need to adjust the particle size of plastic (hereinafter the same applies to waste plastic). Are preferably crushed.
  • it may contain a thermosetting resin or paper.
  • the type of the solvent is not limited as long as it is hardly soluble in water and can dissolve or fluidize the plastic.
  • the solvent which is hardly soluble in water referred to in the present application includes a solvent insoluble in water.
  • monocyclic, bicyclic and tricyclic aromatic compounds and various derivatives thereof, or mixtures thereof are preferred.
  • each distillation fraction of coal tar can also be used to mobilize thermosetting resins and papers, so that it can be pumped to a treatment tank when mixed with water in the next process. Is preferred.
  • coal distillate fractions coal tar
  • Total fraction creosote oil fraction and anthracene oil fraction produced in a coal tar distillation plant can be used, and these may contain coal tar pitch.
  • the mixing ratio of the plastic to the solvent is preferably 5 parts by mass Z 95 5 parts by mass to 40 parts by mass / 60 parts by mass. 5 parts by mass / 9 As the processing amount increases at 5 parts by mass or more, the economy improves. Further, 40 parts by mass or less of Z 60 parts by mass is more advantageous for fluidity.
  • the conditions for melting the plastic it is preferable to melt it by heating to 150 ° C or higher. Heating to 150 ° C or higher is more economical because the plastic has a higher dissolution rate and can be dissolved in a smaller dissolution tank. However, from the point of view of operation, temperatures below about 400 ° C are sufficient. In addition, if the temperature exceeds 250 ° C., the light fraction will be volatilized significantly. In this case, it is desirable to perform the dissolution treatment in a sealed container.
  • water-soluble impurities in the solution or impurities suspended in the solution are extracted into water and then separated and removed.
  • impurities include CaC03, NaBr, KBr, and water-soluble chlorine-containing substances (hereinafter also referred to as water-soluble chlorine content).
  • the water-soluble chlorine component is one that is dissolved in water by being divided into a cation and an anion (cr).
  • Examples of such water-soluble chlorine are NaCl, KC1, H 4 C1, CaCl 2 , MgCl 2 , FeCl 2 , FeCl 3 etc. are mentioned.
  • the mixing treatment with water in this step may be either batch type or continuous type.
  • the treatment temperature is preferably from 1550 to 2550 ° C. If it is 1500 ° C or higher, the mixed state becomes better and the transfer of the chlorine content to water becomes easier. In addition, the cleaning efficiency saturates even when the temperature rises, so economically, it is appropriate that the temperature is 2500 ° C or less.
  • the amount of water added to the solution is preferably 0.1 to 10 times, particularly 1 to 4 times by weight. If it is 0.1 times or more, the operation of phase separation of the solution and water is easy. In addition, even if the amount of water is increased, the extraction amount of water-soluble chlorine is saturated, so it may be about 10 times economically.
  • the solution from which water-soluble impurities have been removed by the water washing step is reacted with hydrogen to decompose the plastic (hereinafter also referred to as a hydrogenolysis reaction).
  • the solvent may be decomposed at the same time.
  • the hydrocracking reaction is preferably performed in the presence of a catalyst.
  • the catalyst used for the hydrocracking reaction when the chlorine content is greatly reduced in the water washing treatment, and the solution contains little chlorine, Co—Mo, Ni—M o, Ni—W-based catalysts, or iron catalysts (iron oxide, iron sulfide, iron sulfate and calcined products thereof). If necessary, these catalysts can be supported on a support such as alumina (A 1 2 0 3 ) or silica (S i 0 2 ). .
  • the noble metal component of the catalyst when the solution contains a large amount of chlorine, the noble metal component of the catalyst is deteriorated by forming a chloride, so use an iron catalyst that maintains the catalytic performance even when it becomes a chloride. It is preferable. In particular, converter dust generated by converter blowing in steelmaking, that is, iron oxide particles, is preferred.
  • the catalyst When the catalyst is used as a granular material, it may have a particle size of about 0.01 to 10 mm, which is usually used. This catalyst may be used in any reaction system such as a fluidized bed, a fixed bed, or a single slurry bed.
  • Any catalyst is preferably added in an amount of 1 to 10% by mass, particularly 3 to 5% by mass, based on the solution. If it is 1% by mass or more, the hydrocracking reaction rate is high. On the other hand, if it is too much, the effect is saturated, so it may be 10% by mass or less.
  • the catalyst may be added before the dissolving step or after the water washing step. In particular, when the plastic contains a large amount of chlorine, it is better to add it from the melting step.
  • the hydrocracking reaction may be carried out in either the liquid phase or the gas phase, the reaction temperature is about 30.0 to 500 ° C, preferably about 400 to 450 ° C, and the pressure is 1.0 to 20. It is about 3MPa (10 to 200 atmospheres), preferably 5.1 to 10. IMP a (50 to 100 atmospheres).
  • a cracked oil is mentioned.
  • the treatment method of the present invention preferably further includes a step of fractionating the product of the hydrocracking step and a step of thermally decomposing at least a part of the heavy fraction of the fractionation.
  • the product obtained in the hydrocracking step is fractionated to obtain useful components such as benzenes and cracked oil.
  • the product of the hydrocracking step may include the solvent used and its cracked product. More specifically, hydrogenated tar fractions (light fractions) corresponding to lighter gas fractions mainly composed of C3 to C4, benzene fractions, creosote oil and anthracene oil, etc. , And heavy fractions.
  • a preferable thermal decomposition temperature is 400 to 600 ° C. Note that this pyrolysis temperature is the temperature when passing through the region of 400 to 600 ° C, such as when charging directly into a coke oven or mixed with coal. It does not matter if the temperature is further increased after pyrolysis.
  • the heavy fraction preferably has a boiling point of 330 ° C or higher.
  • a heavy fraction having a boiling point of 330 ° C. or higher with a very low chlorine content can be obtained.
  • it is an organochlorine compound contained in a heavy fraction with a boiling point of 330 ° C or higher.
  • it is necessary to increase the distillation temperature. When the distillation temperature is increased, polycondensation due to heat occurs, and the aromatic chlorine compound becomes heavier, that is, has a higher boiling point. Therefore, it cannot be distilled and is difficult to separate and recover by distillation.
  • the various pyrolysis methods are described below.
  • At least a part of the heavy fraction is returned to the hydrocracking step and pyrolyzed in the hydrocracking step.
  • At least a part of the heavy fraction can be returned to the dissolution tank and indirectly returned to the hydrocracking step.
  • at least a part of the heavy fraction can be used as a part of the solvent.
  • inorganic substances solid content
  • At least a portion of the heavy fraction can be charged together and pyrolyzed to obtain coke, and at the same time, benzenes such as BTX (benzene, toluene, xylene) can be produced. .
  • BTX benzene, toluene, xylene
  • the method for charging the heavy fraction into the coke oven is not particularly limited. That is, the heavy fraction may be charged directly into a coke oven, or mixed with coal to be converted into cotas and charged together with the coal.
  • the forming is possible, for example, by a method of producing bean charcoal.
  • the particle size of the coal is about 3 mm or less, the contact efficiency between the inorganic matter and the heavy fraction in the coal is improved, and the rate of formation of chloride is increased.
  • the mixing temperature and molding temperature of the heavy fraction and coal are not particularly limited, but 20 to 100 ° C is preferable, more preferably 20 to 100 ° C in terms of improving the fluidity of the heavy fraction. 80 ° C. When the temperature is 100 ° C. or lower, volatilization of the component is easily suppressed, and thus a good working environment is easily maintained.
  • salt fli hydrogen (HC 1) generated by pyrolysis of heavy fractions during high temperature dry distillation in a coke oven is trapped by minerals in the coal and becomes, for example, stable chlorides.
  • most of the chlorine contained in JushitsuTome component reacts with inorganic matter in the coal to form a NaC l, KC and C a C 1 2, stable chlorides such as Mg C 1 2. For this reason, it is difficult to generate harmful substances that corrode equipment such as hydrogen chloride (HC 1) even in high temperature carbonization in a coke oven.
  • At least a part of the heavy fraction is mixed with coal and heated to thermally decompose while reforming the coal.
  • the degree of coalification (R.) of the inferior coal is R Q ⁇ 0.668.
  • the degree of coalification (R.) of the non-slightly caking coal is 0.68 to 0.80.
  • the degree of coalification is the ratio of reflected light when the coal is irradiated with light, and is measured according to JISM 8816.
  • the heat treatment is performed by mixing with the inferior coal that does not become the raw material for Kotas, or the non-slightly caking coal that does not become the raw material for Kotas alone.
  • the heat treatment is preferably performed at 300 to 500 ° C, particularly 350 to 450 ° C.
  • the atmosphere is preferably a nitrogen atmosphere or a reducing atmosphere, and the reaction pressure is preferably 0.1 to 15.2 MPa (1 to 150 atmospheres).
  • the present application is a disintegration tank equipped with a stirrer and a heating device up to 250 ° C., a separator equipped with a heating device up to 25 ° C. and a water injection device, and 500 ° C.
  • An invention of a plastic processing apparatus provided with a pressure reaction vessel capable of withstanding 120 kg / cm 2 G is also provided.
  • the plastic processing apparatus preferably has a fractionator after the pressure reaction vessel.
  • FIG. 1 is a schematic view showing an embodiment of a plastic processing apparatus and a benzene production apparatus according to the present invention.
  • the apparatus configuration according to the present invention is not limited to the case shown in FIG. Hereinafter, it demonstrates according to this schematic.
  • Plastic (hereinafter the same applies to waste plastic) 1 1, coal tar (solvent) 1 2 and catalyst 1 3 are mixed in dissolution tank 1 and dissolved.
  • the operating temperature of the dissolution tank 1 is preferably 1550 to 400 ° C for the reasons described above.
  • the obtained lysate (solution) is sent to the extractor 2 by a pump (not shown) or the like.
  • the plastic coal tar solution layer is supplied to a pressure reaction vessel (hydrocracking reactor) 3.
  • a pressure reaction vessel hydrocracking reactor
  • a plurality of the batch type extractors 2 may be provided.
  • multiple partitions can be attached to one extractor to provide the functions of a mixing area and a stationary area, and the movement of the plastic coal layer solution and water layer overflows between the mixing area and the stationary area. You may make it by such as. '
  • the hydrocracking reaction in the pressure reaction vessel 3 may be carried out in either the liquid phase or the gas phase, and the reaction temperature is about 300 to 500 ° C, preferably 4 0 to 4 to 50 ° C., pressure is about 1.0 to 2 0.3 MPa (10 to 2 200 atmospheres), preferably 9403
  • the pressure reaction vessel 3 is supplied with hydrogen 15 or a gas mainly composed of hydrogen.
  • hydrogen 15 or a gas mainly composed of hydrogen.
  • most of the gas discharged from the pressure reaction vessel 3 is circulated so that the hydrogen concentration is maintained at a predetermined concentration.
  • a part of the exhausted gas is discarded as exhaust gas 21 and hydrogen 15 is made up.
  • it instead of circulating the exhausted gas, it can be used as a heating source for this plant, discarding the entire exhausted gas while supplying the entire amount of hydrogen, or using it for other purposes.
  • thermosetting resins represented by phenol resins and polyethylene terephthalate are heavy fractions (including pitch fractions).
  • coal tar used as a solvent is partly decomposed and lightened by the hydrocracking reaction in the gas, but a part of the coal tar may generate a pitch fraction by the polycondensation reaction.
  • the liquid product discharged from the pressure reaction vessel 3 is sent to a distillation column (fractional distillation column) 6 where a gas fraction mainly composed of C3 to C4 2 2, a benzene fraction 2 3, and creosote It is fractionated into hydrogenated tar fractions (light fractions) 2 4 and heavy fractions 25 corresponding to lighter oils and anthracene oils.
  • a distillation column fractional distillation column 6 where a gas fraction mainly composed of C3 to C4 2 2, a benzene fraction 2 3, and creosote It is fractionated into hydrogenated tar fractions (light fractions) 2 4 and heavy fractions 25 corresponding to lighter oils and anthracene oils.
  • a single distillation column (fractional distillation column) 6 is illustrated, but an atmospheric distillation column and a vacuum distillation column may be provided to subdivide the fractionation.
  • hydrogenated tar fraction (light The mass fraction) 2 4 may be a product, but a part or all of it may be recycled to the dissolution tank 1 and used as the solvent 12.
  • FIG. 2 is a schematic view showing an embodiment of another plastic processing apparatus and a manufacturing apparatus for benzenes according to the present invention.
  • 1 differs from the embodiment shown in FIG. 1 in that a solid-liquid separator, here a centrifugal separator 5 is installed between the pressure reaction vessel 3 and the distillation column (separator) 6, and inorganic substances in the plastic, catalyst, etc. The solid content is separated and removed as residue 29.
  • a high-quality pitch (hydrogenated pitch) containing no solid content can be obtained by further distilling the lighter portion of the bottom of the distillation column 6 with a vacuum distillation column.
  • FIG. 3 is a schematic view showing an embodiment of another plastic processing apparatus according to the present invention.
  • the difference from the embodiment shown in Fig. 1 is that heavy fraction 25 obtained in the fractionation process is mixed with coal 16 (recessive coal) with coal mixer 8 and heated to heat the heavy fraction. It is a device that obtains modified coal 31 at the same time as pyrolysis.
  • coal 16 reactive coal
  • FIG. 4 is a schematic view showing an embodiment of another plastic processing apparatus according to the present invention. The difference from the embodiment shown in FIG. 1 is that heavy fraction 25 obtained in the fractionation process is mixed with coal 16 (recessive coal) with coal mixer 8 and heated to heat the heavy fraction. It is a device that obtains modified coal 31 at the same time as pyrolysis.
  • a stable chloride is formed even in the presence of a small amount of chlorine in the coal mixing process. It is preferable because it is easy.
  • FIG. 4 is a schematic view showing an embodiment of another plastic processing apparatus according to the present invention. The difference from the embodiment shown in FIG
  • This modified coal may be used as it is as a part of the blended coal for the production of coatas, or may be used as a part of the blended coal after removing the oil by a centrifuge or distillation.
  • a liquid-liquid extractor can be provided after the hydrocracking reactor.
  • the amount of chlorine contained is further reduced, which is more preferable because stable chlorides are more easily formed in the coal mixing step.
  • the mixed plastic and anthracene oil dissolved product were sent to a hermetic extractor 2 , and chlorine content 27 such as HC1, FeCl 2 and FeCl 3 was transferred to hot water at 250 ° C.
  • Two extractors were installed and operated alternately.
  • the dechlorinated plastic and anthracene oil melt were supplied to a pressure reactor (hydrogenolysis reactor) 3.
  • the hydrocracking reaction was performed at a temperature of 450 ° C, a reaction pressure of 10. IMP a (100 atm), and a residence time of lhr. At this time, hydrogen gas 15 was supplied at 2.5 Nm 3 Zhr.
  • the hydrocracked oil obtained was removed from residue 29 with a centrifuge 5 and then sent to a distillation column (fractionation column) 6 where a gas fraction 22 composed mainly of C3 to C4 with a boiling point up to 200 ° C. It was fractionated into a fraction 23 mainly composed of benzene, a hydrogenated tar fraction 24, and a hydrogenated pitch fraction (heavy fraction) 25.
  • the hydrogenated tar fraction 24 was divided into a fraction having a boiling point of 200 to 300 ° C, a fraction having a boiling point of 300 to 400 ° C, and a fraction having a boiling point of 400 ° C or higher (distillation apparatus not shown).
  • a solution of plastic and anthracene oil having the same composition as in Invention Example 1 is not passed through an extractor, that is, not dechlorinated by washing with water. Got the minute.
  • the same analysis as in Invention Example 1 was performed, and the results of the analysis are also shown in Table 1.
  • converter dust was added at a rate of 1.5 kg / hr.
  • the residence time in the dissolution tank was 0.5 hr.
  • the mixed plastic and anthracene oil dissolved product were sent to a hermetic type extractor 2 to transfer chlorine content 27 such as HC1, FeCl 2 , and FeCl 3 to 250 ° C hot water.
  • the dechlorinated plastic and anthracene oil melt was supplied to a pressure reactor (hydrocracking reactor) 3.
  • the hydrogenolysis reaction was performed at a temperature of 450 ° C, a reaction pressure of 10. IMP a (100 atm), and a residence time of 1 hr. At this time, hydrogen gas 15 was supplied at 2.5 NmVhr.
  • the obtained hydrocracked oil is sent to a distillation column (fractional distillation column) 6 where a gas fraction 22 mainly composed of C3 to C4 and a fraction containing benzenes having a boiling point of up to 200 ° C (benzene fractions). 23), a light fraction 23 with a boiling point of 200-330 ° C, and a heavy fraction 25 with a boiling point of 330 ° C or higher.
  • coal whit punk charcoal (weakly caking coal) produced in South Africa and mixed with 200 JIS mesh
  • coal whit punk charcoal (weakly caking coal) produced in South Africa and mixed with 200 JIS mesh
  • the heavy fraction was set at 80 ° C to improve transportability, but the molding temperature was room temperature (20-30 ° C), and an amount of 10wt% was added to the coal.
  • Coke was obtained by conducting a can-cooking test of the coal blended with 10 wt% of the obtained coal.
  • 10 wt% of modified coal Invention Example 2 or Witbank coal (Comparative Example 2) was blended with caking coal base blend coal, Two types of blended charcoal were produced.
  • the base coal blends are listed in Table 2, with a degree of coalification (Ro), a maximum Giuser's fluidity (MF), a total inert (TI), and an ash, and a mixture.
  • the can firing test is a firing test using a rectangular parallelepiped steel can (20 liters in volume) having approximately the same length as the 45 cm width of the actual coke oven. It is.
  • the mixed plastic and anthracene oil dissolved product were sent to a hermetic type extractor 2 to transfer chlorine content 27 such as HC1, FeCl 2 , and FeCl 3 to 250 ° C hot water.
  • Two extractors were installed and operated alternately.
  • the dechlorinated plastic and anthracene oil melt was supplied to a pressure reactor (hydrocracking reactor) 3.
  • the hydrogenolysis reaction was performed at a temperature of 450 ° C, a reaction pressure of 10. IMP a (100 atm), and a residence time of 1 hr. At this time, hydrogen gas 15 was supplied at 2.5 Nm 3 / hr.
  • the obtained hydrocracked oil is sent to a distillation column (fractional distillation column) 6 and mainly composed of C3 to C4.
  • the base blended coal consists of four brands of coal (Co) for Cotas (Corts for Cotas), as shown in Table 2 (Coal Degree (Ro), Gisser Maximum Fluidity (MF), Total Inert (TI), Ash, and Mixing (Mixture Ratio)). ) was prepared. And the can firing test was done about each combination charcoal. That is, after 7 hours of dry distillation in a coke oven (not shown) with a furnace temperature of 1100 ° C, water was discharged from the furnace and sprinkled. The packing density of the coal blend was 0. 8TZm 3. After preparing the coatus in this way, the drum strength (DI 3 ° 15 ) of coatus was measured according to JIS. The measurement results are shown in Table 4, and it is clear that the drum strength has improved and the poor coal has been modified. It can also be seen that the heavy fraction is a useful substance.
  • benzene when plastic, particularly waste plastic, is used as a raw material, benzene has a very low chlorine concentration, and useful substances such as cracked oil can be produced. Therefore, it can contribute widely to industry as an excellent waste plastic treatment method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

L'invention concerne un procédé servant à traiter un plastique et consistant à dissoudre un plastique dans un solvant peu soluble dans l'eau, à rincer la solution de plastique obtenue à l'eau et à effectuer l'hydrocraquage de la solution de plastique après rinçage à l'eau. Ce procédé permet d'obtenir des constituants utiles, tels que des benzènes et un distillé pétrolier à faible concentration en chlore, à partir de déchets de plastique.
PCT/JP2007/059403 2006-04-27 2007-04-25 Procédé et dispositif servant à traiter du plastique WO2007126120A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP2006123188A JP2007291290A (ja) 2006-04-27 2006-04-27 プラスチックの処理方法
JP2006-123188 2006-04-27
JP2006122988A JP2007291281A (ja) 2006-04-27 2006-04-27 プラスチックの処理方法
JP2006-122988 2006-04-27
JP2006123187A JP2007291289A (ja) 2006-04-27 2006-04-27 プラスチックの処理方法およびその処理装置ならびにベンゼン類の製造方法およびその製造装置
JP2006-123187 2006-04-27
JP2006130127A JP2007302732A (ja) 2006-05-09 2006-05-09 プラスチックの処理方法およびベンゼン類の製造方法
JP2006-130127 2006-05-09
JP2006-131543 2006-05-10
JP2006131543A JP2007302766A (ja) 2006-05-10 2006-05-10 プラスチックの処理方法および処理装置

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WO2007126120A1 true WO2007126120A1 (fr) 2007-11-08

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009110549A1 (fr) * 2008-03-07 2009-09-11 三井・デュポンフロロケミカル株式会社 Procédé et système de nettoyage de composant électronique
WO2009110548A1 (fr) * 2008-03-07 2009-09-11 三井・デュポンフロロケミカル株式会社 Procédé et système de nettoyage de composant électronique
CN113047839A (zh) * 2021-03-29 2021-06-29 中国矿业大学 巨厚倾斜煤层露天矿排土场规划与端帮资源高效回收方法
WO2022010714A1 (fr) * 2020-07-07 2022-01-13 Saudi Arabian Oil Company Composition de mélange de mazout lourd contenant des déchets de polystyrène dissous
US11499110B2 (en) 2020-09-11 2022-11-15 Uchicago Argonne, Llc Catalytic upcycling of polyolefins into lubricants
US11596935B2 (en) 2019-01-24 2023-03-07 Uchicago Argonne, Llc Catalytic polymer processing
US11780985B2 (en) 2019-08-27 2023-10-10 Uchicago Argonne, Llc Catalytic upcycling of polymers
WO2024030748A1 (fr) * 2022-08-03 2024-02-08 Eastman Chemical Company Procédé de conversion de déchets plastiques fondus ou dissous dans un craqueur catalytique fluidisé et/ou dans une unité d'hydrocraquage

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JPH07216361A (ja) * 1994-01-27 1995-08-15 Kansai Coke & Chem Co Ltd コークスの製造方法
JPH09500412A (ja) * 1993-07-20 1997-01-14 ビーエーエスエフ アクチエンゲゼルシャフト プラスチックをスチームクラッカー中で再利用する方法
JPH09279156A (ja) * 1996-04-11 1997-10-28 Sumikin Manag Kk 廃プラスチックス処理装置と方法
JPH1161148A (ja) * 1997-08-21 1999-03-05 Jgc Corp 廃プラスチックの処理方法
JP2003253038A (ja) * 2002-03-05 2003-09-10 Mitsubishi Materials Corp 樹脂含有廃棄物の熱分解物から塩素を除去する方法と装置
JP2003321682A (ja) * 2002-02-28 2003-11-14 Jfe Steel Kk 廃プラスチックの処理方法

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JPH09500412A (ja) * 1993-07-20 1997-01-14 ビーエーエスエフ アクチエンゲゼルシャフト プラスチックをスチームクラッカー中で再利用する方法
JPH07216361A (ja) * 1994-01-27 1995-08-15 Kansai Coke & Chem Co Ltd コークスの製造方法
JPH09279156A (ja) * 1996-04-11 1997-10-28 Sumikin Manag Kk 廃プラスチックス処理装置と方法
JPH1161148A (ja) * 1997-08-21 1999-03-05 Jgc Corp 廃プラスチックの処理方法
JP2003321682A (ja) * 2002-02-28 2003-11-14 Jfe Steel Kk 廃プラスチックの処理方法
JP2003253038A (ja) * 2002-03-05 2003-09-10 Mitsubishi Materials Corp 樹脂含有廃棄物の熱分解物から塩素を除去する方法と装置

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009110549A1 (fr) * 2008-03-07 2009-09-11 三井・デュポンフロロケミカル株式会社 Procédé et système de nettoyage de composant électronique
WO2009110548A1 (fr) * 2008-03-07 2009-09-11 三井・デュポンフロロケミカル株式会社 Procédé et système de nettoyage de composant électronique
JPWO2009110548A1 (ja) * 2008-03-07 2011-07-14 三井・デュポンフロロケミカル株式会社 電子部品の洗浄方法および洗浄システム
US11596935B2 (en) 2019-01-24 2023-03-07 Uchicago Argonne, Llc Catalytic polymer processing
US11780985B2 (en) 2019-08-27 2023-10-10 Uchicago Argonne, Llc Catalytic upcycling of polymers
WO2022010714A1 (fr) * 2020-07-07 2022-01-13 Saudi Arabian Oil Company Composition de mélange de mazout lourd contenant des déchets de polystyrène dissous
US11499110B2 (en) 2020-09-11 2022-11-15 Uchicago Argonne, Llc Catalytic upcycling of polyolefins into lubricants
CN113047839A (zh) * 2021-03-29 2021-06-29 中国矿业大学 巨厚倾斜煤层露天矿排土场规划与端帮资源高效回收方法
WO2024030748A1 (fr) * 2022-08-03 2024-02-08 Eastman Chemical Company Procédé de conversion de déchets plastiques fondus ou dissous dans un craqueur catalytique fluidisé et/ou dans une unité d'hydrocraquage

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