WO1996031736A1 - Procede pour detruire des dechets de resine - Google Patents

Procede pour detruire des dechets de resine Download PDF

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Publication number
WO1996031736A1
WO1996031736A1 PCT/JP1995/000669 JP9500669W WO9631736A1 WO 1996031736 A1 WO1996031736 A1 WO 1996031736A1 JP 9500669 W JP9500669 W JP 9500669W WO 9631736 A1 WO9631736 A1 WO 9631736A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxygen
container
amount
resin waste
waste
Prior art date
Application number
PCT/JP1995/000669
Other languages
English (en)
Japanese (ja)
Inventor
Yoshio Miyashita
Yoshio Sato
Shoji Ichida
Tokuyoshi Kawai
Original Assignee
Kokan Keisoku Kabushiki Kaisha
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 Kokan Keisoku Kabushiki Kaisha filed Critical Kokan Keisoku Kabushiki Kaisha
Priority to PCT/JP1995/000669 priority Critical patent/WO1996031736A1/fr
Priority to AU21477/95A priority patent/AU2147795A/en
Publication of WO1996031736A1 publication Critical patent/WO1996031736A1/fr

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/12—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of plastics, e.g. rubber
    • 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
    • F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
    • F23G5/085—High-temperature heating means, e.g. plasma, for partly melting the waste
    • 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
    • F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
    • F23G5/12—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating using gaseous or liquid fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
    • F23L2900/00—Special arrangements for supplying or treating air or oxidant for combustion; Injecting inert gas, water or steam into the combustion chamber
    • F23L2900/07007—Special arrangements for supplying or treating air or oxidant for combustion; Injecting inert gas, water or steam into the combustion chamber using specific ranges of oxygen percentage
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery

Definitions

  • This D X N is a carcinogenic harmful substance generated when chlorine-containing organic matter is exposed to high temperatures of several hundred degrees in the presence of oxygen.
  • the incineration of municipal waste and medical waste produces D X N because these contain many plastics.
  • dioxin The combination of PCDD and PCDF is called dioxin.
  • dioxin Generally the most toxic in the die Okishin strong in the 2, 3, 7, 8 tetrachloride para dioxin (2, 3, 7, 8-T 4 CDD) is, is used as a herbicide and wood preservative Phenol, 2,4,5-trichlorophenolic acid known as a defoliant, etc. are also contained as impurities.
  • the chemical structural formula of DXN is shown in FIG. As is clear from this structural formula, the compound has a chemical structural formula in which one or two oxygen atoms are bonded to two chlorine-containing benzene rings.
  • TEZ toxicity conversion factor
  • An object of the present invention is to provide a method for treating resin waste that does not generate DXN, and a method for treating gas generated when treating resin waste as effectively as possible. I do.
  • Oxygen ratio supplied oxygen amount Z (CX32 2 + H '16/2)
  • oxygen supply amount oxygen supplied from outside the container (kg).
  • C carbon amount (kg) of resin waste in the container combined with the supply oxygen
  • H ′ carbon supply amount in the container combined with the supply oxygen The amount obtained by subtracting the amount of hydrogen (kg) that combines with the halogen element in the resin waste in the container from the amount of hydrogen (kg) in the resin waste
  • Oxygen ratio oxygen supply Z (Cx32 no 12 + H 'X 16/2)
  • supplied oxygen amount oxygen supplied from outside the container (kg)
  • C amount of carbon in resin waste and fuel in the container combined with the supplied oxygen (kg)
  • H ′ combined with the supplied oxygen
  • the supply of the oxygen or the oxygen and the fuel is The method for treating resin waste according to claim 1 or 2, characterized in that the method is carried out by an elverner.
  • the resin waste is a hydrocarbon resin, a resin containing chlorine, a resin containing fluoride, or another organic compound. And a method for treating resin waste.
  • FIG. 1 is a diagram showing the chemical structure of D XN.
  • FIG. 2 is a diagram showing an outline of a pyrolysis furnace used for the present invention. Detailed description of the invention
  • Resins do not necessarily have a benzene ring, but resins contain so-called hydrocarbons and chlorine, and when these resins are burned in the air, their effects are not obvious. It is presumed that dioxin (DXN) is formed by the formation of a benzene ring containing, and the oxygen contained in the atmosphere bonding to the benzene ring containing chlorine. In general, it is said that the DXN generation reaction generates DXN at about 30 O'C during the cooling process when the DXN precursor generated at a high temperature.
  • DXN dioxin
  • resin waste means various natural and synthetic resin waste such as various waste plastics, for example, polyethylene, vinyl chloride, polypropylene, polystyrene, polychlorinated biphenyl, and waste oil (mechanical oil). The present invention covers all of these.
  • the waste contained in the pyrolysis vessel is heated and burned by supplying oxygen or fuel and oxygen into the vessel when the oxygen ratio defined by the following formula is 1 or less, and the temperature is 500 or more. Decompose by heating.
  • Oxygen ratio supplied oxygen amount (Cx 32 12 + H 'X 16/2)
  • “combined with the supplied oxygen” means the amount of carbon or hydrogen in the resin waste and fuel that oxidize and react with oxygen supplied from the outside, for example, in the resin waste and fuel. If carbon or hydrogen has unburned parts, this part is not included. In that sense, it means the part that actually burned or reacted.
  • ⁇ ' is the amount of hydrogen obtained by subtracting the amount of hydrogen combined with halogen elements in the resin waste in the container from the amount of hydrogen in the resin waste and fuel in the container that combines with oxygen.
  • resin waste contains halogen elements such as chlorine or fluorine. These elements combine with hydrogen during thermal decomposition to generate HC1, HF, etc. It has been reduced. Therefore, the oxygen ratio is 1, the supplied oxygen so that burning the c and H in the fuel and the resin to just C 0 2 and 0, supplies the oxygen amount UNA by oxygen gas is not present in the combustion gases Means that. Since the amount of oxygen in the resin is generally small, this may be ignored in the calculation.
  • fuel such as coke oven gas (C gas) and propane can be used as the fuel.
  • a so-called oxy-fuel burner from the viewpoint of efficiently burning the fuel.
  • Air may be used as the oxygen source, but pure oxygen is more preferable in terms of efficiency. If the oxygen ratio is too low, the amount of gas generated after pyrolysis increases, which is not desirable for using the generated gas. Therefore, the oxygen ratio is desirably 0.3 or more.
  • a modifying agent such as water or steam can be added.
  • the thermal decomposition temperature is preferably 500 ° C. or higher, more preferably 600 ° C. or higher. If it is less than 500, the carbonization speed is too low to be practical.
  • the carbonization pressure is desirably 1.5 atmospheres or less. If the pressure exceeds 1.5 atm, the equipment cost will increase.
  • the dimensions of the pyrolysis vessel 2 are a stainless steel vessel having an inner diameter of 300 mm and a height of about 500 mm, and can be heated from outside by a heater 4, for example, an electric heater.
  • a heater 4 for example, an electric heater.
  • the outside of the stainless steel pyrolysis vessel 2 is surrounded by a heat insulating material 6 to prevent heat dissipation. Resins can be charged into the inside of the pyrolysis vessel 2 and kept in a sealed state. Before the start of heating, an inert gas such as nitrogen The inside air is exhausted from the gas exhaust pipe 8 to the outside.
  • oxygen is supplied from the oxygen pipe 20, or coke oven gas is supplied from the oxygen and fuel pipe 18 to supply the oxygen fuel burner 7.
  • the generated decomposition gas first passes through a filter 10 provided with a layer of paper or the like. The tars generated here are captured, and the decomposed gas passes through the DXN collector 12.
  • the collecting device 12 consists of a plurality of collecting bottles immersed in ice water, a collecting bottle containing a diethylene glycol solution, and a container containing XAD-2 resin, and captures DXN in the decomposition gas that has passed through. Gather.
  • the amount of decomposed gas from which DXN has been collected is measured by a gas meter 13, and a part of it is collected in Tetra Pak 14. Decomposed gas collected in Tetra Vac 14 is used for analysis.
  • the furnace can be kept at a temperature of six hundred to one 200 e C, it is possible to decompose the resins to hydrocarbons.
  • the above is the experimental apparatus used in the example of the present invention.
  • PE polyethylene
  • PVC polyvinyl chloride
  • Table 1 shows the elemental analysis of polyethylene (PE) and polyvinyl chloride (PVC) used in the following examples. These typical resins have been shown to contain mainly carbon, hydrogen and large amounts of chlorine.
  • Table 2 shows the composition of the coke oven gas (C gas) used.
  • PVC was used in the experiments as a typical example of chlorine-containing resins, particularly in that they contain large amounts of chlorine.
  • Table 3 shows the level of the experiment. That is, to investigate the decomposition behavior of PE and PVC.
  • each of these resins was charged in the thermal decomposition furnace shown in Fig. 2 in an amount of 50 gZ, respectively, and pyrolyzed at 500 to 1200 ° C for about 120 minutes.
  • the unburned matter passed through the grate 202 and was discharged from the rotary valve 204 to the outside of the furnace.
  • the inside of the pyrolysis vessel was first purged with pure nitrogen gas, sufficient air was removed, and then dry distillation was started.
  • C gas is supplied at 50 ⁇ / min as fuel, and oxygen gas is supplied at the same time.
  • the target oxygen ratio is about 0.2, 0.5, 0.8. , 1.1 were performed twice. In experiments without fuel, the target oxygen ratio was set to 0.8 and 1.1.
  • Table 4 shows the results of pyrolysis of PE
  • Table 5 shows the results of pyrolysis of PVC.
  • the oxygen ratio was calculated from the amount of oxygen actually supplied from the material balance, and is shown in these tables.
  • the generated gas, tar and residue were analyzed by PCDD and PCDF.
  • the oxygen ratio of about 0.8 or less DXN is a both 0.0 at 1 ng / Nm 3 or less, or 0.0 1 NgZg hereinafter, even if these were tentatively dumping disposal, no problem DXN could be reduced to an unacceptable level.
  • the smaller the oxygen ratio the more gas components such as CO gas and methane, and it becomes an effective fuel.
  • the amount of tar generated increases.
  • PE Polyethylene (one [CH 2 CH 2] n -),
  • PVC PVC (one [CH 2 CHC 1]verbone) 2 Composition of coke oven gas Vo l%
  • D XN is reduced by isolating resin waste from the atmosphere and performing pyrolysis at an oxygen ratio of 1 or less and at least 500 ° C. or more, preferably 600 ° C. or more. It can be thermally decomposed into gas, tar, and residue that do not contain. Therefore, the principle of the present invention is an invention that can be applied to a conventional refuse incinerator or an incinerator for industrial waste. At the same time, the treatment method of the present invention is a method of recovering fuel gas that can be effectively reused, and is a very useful invention in the public health, health, and industry.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Environmental & Geological Engineering (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Gasification And Melting Of Waste (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé pour détruire des déchets de résine qui ne produit pas de dioxine et qui consiste à charger ces résines dans un conteneur étanche à l'air et à chauffer et brûler les résines en introduisant de l'oxygène dans le récipient avec un rapport d'oxygène supérieur à 1, ce rapport étant défini par la formule: rapport d'oxygène = quantité de charge d'oxygène/(C x 32/12 + H' x 16/2). Les déchets subissent une décomposition thermique par chauffage à une température qui n'est pas inférieure à 500 °C. En outre, la présente invention concerne un procédé de décomposition thermique des résines dans le conteneur, consistant à ajouter un carburant ainsi que de l'oxygène, avec un rapport d'oxygène qui ne dépasse pas 1, lorsque cela est nécessaire.
PCT/JP1995/000669 1995-04-06 1995-04-06 Procede pour detruire des dechets de resine WO1996031736A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP1995/000669 WO1996031736A1 (fr) 1995-04-06 1995-04-06 Procede pour detruire des dechets de resine
AU21477/95A AU2147795A (en) 1995-04-06 1995-04-06 Method of disposing of resin wastes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1995/000669 WO1996031736A1 (fr) 1995-04-06 1995-04-06 Procede pour detruire des dechets de resine

Publications (1)

Publication Number Publication Date
WO1996031736A1 true WO1996031736A1 (fr) 1996-10-10

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WO (1) WO1996031736A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003031538A1 (fr) * 2001-10-03 2003-04-17 Sony Corporation Procede de recuperation d'hydrogene a partir de residus de resine, procede de production d'hydrogene a partir de residus de resine et dispositif de production d'hydrogene a partir de residus de resine

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04225711A (ja) * 1990-12-06 1992-08-14 Leonardus M M Nevels 種々の廃棄物を燃焼させる方法、それに使用される室炉および包括的廃棄物燃焼設備
JPH04243589A (ja) * 1991-01-22 1992-08-31 Sumitomo Metal Ind Ltd 含炭素廃材の処理方法
JPH04313610A (ja) * 1991-04-12 1992-11-05 Hitachi Zosen Corp ごみ焼却方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04225711A (ja) * 1990-12-06 1992-08-14 Leonardus M M Nevels 種々の廃棄物を燃焼させる方法、それに使用される室炉および包括的廃棄物燃焼設備
JPH04243589A (ja) * 1991-01-22 1992-08-31 Sumitomo Metal Ind Ltd 含炭素廃材の処理方法
JPH04313610A (ja) * 1991-04-12 1992-11-05 Hitachi Zosen Corp ごみ焼却方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003031538A1 (fr) * 2001-10-03 2003-04-17 Sony Corporation Procede de recuperation d'hydrogene a partir de residus de resine, procede de production d'hydrogene a partir de residus de resine et dispositif de production d'hydrogene a partir de residus de resine

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Publication number Publication date
AU2147795A (en) 1996-10-23

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