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WO2018061404A1 - Procédé de traitement de déchets contenant du carbone - Google Patents

Procédé de traitement de déchets contenant du carbone Download PDF

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Publication number
WO2018061404A1
WO2018061404A1 PCT/JP2017/025384 JP2017025384W WO2018061404A1 WO 2018061404 A1 WO2018061404 A1 WO 2018061404A1 JP 2017025384 W JP2017025384 W JP 2017025384W WO 2018061404 A1 WO2018061404 A1 WO 2018061404A1
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WO
WIPO (PCT)
Prior art keywords
carbon
waste
containing waste
ozone
surfactant
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.)
Ceased
Application number
PCT/JP2017/025384
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English (en)
Japanese (ja)
Inventor
雄哉 佐野
香奈 宮武
淳一 寺崎
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.)
Taiheiyo Cement Corp
Original Assignee
Taiheiyo Cement 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
Priority claimed from JP2017029529A external-priority patent/JP6858589B2/ja
Priority claimed from JP2017029722A external-priority patent/JP6762890B2/ja
Application filed by Taiheiyo Cement Corp filed Critical Taiheiyo Cement Corp
Priority to CN201780059424.7A priority Critical patent/CN109790979B/zh
Publication of WO2018061404A1 publication Critical patent/WO2018061404A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/38—Stirring or kneading
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • 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
    • Y02W30/20—Waste processing or separation
    • 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
    • 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
    • Y02W30/78—Recycling of wood or furniture waste
    • 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
    • Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]

Definitions

  • the present invention relates to a method for incinerating and treating carbon-containing waste, particularly waste plastic containing carbon fiber.
  • CFRP Carbon Fiber Reinforced Plastics
  • waste plastic including carbon fiber, BOF (Biomass oil fuel), ASR (Automobile shredder residue), RPF (Refuse derived paper and plastics densified fuel), RDF (Refuse derived fuel) ), Wood waste, waste tires, rubber waste, water-absorbing polymer waste, municipal waste, thermosetting and thermoplastic resin waste, FRP (Fiber reinforced plastics), carbon fiber waste, optical fiber waste,
  • BOF Biomass oil fuel
  • ASR Automatic mobile shredder residue
  • RPF Refuse derived paper and plastics densified fuel
  • RDF Refuse derived fuel
  • Wood waste waste tires, rubber waste, water-absorbing polymer waste, municipal waste, thermosetting and thermoplastic resin waste
  • FRP Fiber reinforced plastics
  • carbon fiber waste optical fiber waste
  • the amount of waste containing carbon compounds such as solar cell waste is also increasing.
  • the carbon-containing waste is pulverized so that the average particle diameter is 3 mm or less, and then the pulverized carbon-containing waste is treated with a cement kiln.
  • a treatment method that can omit the treatment of removing the carbon compound in advance.
  • Patent Document 1 it is necessary to finely pulverize a high-strength carbon-containing waste until it becomes extremely small particles having an average particle diameter of 3 mm or less, and much labor is required for the pulverization. There was a problem of becoming.
  • This invention is made
  • a method for treating a carbon-containing waste according to the present invention is a method for treating a carbon-containing waste in which carbon-containing waste is incinerated, and the carbon-containing waste and the following (1) or After contacting the processing accelerator containing the following (2), the carbon-containing waste is incinerated.
  • (1) Surfactant and hydrogen peroxide (2) Ozone
  • the surfactant improves the wettability of the carbon-containing waste. So hydrogen peroxide is in full contact with the carbon-containing waste.
  • the oxygen contained in the hydrogen peroxide and the carbon compound contained in the carbon-containing waste react efficiently, so that the combustibility of the carbon-containing waste is sufficiently enhanced.
  • the effect of improving the flammability of the carbon compound by hydrogen peroxide in the present invention is that the hydrogen peroxide supplied to the incineration process (for example, incineration equipment such as cement kiln) dissociates in a relatively low temperature range and becomes active oxygen. It is presumed that this is an effect caused by releasing radicals and the active oxygen radicals promoting the combustion reaction of the carbon compound.
  • ozone oxidation when ozone comes into contact with the surface of carbon-containing waste or the inner surface of internal voids (voids) of the carbon-containing waste.
  • a phenomenon in which carbon-carbon double bonds are oxidatively cleaved or a crack in the organic polymer called ozone cracking occurs, or the same or similar phenomenon occurs in carbon-containing waste, and combustion of the carbon-containing waste It is estimated that the sex will improve. Thereby, at the time of incineration, since the combustibility of the carbon compound contained in the carbon-containing waste is improved, the combustibility of the carbon-containing waste is sufficiently enhanced.
  • the method for treating carbon-containing waste of the present invention it is not necessary to remove the carbon compound in advance, and the average particle size of the carbon-containing waste is not reduced to an extremely small size such as 3 mm or less. Therefore, the carbon compound contained in the carbon-containing waste can be sufficiently burned with little effort.
  • the treatment accelerator when a surfactant and hydrogen peroxide are used as the treatment accelerator, the treatment accelerator includes (1) the surfactant and hydrogen peroxide, It is preferable to reduce the diameter by bringing a surfactant into contact with the carbon-containing waste, and further bringing it into contact with hydrogen peroxide, and then incinerating the carbon-containing waste.
  • the combustibility improving effect is further enhanced.
  • the surfactant since the surfactant is brought into contact with the carbon-containing waste to reduce the diameter, the surfactant suppresses dust generation when reducing the diameter of the carbon-containing waste or after reducing the diameter of the carbon-containing waste. be able to.
  • the treatment accelerator when a surfactant and hydrogen peroxide are used as the treatment accelerator, the treatment accelerator includes (1) the surfactant and hydrogen peroxide,
  • the amount of the hydrogen peroxide is preferably 15 parts by mass or more and 100 parts by mass or less when the amount of the carbon-containing waste is 100 parts by mass.
  • the upper limit of the amount of hydrogen peroxide is not restricted from the viewpoint of improving the combustibility of the carbon-containing waste.
  • the amount of carbon-containing waste is 100 parts by mass, if the amount of hydrogen peroxide exceeds 100 parts by mass, the cost increases, which is not preferable.
  • the treatment accelerator when a surfactant and hydrogen peroxide are used as the treatment accelerator, the treatment accelerator includes (1) the surfactant and hydrogen peroxide,
  • the amount of the surfactant is preferably 0.01 parts by mass or more and 25 parts by mass or less when the amount of the hydrogen peroxide is 100 parts by mass.
  • the upper limit of the amount of the surfactant is not restricted from the viewpoint of improving the combustibility of the carbon-containing waste.
  • the amount of hydrogen peroxide is 100 parts by mass, if the amount of the surfactant exceeds 25 parts by mass, the cost increases, which is not preferable.
  • the treatment accelerator when ozone is used as the treatment accelerator, the treatment accelerator contains the (2) ozone, and the ozone has an ozone concentration of 100 ppm or more, and It is preferable to contact with the carbon-containing waste in the form of a gas that is 6000 ppm or less. If the ozone concentration in the form of gas is less than 100 ppm, the combustibility improvement effect of the carbon-containing waste may not be sufficiently obtained. On the other hand, the upper limit of the ozone concentration is not restricted from the viewpoint of improving the combustibility of the carbon-containing waste. However, from the viewpoint of the cost for generating ozone, when the ozone concentration in the form of gas exceeds 6000 ppm, the cost increases, which is not preferable.
  • the treatment accelerator when ozone is used as the treatment accelerator, contains (2) ozone, and the ozone has an ozone concentration of 1 ppm or more, and It is preferable to contact with the carbon-containing waste in the form of a liquid that is 50 ppm or less. If the ozone concentration in the liquid form is less than 1 ppm, the combustibility improvement effect of the carbon-containing waste may not be sufficiently obtained. On the other hand, the upper limit of the ozone concentration is not restricted from the viewpoint of improving the combustibility of the carbon-containing waste, as in the case of the gas form described above. However, from the viewpoint of the cost for ozone generation and the like, when the ozone concentration in the liquid form exceeds 50 ppm, the cost increases, which is not preferable.
  • the treatment accelerator when ozone is used as the treatment accelerator, the treatment accelerator contains (2) ozone, and a surfactant is further added to the carbon-containing waste. It is preferable to make it contact. According to this, since the wettability of the carbon-containing waste is improved by the surfactant, ozone is in sufficient contact with the carbon-containing waste, particularly when the form is liquid, for example. As a result, a better combustibility improving effect can be obtained.
  • the treatment accelerator when ozone is used as the treatment accelerator, the treatment accelerator contains (2) ozone, and a surfactant is brought into contact with the carbon-containing waste. It is preferable to incinerate the carbon-containing waste after reducing the diameter and further contacting ozone with it. According to this, since the carbon-containing waste is reduced in size and brought into contact with ozone, the combustibility improving effect is further enhanced. In addition, since the surfactant is brought into contact with the carbon-containing waste to reduce the diameter, the surfactant suppresses dust generation when reducing the diameter of the carbon-containing waste or after reducing the diameter of the carbon-containing waste. be able to.
  • the average particle size of the carbon-containing waste is preferably 10 mm or less.
  • the combustibility improving effect can be obtained without extremely reducing the average particle size of the carbon-containing waste, but the effect is particularly increased when the average particle size is reduced to about 10 mm.
  • the carbon-containing waste is carbon fiber reinforced plastic (CFRP) waste (hereinafter referred to as “waste CFRP”), BOF ( Biomass oil fuel), ASR (Automobile shredder residue), RPF (Refuse paper and plastics densified fuel), RDF (Refuse derived fuel), wood waste, waste tire, rubber waste, water-absorbing polymer waste, municipal waste, thermosetting One or more wastes selected from the group consisting of wastes of thermoplastic and thermoplastic resins, waste FRP (Fiber reinforced plastics), carbon fiber wastes, optical fiber wastes, and solar cell wastes Is preferred. Since these wastes contain carbon compounds, when these wastes are treatment objects, they can be treated effectively by the above method.
  • CFRP carbon fiber reinforced plastic
  • the carbon-containing waste contains carbon fibers.
  • the object to be treated is a waste containing a carbon compound, a combustion promoting effect can be obtained.
  • a particularly high combustion promoting effect is obtained with respect to the carbon compound being carbon fiber.
  • the carbon-containing waste is brought into contact with the treatment accelerator (a combination of a surfactant and hydrogen peroxide or ozone), and then the carbon-containing waste is contacted. May be incinerated in a cement production facility.
  • the treatment accelerator a combination of a surfactant and hydrogen peroxide or ozone
  • the present invention relates to a carbon-containing waste processing method for incinerating and processing carbon-containing waste.
  • the treatment object may be any waste containing a carbon compound and is not particularly limited. Specifically, for example, waste CFRP, BOF, ASR, RPF, RDF, wood waste, waste tire, rubber waste Water-absorbing polymer waste, municipal waste, thermosetting / thermoplastic resin waste, waste FRP, carbon fiber waste, optical fiber waste, solar cell waste, and the like.
  • waste CFRP waste containing a carbon compound
  • BOF waste containing a carbon compound
  • a treatment accelerator is brought into contact with the carbon-containing waste that is the treatment target.
  • a processing accelerator a combination of a surfactant and hydrogen peroxide or ozone is used.
  • the surfactant may be at least one selected from anionic, nonionic, and cationic surfactants, and anionic or nonionic surfactants are particularly preferable.
  • Anionic surfactants include, for example, sodium alkyl ether sulfate, sodium alkyl sulfate, sodium linear alkylbenzene sulfonate (LAS), fatty acid sodium, fatty acid potassium, alpha sulfo fatty acid ester sodium, alpha olefin sulfonic acid sodium salt, Examples include sodium alkyl sulfonate.
  • nonionic surfactants include sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and the like.
  • the amount of the surfactant is from 0.1 parts by weight to 10 parts by weight, preferably from 0.5 parts by weight to 6 parts by weight, more preferably 1 when the amount of the carbon-containing waste is 100 parts by weight. It is not less than 3 parts by mass.
  • the amount of the surfactant is 0.01 parts by mass or more and 25 parts by mass or less, preferably 0.2 parts by mass or more and 20 parts by mass or less, more preferably when the amount of hydrogen peroxide is 100 parts by mass. 0.3 parts by mass or more and 15 parts by mass or less.
  • the lower limit of the amount of the surfactant if the amount is less than the above range, the effect of improving the combustibility of the carbon-containing waste may not be obtained.
  • the upper limit of the amount of surfactant is not restricted from the viewpoint of improving the combustibility of carbon-containing waste.
  • a surfactant is added beyond the above range, it is difficult to obtain an improvement effect according to the amount of the surfactant used, and the cost increases.
  • the purity of hydrogen peroxide is not particularly limited, and a normally available material such as a 30% aqueous solution may be used.
  • the amount of hydrogen peroxide is 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 45 parts by mass or more when the amount of carbon-containing waste is 100 parts by mass.
  • the lower limit of the amount of hydrogen peroxide when the amount of carbon-containing waste is 100 parts by mass, if the amount of hydrogen peroxide is less than 15 parts by mass, the carbon-containing waste is sufficiently improved in combustibility. May not be obtained.
  • the surfactant and hydrogen peroxide may act on the carbon-containing waste.
  • a surfactant and / or hydrogen peroxide may be dropped, sprayed, applied, or the like on a carbon-containing waste, and if necessary, operations such as mixing and stirring are performed. You may give it.
  • the carbon-containing waste may be impregnated in a solution containing a surfactant and / or hydrogen peroxide, or the carbon-containing waste may be impregnated while the carbon-containing waste is swung as necessary.
  • the carbon-containing waste can be left and exposed in an atmosphere in which the surfactant and / or hydrogen peroxide is vaporized, or the carbon-containing waste can be swung as necessary in the atmosphere. Or may be exposed. More typically, for example, a method in which an environment in which thermal decomposition of hydrogen peroxide occurs around the carbon-containing waste inside the incineration facility may be used.
  • Surfactant and hydrogen peroxide may be used in a mixed state or in different forms.
  • the mixing method is not particularly limited, and any method may be used as long as it is a general liquid mixing method.
  • a predetermined amount of a surfactant may be added to hydrogen peroxide having a high mixing ratio and then mixed by stirring.
  • you may prepare and use the aqueous solution which contains both.
  • the surfactant and hydrogen peroxide are used in different forms, the form of the aqueous solution can be prepared and used separately.
  • an aqueous solution containing a surfactant when preparing an aqueous solution containing a surfactant, it is prepared by adding 0.1 to 30 parts by mass of a surfactant to 100 parts by mass of water from the viewpoint of not increasing the viscosity of the aqueous solution. It is preferable that it is prepared by adding 1 part by mass to 10 parts by mass.
  • the timing of bringing the surfactant and hydrogen peroxide into contact with the carbon-containing waste there is no particular limitation on the timing of bringing the surfactant and hydrogen peroxide into contact with the carbon-containing waste. That is, for example, it may be before the carbon-containing waste is put into the incineration facility, at the same time as the input, or after the input.
  • the timing of bringing them into contact with the carbon-containing waste there is no particular limitation on the timing of bringing them into contact with the carbon-containing waste. That is, the surfactant may be brought into contact with the carbon-containing waste prior to hydrogen peroxide, may be brought into contact at the same time, or the surfactant may be brought into contact with the carbon-containing waste after hydrogen peroxide. .
  • a surfactant is brought into contact with the carbon-containing waste to reduce the diameter, and hydrogen peroxide is further brought into contact therewith. According to this, the combustibility improvement effect is further enhanced by the small diameter. Further, the surfactant suppresses the generation of dust when the carbon-containing waste is reduced in diameter or after the carbon-containing waste is reduced in diameter.
  • timing of bringing the surfactant and hydrogen peroxide into contact with the carbon-containing waste there is no particular limitation on the timing of bringing the surfactant and hydrogen peroxide into contact with the carbon-containing waste. That is, for example, it may be before the carbon-containing waste is put into the incineration facility, at the same time as the input, or after the input. More specifically, for example, after adding a surfactant and hydrogen peroxide dropwise to a carbon-containing waste having a reduced diameter, or impregnating a carbon-containing waste having a reduced diameter in a solution containing the surfactant and hydrogen peroxide. Or after adding hydrogen peroxide to carbon-containing waste that has been reduced in diameter by adding a surfactant, or impregnating hydrogen-containing waste that has been reduced in diameter by adding surfactant to hydrogen peroxide.
  • it may be a method of introducing them into the incineration facility, or when introducing the carbon-containing waste having a reduced diameter into the incineration facility, or after the introduction, the surfactant and the peroxide inside the incineration facility. After spraying hydrogen and bringing them into contact with the inside of the incineration facility, or introducing a carbon-containing waste reduced in diameter by adding a surfactant to the incineration facility, spraying hydrogen peroxide inside the incineration facility Connect them inside the incinerator. It may be a method of.
  • ozone when ozone is used as the treatment accelerator, there is no particular limitation on the method of bringing ozone into contact with the carbon-containing waste. That is, any method can be used as long as ozone can exist around the carbon-containing waste. Therefore, ozone may be contacted in the form of gas, or ozone may be contacted in the form of liquid. Specifically, for example, a method of exposing the carbon-containing waste to a gas containing ozone in an airtight container, or a method of immersing the carbon-containing waste in a solution containing ozone can be used.
  • the method of exposing to ozone in a sealed container it is preferable to expose to an atmosphere having an ozone concentration of 100 ppm or more for 1 hour or more, and more preferable to expose to an atmosphere having an ozone concentration of 500 ppm or more for 3 hours or more.
  • the method of immersing in a solution containing ozone it is preferable to immerse in a solution having an ozone concentration of 1 ppm or more for 1 hour or more, and more preferable to immerse in a solution having an ozone concentration of 10 ppm or more for 1 hour or more.
  • the solvent is preferably water from the viewpoint of ease of treatment. That is, it is preferable to use ozone water.
  • Ozone may be obtained, for example, from an ozone generator having the specifications described in JIS B-9946 “Ozone treatment equipment for wastewater and irrigation water—specification items and ozone concentration measurement method”. Specifically, for example, after separating nitrogen from air as a raw material gas by an oxygen concentrator to generate oxygen gas having a purity of 90% or more, the oxygen gas converted into ozone by an ozonizer is used. Can do.
  • Ozone concentration in the atmosphere ozone generation amount of the ozone generator (mg / hour) / Space volume (m 3 ) /2.14 (1) in which gas exists in the sealed container
  • Examples of the method for preparing a solution containing ozone include a pressure dissolution method in which ozone generated by an ozone generator is dissolved in a solvent such as water, a bubble-free gas dissolution method, a bubble dissolution method, a diaphragm dissolution method, and a packed bed dissolution method. It is done. Moreover, the direct electrolysis method etc. which do not require an ozone generator may be used. Among these, from the viewpoint of obtaining high-concentration ozone water, a pressure dissolution method and a bubble-free gas dissolution method are preferable.
  • the surfactant when using a solution containing ozone, the surfactant is included in the solution, or the surfactant is applied to the carbon-containing waste in advance or sprayed to wet the carbon-containing waste. It is preferable to improve the property. Thereby, the further favorable combustibility improvement effect is acquired.
  • the surfactant may be one or more of various anionic, nonionic or cationic surfactants, and among them, one of two types of surfactants, anionic and nonionic. The above is preferable.
  • anionic surfactants include sodium alkyl ether sulfate, sodium alkyl sulfate, sodium linear alkylbenzene sulfonate (LAS), and fatty acid sodium
  • nonionic surfactants include sucrose fatty acid esters and sorbitan fatty acids. Examples include esters, polyoxyethylene sorbitan fatty acid esters, and fatty acid alkanolamides.
  • the carbon-containing waste may be brought into contact with a surfactant to reduce the diameter, and ozone may be further contacted therewith.
  • a surfactant to reduce the diameter
  • ozone may be further contacted therewith.
  • the combustibility improvement effect is further enhanced by the small diameter.
  • the surfactant suppresses the generation of dust when the carbon-containing waste is reduced in diameter or after the carbon-containing waste is reduced in diameter.
  • the amount of the surfactant is 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.5 parts by mass or more and 6 parts by mass or less, when the amount of the carbon-containing waste is 100 parts by mass. Preferably they are 1 mass part or more and 3 mass parts or less.
  • the amount of the surfactant to be contained is 0.01 parts by mass or more when the amount of the liquid that dissolves ozone is 100 parts by mass.
  • the amount is preferably 1 part by mass or less.
  • the amount of the surfactant used is less than 0.01 parts by mass, the wettability of the carbon-containing waste containing a highly hydrophobic carbon compound may not be improved.
  • the amount exceeds 1 part by mass the surfactant is used. In some cases, the effect of improving wettability according to the amount of use of is not recognized.
  • CFRP Carbon fiber reinforced plastics
  • CFRP Carbon Fiber Reinforced Plastics
  • the carbon fiber content is generally about 30% to 80% by mass.
  • the carbon fiber content of CFRP can be determined by a test method based on JIS K 7075 “Test method for fiber content and void ratio of carbon fiber reinforced plastic”.
  • the carbon fiber used in CFRP a fiber formed of graphite-like carbon and having excellent mechanical properties such as rigidity is used.
  • a polyacrylonitrile-based, pitch-based, or cellulose-based fiber is heated to 150 ° C. to 400 ° C. in an oxidizing atmosphere and subjected to flame resistance treatment, and then in an inert atmosphere.
  • activated carbon fibers activated in a semi-active atmosphere such as water vapor are listed.
  • thermoplastic resin As a matrix material used in CFRP, a thermoplastic resin or a thermosetting resin is used.
  • the thermoplastic resin include polyamide resin, polypropylene resin, nylon resin, and the like.
  • thermosetting resin an epoxy resin, unsaturated polyester resin, a polyimide resin, a bismaleimide resin, a phenol resin etc. are mentioned, for example.
  • the main material of the tire is the natural rubber (cis1,4-polyisoprene) for large tires for trucks, and synthetic rubber (SBR, styrene-butadiene random copolymer) for small tires for passenger cars.
  • rubber is 40 mass% to 60 mass%
  • carbon black and sulfur are added 20 mass% to 40 mass%
  • steel and textile tire cords are 10 mass% to 20 mass%
  • bead wires are 3 mass%.
  • the mass is set to 10% by mass.
  • waste CFRP or waste tire which is a CFRP waste composed of the above components
  • a pulverization facility such as a rotary cutter type shear crusher
  • the diameter is reduced to a predetermined size by crushing equipment such as a crusher, a roll mill, a roller mill, or a crusher.
  • pulverization in the stage coarsely crushed to 50 mm or less it is preferable to attach a classification device such as a separator to the subsequent pulverization equipment.
  • waste CFRP In the treatment method of the present invention, it is not always necessary to reduce the diameter, which requires excessive labor. However, in order to perform the treatment efficiently, it is preferable to reduce the diameter of the waste CFRP or the waste tire to some extent. Specifically, in the case of waste CFRP, it is 10 mm or less, preferably 7 mm or less. In the case of a waste tire, it is 50 mm or less, preferably 30 mm or less.
  • the average particle size of the waste CFRP or the waste tire after the diameter reduction treatment is the sieve defined in JIS Z 8801 “Sieving for test-Part 1: Metal mesh sieve” after drying after the diameter reduction treatment. Can be obtained by calculating the diameter corresponding to 50% by mass of the sample remaining on the sieve.
  • the method of bringing the waste CFRP or waste tire having a reduced diameter into contact with the surfactant and hydrogen peroxide is an excessive amount around the waste CFRP or the waste tire. Any method may be used as long as the environment in which thermal decomposition of hydrogen oxide occurs is configured in a cement kiln. Further, in reducing the diameter of waste CFRP or waste tire, a surfactant is dropped on the waste CFRP or waste tire, and then the diameter is reduced to obtain waste CFRP or waste tire containing the surfactant. Alternatively, the waste CFRP containing or waste tire may be contacted with hydrogen peroxide.
  • waste CFRP or waste tire having a reduced diameter for example, after a surfactant and hydrogen peroxide are dropped onto waste CFRP or waste tire having a reduced diameter, or after impregnating waste CFRP or waste tire having a reduced diameter on a surfactant and hydrogen peroxide.
  • it may be a method of throwing them into the cement kiln, or after throwing the waste CFRP or waste tire having a reduced diameter into the cement kiln, spraying a surfactant and hydrogen peroxide inside the cement kiln.
  • the place where the waste CFRP or the waste tire is charged into the cement kiln is not particularly limited, and may be from the front side of the kiln (kiln burner side), from the kiln bottom side, or from the calcining furnace.
  • the boiling point of hydrogen peroxide is 141 ° C. (purity 90%) and hydrogen peroxide is thermally decomposed immediately when it is put into a cement kiln, in order to efficiently use the effect of improving the combustibility by hydrogen peroxide.
  • the surfactant and hydrogen peroxide are simultaneously or substantially simultaneously sent from a common or very close location to the cement kiln. It is preferable to input.
  • the first blowing port of waste CFRP or waste tire is installed in a kiln burner or the like, and a surfactant and hydrogen peroxide are adjacent to the first blowing port.
  • a second blowing port made of only hydrogen peroxide may be installed.
  • waste CFRP or waste tire is heated inside the cement kiln together with the surfactant and hydrogen peroxide brought into contact therewith.
  • the heating temperature is preferably set to a temperature exceeding the combustion temperature range of fixed carbon (500 ° C. to 800 ° C.).
  • fixed carbon refers to a carbon compound that exists in a form that does not volatilize in the carbon-containing waste, and includes carbon fibers contained in the waste CFRP.
  • the temperature of the atmospheric gas containing ozone is preferably 5 ° C or higher and 50 ° C or lower, more preferably 10 ° C or higher and 50 ° C or lower, and more preferably 20 ° C or higher and 50 ° C or lower.
  • the temperature is lower than 5 ° C., an ice layer may be formed on the surface of the waste CFRP or the waste tire, and there is a possibility that contact between the waste CFRP or the waste tire and ozone is inhibited.
  • the temperature exceeds 50 degreeC a special heating apparatus is required.
  • such sealed containers When using a method in which waste CFRP or tires are exposed to an atmospheric gas containing ozone in a sealed container, such sealed containers are provided with a waste CFRP or waste tire input mechanism and discharge mechanism, and a gas containing ozone introduction mechanism and discharge.
  • a mechanism, and an introduction mechanism and a discharge mechanism that can introduce air into the sealed container when necessary may be provided.
  • the introduction mechanism and the discharge mechanism for the gas containing ozone and the air may be shared by both gases.
  • the closed container is provided with a stirring mechanism.
  • the stirring mechanism may be one used for a general powder and particle stirring device such as a stirring blade, or may be air blending.
  • the ozone concentration in the atmospheric gas in contact with the waste CFRP or the waste tire in the closed container is preferably 100 ppm or more, more preferably 300 ppm or more, and particularly preferably 700 ppm or more.
  • the ozone concentration in the atmosphere gas is less than 100 ppm, the time for exposing the waste CFRP or the waste tire to the atmosphere gas becomes longer, so that the processing efficiency is lowered.
  • the upper limit of the ozone concentration in the atmospheric gas is not restricted from the viewpoint of improving the combustibility of waste CFRP or waste tires, but if it exceeds 6000 ppm, it is not preferable because large equipment is required for the production of ozone.
  • the time during which the waste CFRP or the waste tire is exposed to the atmospheric gas containing ozone in the sealed container depends on the ozone concentration in the atmospheric gas, but is preferably 1 hour or more, more preferably 2 hours or more, particularly preferably. Is more than 3 hours. When the exposure time is less than 1 hour, there may be a case where the effect of improving the combustibility of waste CFRP or waste tire by ozone cannot be obtained sufficiently.
  • the temperature of ozone water is preferably 5 ° C. or higher and 30 ° C. or lower, more preferably 5 ° C. or higher and 25 ° C. or lower, and particularly preferably 5 ° C. or higher and 20 ° C. or lower. If the temperature of the ozone water is less than 5 ° C, there is a risk of equipment failure due to freezing. If the temperature of the ozone water exceeds 30 ° C, the ozone concentration of the ozone water decreases.
  • the volume ratio of ozone water immersed in waste CFRP or waste tire is preferably 1/1 or more, more preferably 2/1 or more, and particularly preferably 4/1 or more.
  • the volume ratio of ozone water immersed in waste CFRP or waste tire is less than 1/1, there may be waste CFRP or waste tire that does not sufficiently contact ozone.
  • the time for immersing the waste CFRP or the waste tire in ozone water depends on the ozone concentration in the ozone water, but is preferably 1 hour or more, more preferably 2 hours or more, and particularly preferably 3 hours or more. When the immersion time is less than 1 hour, the effect of improving the combustibility of waste CFRP or waste tire by ozone may not be sufficient.
  • a stirring mechanism is attached to the sealed container. By stirring the ozone water in which the waste CFRP or the waste tire is immersed, all surfaces of the waste CFRP or the waste tire having a reduced diameter are helped to come into contact with the ozone water uniformly.
  • the stirring mechanism should just be used for common slurry stirring apparatuses, such as a stirring blade.
  • the waste CFRP when treating the waste CFRP, it is preferable to contain a surfactant in the ozone water in order to improve the wettability of the waste CFRP containing the carbon fiber that is hydrophobic in particular.
  • the amount of the surfactant used is preferably 0.01 parts by mass or more and 1 part by mass or less when the amount of ozone water is 100 parts by mass.
  • the usage-amount of surfactant is less than 0.01 mass part, the wettability of the waste CFRP containing carbon fiber with high hydrophobicity may not be improved.
  • it exceeds 1 mass part the improvement effect of the wettability according to the usage-amount of surfactant may not be recognized.
  • waste CFRP or waste tire that has been contacted with ozone is heated inside the cement kiln. After the immersion in ozone water, the recovered waste CFRP or waste tire does not need to be dried.
  • waste CFRP or waste tires that have been exposed to ozone-containing atmospheric gas or immersed in ozone water and have been subjected to the combustion improvement effect by ozone have improved flammability even when left in the air. There is no decline.
  • the location of waste CFRP or waste tires into the cement kiln is not particularly limited and is from the front side of the kiln (kiln burner side). However, it may be from the kiln bottom side, or may be used in a calcining furnace.
  • the waste CFRP is preferably added to a location having a temperature exceeding the combustion temperature range (500 ° C. to 800 ° C.) of the carbon fiber contained in the waste CFRP.
  • waste CFRP or waste tire is described as a processing object, and an example of a cement kiln that is a cement manufacturing facility is described as an incineration facility for carbon-containing waste, but in the processing method of the present invention, Of course, incineration may be performed using incineration equipment other than cement kiln.
  • waste CFRP was demonstrated as one of the process target objects, this is that the method according to the present invention can obtain a particularly high combustion promotion effect for the carbon compound being carbon fiber. This is because it is possible.
  • the object to be treated by the method according to the present invention is not limited to waste containing carbon fibers as a carbon compound, and may include, for example, carbon compounds other than carbon fibers, such as waste tires. .
  • test results relating to the processing method of the present invention that is, examples of the processing method of the present invention.
  • each test level was set as follows.
  • Test 2 Carbon-containing waste: Waste tire Sample size of waste tire: 3 x 3 x 3 mm Hydrogen peroxide: Same as Test 1
  • Surfactant Same as Test 1
  • Usage of surfactant and hydrogen peroxide Exposed carbon-containing waste with surfactant applied in an atmosphere where hydrogen peroxide was vaporized Assuming the conditions, the surfactant is dropped onto the waste tire and mixed, so that the waste tire coated with the surfactant on its surface is not allowed to be impregnated with hydrogen peroxide in advance. Hydrogen oxide was added dropwise and heated simultaneously. Table 2 shows the amount of surfactant applied to the waste tire and the amount of hydrogen peroxide added.
  • the former weight reduction rate with respect to room temperature weight
  • the latter weight reduction rate with respect to the weight of fixed carbon
  • test results of the flammability evaluation test 1 are shown in Table 1 for waste CFRP and in Table 2 for waste tires.
  • the waste CFRP (Examples 1 to 5) contacted with hydrogen peroxide and a surfactant at the stage of heating to 700 ° C. was almost burned out.
  • the fixed carbon (carbon fiber) of the waste CFRP is heated to 700 ° C.
  • Example 6 the waste tire (Example 6) in which hydrogen peroxide and the surfactant were brought into contact with each other when heated to 600 ° C. was almost burned out, whereas hydrogen peroxide and About 20% of the waste tire (Comparative Example 3) that was not brought into contact with the surfactant remained unburned at that stage. Furthermore, when comparing the flammability of fixed carbon (carbon fiber), in Example 6 using hydrogen peroxide and a surfactant, the fixed carbon of the waste tire was almost burned out when heated to 600 ° C. On the other hand, in Comparative Example 3 in which hydrogen peroxide and a surfactant were not used, approximately 60% of the fixed carbon of the waste tire remained unburned at that stage.
  • FIG. 1 shows weight reduction curves in the heating processes of Example 3, Comparative Example 1 and Comparative Example 2.
  • FIG. 2 shows weight loss curves in the heating processes of Example 6 and Comparative Example 3.
  • two regions on the low temperature side region corresponding to 300 to 400 ° C. and region corresponding to 450 to 550 ° C.
  • This is a weight reduction due to combustion of volatile carbon such as resin
  • the weight loss region (region of 550 ° C. or higher) on the highest temperature side is mainly weight reduction due to combustion of fixed carbon such as carbon fiber. Therefore, it can be seen from FIGS.
  • Example 3 and Example 6 that the methods of the present invention (Example 3 and Example 6) are particularly effective in promoting the flammability of fixed carbon. Furthermore, it can be seen from FIG. 1 that only by adding hydrogen peroxide (Comparative Example 2), a sufficient combustion promoting effect cannot be obtained.
  • each test level was set as shown in ⁇ Test 3 >> below.
  • Test 3 Carbon-containing waste: Waste CFRP as in Test Example 1 (carbon fiber content: 58% by mass) Sample size of waste CFRP: 5 types of average particle diameters of 16 mm, 9.5 mm, 6.7 mm, 4.75 mm and 2.8 mm Hydrogen peroxide: Same as Test Example 1 Surfactant: Same as Test Example 1 Surface activity Agent and hydrogen peroxide use method: The amount of hydrogen peroxide and surfactant to be contacted with each waste CFRP is the amount of hydrogen peroxide (purity 30%) when the amount of waste CFRP is 100 parts by mass. 150 parts by mass and the amount of the surfactant were 5 parts by mass (the test level of Example 3 of Test Example 1 was used).
  • the waste CFRP, hydrogen peroxide, and surfactant are placed in the same sample container immediately before being put into the heating electric furnace described below, and heated in an electric furnace in an air atmosphere set at 1400 ° C. for 3 minutes, after heating.
  • the presence or absence of unburned carbon fiber in the waste CFRP was evaluated.
  • This heating condition is a condition that simulates the case where the combustion treatment is performed by putting the cement kiln in the front part of the kiln.
  • the weight of the fixed carbon (carbon fiber) in the combustion temperature range 500 to 800 ° C.
  • the weight reduction rate for the fixed carbon (carbon fiber) combustion temperature range 500 to 800 ° C is also obtained for the sample before heating.
  • the ratio was evaluated as the residual rate (mass%) of fixed carbon (carbon fiber).
  • the test results of the particle size evaluation test 1 are shown in Table 3 below.
  • the combustibility improvement effect by using a combination of a surfactant and hydrogen peroxide as a processing accelerator may be greater. It became clear.
  • each test level was set as follows.
  • Waste CFRP Carbon-containing waste: Waste CFRP (carbon fiber content: 58% by mass) Sample size of waste CFRP: average particle diameter 1mm Ozone contact method: immersion in ozone water with surfactant ozone water: ozone concentration 50ppm
  • Surfactant Sodium linear alkylbenzene sulfonate, linear alkylbenzene sulfonic acid, and sodium alkyl ether sulfate ester (Lion Corporation: Mama Lemon (trade name))
  • Surfactant concentration 0.01 parts by mass (0.01% by mass) with respect to 100 parts by mass of the total amount of ozone water
  • the obtained exposed or immersed sample was heated at a heating rate of 10 ° C./min, and the weight loss rate was measured in the temperature range from room temperature to 1000 ° C.
  • the weight reduction rate is measured using a thermogravimetric / differential heat measuring device (manufactured by Netch Japan Co., Ltd .: TG-DTA 2020SR (trade name)).
  • the total combustion rate and the combustion rate of fixed carbon in waste CFRP or waste tire were calculated.
  • test results of the flammability evaluation test 2 are shown in Tables 4 and 5 for waste CFRP, and in Tables 6 and 7 for waste tires. Moreover, each thermogravimetric curve is shown in FIG.3 and FIG.4.
  • Example 6 the waste tires exposed to the ozone atmosphere (Examples 10 and 11) burned out when heated to 600 ° C., but were not in contact with ozone.
  • Example 5 the sample did not burn out unless heated to 650 ° C.
  • Table 7 when the flammability of fixed carbon was compared, in Example 10 and Example 11 in contact with ozone, the fixed carbon of the waste tire was burned out when heated to 580 ° C.
  • Comparative Example 5 that was not in contact with ozone, there was 10% unburned residue even when heated to 600 ° C.
  • Example 10 and Example 11 were comparable, it was considered that a sufficient flammability improving effect could be obtained even when the exposure time was shorter than 1 hour for the waste tire.
  • the ozone atmosphere to be brought into contact with each sample was the same as that in the flammability evaluation test 2, and the exposure time of the waste CFRP in the ozone atmosphere was 3 hours (the same as in Example 8 of the flammability evaluation test 2).
  • the exposure time of the waste CFRP in the ozone atmosphere was 3 hours (the same as in Example 8 of the flammability evaluation test 2).
  • one not exposed to an ozone atmosphere was prepared (same as Comparative Example 4 in Combustibility Evaluation Test 2).
  • the sample was heated in an electric furnace in an air atmosphere set at a temperature of 1400 ° C. for 3 minutes, and the residual rate of fixed carbon (carbon fiber) remaining in the heated sample without burning was determined as in Test Example 2. Evaluation was performed in the same manner. The test results of the particle size evaluation test 2 are shown in Table 8.

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Abstract

L'invention concerne un procédé de traitement de déchets contenant du carbone, permettant de brûler suffisamment les déchets contenant du carbone en utilisant moins de main-d'œuvre. Les déchets contenant du carbone et, en tant qu'accélérateur de traitement, de l'ozone ou une combinaison d'un tensioactif et de peroxyde d'hydrogène, sont mis en contact, et les déchets contenant du carbone sont ensuite incinérés.
PCT/JP2017/025384 2016-09-29 2017-07-12 Procédé de traitement de déchets contenant du carbone Ceased WO2018061404A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0518654U (ja) * 1991-08-19 1993-03-09 ホクセイ機装株式会社 ゴム廃棄物の処理装置
JPH1123793A (ja) * 1997-06-27 1999-01-29 Toshiba Corp イオン交換樹脂の処理方法
JP2001261883A (ja) * 2000-03-23 2001-09-26 Okayama Prefecture 加硫ゴムの再生方法
JP2003114298A (ja) * 2001-10-04 2003-04-18 Hitachi Ltd 廃棄物処理装置及び処理方法
JP2006145543A (ja) * 2004-11-24 2006-06-08 Korea Hydro & Nuclear Power Co Ltd 遷移金属含有の廃樹脂のガラス化装置及び方法
JP2006212581A (ja) * 2005-02-04 2006-08-17 Mitsubishi Heavy Ind Ltd 有機性廃棄物の処理方法
JP2011137615A (ja) * 2009-12-28 2011-07-14 Akio Tsubota 熱分解処理装置
JP2012031559A (ja) * 2010-07-05 2012-02-16 Taiyo Nippon Sanso Corp 酸化処理方法及び酸化処理装置
JP2015160888A (ja) * 2014-02-27 2015-09-07 株式会社東芝 使用済みイオン交換樹脂の処理方法及び処理装置
JP2016123973A (ja) * 2014-12-26 2016-07-11 ユニ・チャーム株式会社 使用済み吸収性物品のリサイクル方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0518654U (ja) * 1991-08-19 1993-03-09 ホクセイ機装株式会社 ゴム廃棄物の処理装置
JPH1123793A (ja) * 1997-06-27 1999-01-29 Toshiba Corp イオン交換樹脂の処理方法
JP2001261883A (ja) * 2000-03-23 2001-09-26 Okayama Prefecture 加硫ゴムの再生方法
JP2003114298A (ja) * 2001-10-04 2003-04-18 Hitachi Ltd 廃棄物処理装置及び処理方法
JP2006145543A (ja) * 2004-11-24 2006-06-08 Korea Hydro & Nuclear Power Co Ltd 遷移金属含有の廃樹脂のガラス化装置及び方法
JP2006212581A (ja) * 2005-02-04 2006-08-17 Mitsubishi Heavy Ind Ltd 有機性廃棄物の処理方法
JP2011137615A (ja) * 2009-12-28 2011-07-14 Akio Tsubota 熱分解処理装置
JP2012031559A (ja) * 2010-07-05 2012-02-16 Taiyo Nippon Sanso Corp 酸化処理方法及び酸化処理装置
JP2015160888A (ja) * 2014-02-27 2015-09-07 株式会社東芝 使用済みイオン交換樹脂の処理方法及び処理装置
JP2016123973A (ja) * 2014-12-26 2016-07-11 ユニ・チャーム株式会社 使用済み吸収性物品のリサイクル方法

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