WO2003026745A1 - Method and apparatus for rendering polychlorinated biphenyl harmless - Google Patents

Method and apparatus for rendering polychlorinated biphenyl harmless Download PDF

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Publication number
WO2003026745A1
WO2003026745A1 PCT/JP2001/008172 JP0108172W WO03026745A1 WO 2003026745 A1 WO2003026745 A1 WO 2003026745A1 JP 0108172 W JP0108172 W JP 0108172W WO 03026745 A1 WO03026745 A1 WO 03026745A1
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WO
WIPO (PCT)
Prior art keywords
emulsified
electric resistance
ultrasonic emulsifier
polychlorinated biphenyl
melting furnace
Prior art date
Application number
PCT/JP2001/008172
Other languages
French (fr)
Japanese (ja)
Inventor
Hideo Katayama
Original Assignee
Anzai, Setsu
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 Anzai, Setsu filed Critical Anzai, Setsu
Priority to PCT/JP2001/008172 priority Critical patent/WO2003026745A1/en
Publication of WO2003026745A1 publication Critical patent/WO2003026745A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/32—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by treatment in molten chemical reagent, e.g. salts or metals
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/411—Emulsifying using electrical or magnetic fields, heat or vibrations
    • B01F23/4111—Emulsifying using electrical or magnetic fields, heat or vibrations using vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/49—Mixing systems, i.e. flow charts or diagrams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/10—Apparatus specially adapted for treating harmful chemical agents; Details thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/14—Waste material, e.g. to be disposed of
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
    • F27B3/08—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces heated electrically, with or without any other source of heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D11/00—Arrangement of elements for electric heating in or on furnaces
    • F27D11/02—Ohmic resistance heating
    • F27D11/04—Ohmic resistance heating with direct passage of current through the material being heated

Definitions

  • the present invention belongs to the technical field of a method and an apparatus for detoxifying polychlorinated biphenyl (PCB).
  • PCB to be treated in the present invention refers to a liquid such as oil alone or a solvent containing PCB alone or PCB. Background art
  • PCBs are physically and logically stable, and have excellent heat resistance and electrical insulation properties. It has been widely used in industrial products such as oils, lubricants and inks.
  • PCB production has been discontinued since these PCB-containing substances proved to be harmful to the human body and environmental pollutants that are difficult to decompose in nature. Used PCB-containing substances have been recovered, or products containing PCBs that have been stored are desired to be detoxified.
  • Japanese Patent Application Laid-Open No. 7-241352 proposes a method in which a PCB is heated to a temperature higher than or equal to ⁇ ⁇ ⁇ and then added to a metal refining furnace to heat the PC ⁇ . ing. '
  • PCBs are chemically stable and nonflammable, and if they are forcibly pyrolyzed, toxic and toxic substances such as chlorine and sulfide will be generated. Les is in reality a possible treatment by the high-temperature combustion, 0
  • An object of the present invention is to solve the conventional problems described above, and an object of the present invention is to provide a method and an apparatus for detoxifying polychlorinated biphenyls, which are inexpensive in equipment and processing cost and generate less harmful substances. Disclosure of the invention
  • the method for detoxifying polychlorinated biphenyls comprises mixing a polychlorinated biphenyl solution and alumina oxide with silicon dioxide into an ultrasonic emulsifier, emulsifying the mixture, and emulsifying the milk.
  • the emulsified hybrid material is dropped onto the molten metal in the electric resistance melting furnace, and the temperature is set at 150 ° C. to 200 ° C. It is characterized by being melted and processed into a glass at the temperature of C.
  • the present inventor has found through experiments that the polychlorinated biphenyl liquid and alumina oxide silicon dioxide can be emulsified by ultrasonic energy to form a kind of clay, and this is known as an electric resistance melting furnace. It has been demonstrated that it can be melted by using.
  • the detoxifying device for the polychlorinated biphenyls of the present invention is connected to the polychlorinated biphenyl liquid storage tank 1 connected to the ultrasonic emulsifier 2 and connected to the ultrasonic emulsifier via a mouthpiece kiln 3.
  • Alumina oxide '' silicon dioxide storage tank 4 connected to ultrasonic emulsifier via monitoring section 8 and electric resistance measuring section 9, and ultrasonic milk tank
  • a feed pack tube 22 for feeding the resulting emulsified hybrid material back to an ultrasonic mixer, and measuring the milky state of the emulsified hybrid material by the electric resistance measuring unit and feeding the incomplete emulsified hybrid material to the feed pack.
  • FIG. 1 is a configuration diagram showing one embodiment of a detoxifying apparatus for polychlorinated phenyl according to the present invention.
  • the storage tank 1 for the polychloride biphenyl liquid is connected to an ultrasonic emulsifier 2 via a solenoid valve VI, a pipe 20 and a pump P1, and a mixture of acid alumina and diacid sodium.
  • the storage tank 4 is connected to the ultrasonic emulsifier 2 via a solenoid valve V4, a rotary kiln 3, a pipe 23, and a solenoid valve V9.
  • a polychlorinated biphenyl liquid and a mixed material of alumina oxide and silicon dioxide are emulsified and mixed with ultrasonic energy, and the emulsified mixed material is supplied by a solenoid valve V2 and a pump P2.
  • Piping 21, monitoring unit 8, electric resistance measuring unit 9, solenoid valve V 5 are sent to electric resistance melting furnace 5, where the melting temperature is 1 500 to 200 0 Melted at 0, Gala The material is in a state where it is molten.
  • the vitreous molten material is discharged from the discharge part 11 to the outside of the electric resistance melting furnace 5 and the molten glass material is hardened, so that the polychlorinated biphenyl is converted into an alumina oxide / dioxide material. Glass material.
  • the monitoring unit 8 connected to the pipe 21 has a glass window to check the emulsified state of the polychloride biphenyl material emulsified and mixed by the ultrasonic emulsifier 2 and the alumina oxide ' Can be.
  • the electric resistance measurement unit 9 automatically measures the electric resistance value of the mixed material and sends this signal to the automatic control unit 10. If the electric resistance value is high (the emulsification degree is low), the piping 2 The solenoid valve V5 provided in 1 is closed by the automatic control unit 10 to prevent the imperfect mixed material from entering the electric resistance melting furnace 5, and at the same time, the solenoid valve V6 is opened and the pump is opened. The incomplete hybrid material is fed into the ultrasonic emulsifier 2 via the feed pack tube 22 by P 2.
  • Exhaust gas from the electric resistance melting furnace 5 is sent to an exhaust chamber 7 by an exhaust fan F1 provided in an exhaust pipe 24, and is exhausted by an exhaust gas treatment filter and a catalyst inside the exhaust chamber 7, and The exhaust gas is exhausted from the chimney 12 into the space as exhaust gas that does not pollute the environment as much as possible.
  • a sensor group 6 provided in the exhaust pipe 25 detects harmful gases contained in the exhaust gas from the exhaust chamber 7, and when the gas exceeds the reference value, the automatic control unit 13 operates to activate the fan F 1. Stop, close the solenoid valves V7 and V8, stop the air inside the air chamber 7 and hold it inside the exhaust chamber 7 for an arbitrary period of time. When the value of the sensor group 6 becomes equal to or less than the reference value, the solenoid valves V7 and V8 are opened by the automatic control unit 13, and the exhaust fan F1 operates to perform normal exhaust.
  • FIG. 1 is a configuration diagram showing one embodiment of a polychlorinated biphenyl detoxifying apparatus of the present invention.
  • FIG. 2 shows an example of an electric resistance melting furnace according to the present invention.
  • FIG. 2 (A) is a longitudinal sectional view
  • FIG. 2 (B) is a sectional view taken along line BB of FIG. 2 (A)
  • FIG. FIG. 3 is a diagram showing a circuit.
  • Fig. 1 shows an example of the electric resistance type melting furnace 5 of Fig. 1;
  • Fig. 1 (A) is a longitudinal sectional view
  • Fig. 1 (B) is a sectional view taken along line BB of Fig. 1 (A)
  • Fig. 1 (C) shows an electric circuit.
  • FIG. 1 In FIGS. (A) and (B), the metal melt 31 below the emulsified hybrid 30 is obtained by melting metal waste before the emulsified hybrid 30 is melted.
  • the emulsified hybrid material 30 is deposited on the upper surface of the metal melt 31.
  • two graphite electrodes 33a, 33b having a rectangular cross section are arranged so as to be able to move up and down through the ceiling 32, and the outer peripheral surfaces of the graphite electrodes 33a, 33b are The tip is buried in a metal melt 31, and the emulsified hybrid material 30 is dropped on the metal melt 31.
  • a power supply cape notch 34a, 34b is connected to the black mouth and the electrodes 33a, 33b.
  • the power supply cape clamps 34a and 34b are connected to the single-phase power supply terminal 35b.35c on the secondary side of the power transformer 35, and are connected to the primary side of the power transformer 35.
  • the connection terminals U, B, and W on the side 35a are connected to a three-phase power supply.
  • the electrode according to this example has the advantage of increasing the structural strength of each electrode by covering the outer peripheral surface of graphite material with molybdenum M, and has the advantage that it can be used up to about 2600 in terms of temperature. Even if the hybrid material or the waste metal piece hits the electrode, the electrode is less likely to be damaged, and the processing cost can be reduced accordingly. Then, the melted emulsified hybrid material 30 is formed into a harmless glass and discharged to the outside, and the harmless metals introduced into the melting furnace 5 are melted to form an alloy material and discharged to the outside.
  • a polychlorinated biphenyl liquid is mixed with a powder material of alumina oxide / silicon dioxide, emulsified and mixed to form a kind of clay. Since this emulsified hybrid material is instantaneously melted at a high temperature in an electric resistance melting furnace, the emulsified hybrid material becomes glassy with alumina oxide and silicon dioxide. The harmful gas components in the exhaust gas will be below the standard due to the filter and catalyst inside the safety chamber.
  • the glassy material is chemically stable and detoxified, so that it can be used for road materials and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
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  • Dispersion Chemistry (AREA)
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Abstract

A method for rendering polychlorinated biphenyl harmless, which comprises feeding a liquid containing polychlorinated biphenyl and a mixture of an aluminum oxide and silicon dioxide to an ultrasonic emulsifier (2), conducting an emulsification, allowing the resultant emulsified mixture to fall onto a molten metal in an electric resistance type melting furnace (5) and melt it at a temperature of 1500 to 2000 °, to thereby convert it to a material of a glassy state. The method can be used for rendering polychlorinated biphenyl harmless at low equipment and operation costs with reduced generation of hazardous substances.

Description

明細書 ポリ塩化ビフエエールの無害化方法および装置 技術分野  Description Method and apparatus for detoxifying polychlorinated biphenyls
本発明は、 ポリ塩化ビフエニール （PCB) の無害化方法および装置の 技術分野に属する。なお、本発明で処理する PC Bは、 PCB単独または P C Bを含む油、 溶剤などの液体をいう。 背景技術  The present invention belongs to the technical field of a method and an apparatus for detoxifying polychlorinated biphenyl (PCB). The PCB to be treated in the present invention refers to a liquid such as oil alone or a solvent containing PCB alone or PCB. Background art
PCBは、 物理的およぴィヒ学的に安定であり、 耐熱性および電気絶縁性 に優れるため、 単独でまたは他の鉱物油あるいは絶縁油と混合し、 電気機 器の絶縁油、 熱媒体、 潤滑油、 インキなどにおいて広く工業用製品に使用 されてきた。  PCBs are physically and logically stable, and have excellent heat resistance and electrical insulation properties. It has been widely used in industrial products such as oils, lubricants and inks.
し力 しながら、 これらの PC B含有物質は人体に有害であり、 かつ、 自 然界での分解が困難な環境汚染物質であることが判明して以来、 P C Bの 生産は中止され、 他方、 使用済みの PC B含有物質は回収され、 または保 管されていた P C Bを含む製品は、 その無害化処理が望まれている。  However, PCB production has been discontinued since these PCB-containing substances proved to be harmful to the human body and environmental pollutants that are difficult to decompose in nature. Used PCB-containing substances have been recovered, or products containing PCBs that have been stored are desired to be detoxified.
従来、 PCBを無害化処理する方法として、 化学的処理、 高温燃焼によ る処理、 金属ナトリウムによる処理などの研究、 開発が行われているが、 いずれの方法も、 設備おょぴ処理コスト、 有毒ガスの処理などの問題があ り、 現在、 世界的に見ても実用化段階には至っておらず、 廃棄された PC Bを容器に保存して放置しているのが現状である。  Conventionally, research and development have been conducted on detoxifying PCBs, such as chemical treatment, treatment by high-temperature combustion, and treatment with metallic sodium.Either method requires equipment and treatment costs, Due to problems such as the treatment of toxic gases, it has not yet reached the stage of practical use worldwide, and currently discarded PCBs are stored in containers and left unattended.
例えば、特開平 7— 241352号公報においては、 PCBを Ι Ι Ο ΟΌ 以上の高温.〖こおいて,する金属精鍊'溶解炉に添加し、 P C Βを熱;^^さ せる方法を提案している。 '  For example, Japanese Patent Application Laid-Open No. 7-241352 proposes a method in which a PCB is heated to a temperature higher than or equal to Ι Ι 〖添加 and then added to a metal refining furnace to heat the PC 熱. ing. '
しかしながら、 PCBは、化学的に安定であり、また不燃性であるため、 無理に熱分解させると、塩素系、硫化系の猛毒の有害物質が発生するので、 廃ガス対策に莫大な費用がかかり現実的には高温燃焼による処理はできな レ、0 However, PCBs are chemically stable and nonflammable, and if they are forcibly pyrolyzed, toxic and toxic substances such as chlorine and sulfide will be generated. Les is in reality a possible treatment by the high-temperature combustion, 0
本発明は、 上記従来の問題を解決するものであって、 設備および処理コ ストが安く、 しかも有害物質の発生が少ないポリ塩化ビフエエールの無害 化方法および装置を提供することを目的とする。 発明の開示 An object of the present invention is to solve the conventional problems described above, and an object of the present invention is to provide a method and an apparatus for detoxifying polychlorinated biphenyls, which are inexpensive in equipment and processing cost and generate less harmful substances. Disclosure of the invention
上記目的を達成するために、 本発明のポリ塩化ビフエユールの無害化方 法は、 ポリ塩化ビフェユール液と酸化アルミナぉよぴ二酸化ケイ素を超音 波乳化器に混入、 乳化させ、 乳ィヒされた乳化混成材を電気抵抗式溶融炉内 の溶融メタル上に投下し、 1 5 0 0 °Cないし 2 0 0 0。Cの温度で溶融、 ガ ラス状に処理してなることを特徴としている。  In order to achieve the above object, the method for detoxifying polychlorinated biphenyls according to the present invention comprises mixing a polychlorinated biphenyl solution and alumina oxide with silicon dioxide into an ultrasonic emulsifier, emulsifying the mixture, and emulsifying the milk. The emulsified hybrid material is dropped onto the molten metal in the electric resistance melting furnace, and the temperature is set at 150 ° C. to 200 ° C. It is characterized by being melted and processed into a glass at the temperature of C.
本発明者は、 ポリ塩化ビブェニール液と酸化アルミナぉよぴニ酸化ケィ 素を超音波エネルギーにより乳化させ、 一種の粘土状とすることが出来る 事を実験により発見し、 これを電気抵抗式溶融炉で溶融できることを実証 している。  The present inventor has found through experiments that the polychlorinated biphenyl liquid and alumina oxide silicon dioxide can be emulsified by ultrasonic energy to form a kind of clay, and this is known as an electric resistance melting furnace. It has been demonstrated that it can be melted by using.
また、 本発明のポリ塩ィ匕ビフエ二一ルの無害化装置は、 超音波乳化器 2 に接続されたポリ塩化ビフエニール液貯蔵タンク 1と、 超音波乳化器に口 一タリーキルン 3を介して接続された酸化アルミナ '二酸化ケイ素貯蔵タ ンク 4と、 超音波乳化器に監視部 8および電気抵抗測定部 9を介して接続 された電気抵抗式溶融炉 5と、 超音波乳ィヒ器により得られた乳化混成材を 超音波孚しィ匕器にフィードバックさせるフィードパック管 2 2と、 前記電気 抵抗測定部により乳化混成材の乳ィヒ状態を測定し不完全の乳化混成材をフ ィ一ドパック管を介して超音波乳化器にフィ一ドパックさせる自動制御部 In addition, the detoxifying device for the polychlorinated biphenyls of the present invention is connected to the polychlorinated biphenyl liquid storage tank 1 connected to the ultrasonic emulsifier 2 and connected to the ultrasonic emulsifier via a mouthpiece kiln 3. Alumina oxide '' silicon dioxide storage tank 4, electric resistance type melting furnace 5 connected to ultrasonic emulsifier via monitoring section 8 and electric resistance measuring section 9, and ultrasonic milk tank A feed pack tube 22 for feeding the resulting emulsified hybrid material back to an ultrasonic mixer, and measuring the milky state of the emulsified hybrid material by the electric resistance measuring unit and feeding the incomplete emulsified hybrid material to the feed pack. Automatic control unit to feed pack the ultrasonic emulsifier through a tube
1 0とを備えたことを特徴とする。 10 is provided.
なお、 上記構成に付加した番号は、 本発明の理解を容易にするために図 面と対比させるものであり、 これにより本発明の構成が何ら限定されるも のではない。  Note that the numbers added to the above configuration are compared with the drawings for easy understanding of the present invention, and the configuration of the present invention is not limited by this.
以下、 本発明の実施の形態を図面を参照しつつ説明する。  Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図 1は、 本発明のポリ塩ィヒビフエニールの無害化装置の 1実施形態を示 す構成図である。  FIG. 1 is a configuration diagram showing one embodiment of a detoxifying apparatus for polychlorinated phenyl according to the present invention.
ポリ塩ィ匕ビフエニール液の貯蔵タンク 1は、 電磁弁 V I， 配管 2 0、 ポ ンプ P 1を介して超音波乳化器 2に接続され、 また、 酸ィヒアルミナ'ニ酸ィ匕 ケィ素の混合材貯蔵タンク 4は、 電磁弁 V 4、 ロータリ一キルン 3、 配管 2 3、 電磁弁 V 9を介して超音波乳化器 2に接続されている。  The storage tank 1 for the polychloride biphenyl liquid is connected to an ultrasonic emulsifier 2 via a solenoid valve VI, a pipe 20 and a pump P1, and a mixture of acid alumina and diacid sodium. The storage tank 4 is connected to the ultrasonic emulsifier 2 via a solenoid valve V4, a rotary kiln 3, a pipe 23, and a solenoid valve V9.
超音波乳ィ匕器 2においては、 ポリ塩化ビフェニール液と酸化アルミナ.二 酸化ケィ素の混合材とが超音波エネルギーで乳化混成されて、 この乳化混 成材は、 電磁弁 V 2、 ポンプ P 2、 配管 2 1、 監視部 8、 電気抵抗測定部 9、 電磁弁 V 5を経て電気抵抗式溶融炉 5に送られ、 この電気抵抗式溶融 炉 5において、 溶融温度 1 5 0 0 ないし 2 0 0 0 で溶融されて、 ガラ ス材が溶融しているような状態になる。 In the ultrasonic mixer 2, a polychlorinated biphenyl liquid and a mixed material of alumina oxide and silicon dioxide are emulsified and mixed with ultrasonic energy, and the emulsified mixed material is supplied by a solenoid valve V2 and a pump P2. , Piping 21, monitoring unit 8, electric resistance measuring unit 9, solenoid valve V 5, are sent to electric resistance melting furnace 5, where the melting temperature is 1 500 to 200 0 Melted at 0, Gala The material is in a state where it is molten.
このガラス状溶融材は電気抵抗式溶融炉 5の外部に排出部 1 1から排出 され、 溶けた状態のガラス材が硬化されることにより、 ポリ塩化ビフエ二 —ルが酸化アルミナ ·二酸化ケィ素材とからなるガラス材となる。  The vitreous molten material is discharged from the discharge part 11 to the outside of the electric resistance melting furnace 5 and the molten glass material is hardened, so that the polychlorinated biphenyl is converted into an alumina oxide / dioxide material. Glass material.
配管 2 1に接続してある監視部 8には、 ガラス窓があり、 超音波乳化器 2で乳化混成されたポリ塩ィ匕ビフェニール材と酸化アルミナ'二酸化ケィ 素材との乳化混成状態を見ることができる。  The monitoring unit 8 connected to the pipe 21 has a glass window to check the emulsified state of the polychloride biphenyl material emulsified and mixed by the ultrasonic emulsifier 2 and the alumina oxide ' Can be.
また、 電気抵抗測定部 9で乳ィ匕混成材の電気抵抗値を自動的に測定し、こ の信号を自動制御部 1 0に送り、 抵抗値が高い （乳化度合いが低い） 場合 は、 配管 2 1に設けてある電磁弁 V 5が自動制御部 1 0により閉められ、 電気抵抗式溶融炉 5に不完全な乳ィ匕混成材がいかないようにすると同時に、 電磁弁 V 6を開いてポンプ P 2により不完全な混成材をフィードパック管 2 2を経て、 超音波乳化器 2にフィードパックさせる。  In addition, the electric resistance measurement unit 9 automatically measures the electric resistance value of the mixed material and sends this signal to the automatic control unit 10. If the electric resistance value is high (the emulsification degree is low), the piping 2 The solenoid valve V5 provided in 1 is closed by the automatic control unit 10 to prevent the imperfect mixed material from entering the electric resistance melting furnace 5, and at the same time, the solenoid valve V6 is opened and the pump is opened. The incomplete hybrid material is fed into the ultrasonic emulsifier 2 via the feed pack tube 22 by P 2.
このとき、 ポンプ P 1は停止し、 電磁弁 V I、 V 4は閉じ、 ロータリー キルン 3の回転は停止させる。  At this time, the pump P1 is stopped, the solenoid valves VI and V4 are closed, and the rotation of the rotary kiln 3 is stopped.
次に、 任意の時間経過後、 電気抵抗測定部 9で、 乳化混成材の抵抗値が 規定値になれば、 閉じられた電磁弁 V I、 V 4、 V 5が開かれて、 ポンプ 1、 口一タリーキルン 3が回転して通常の運転状態に戻る。  Next, after the elapse of an arbitrary time, when the resistance value of the emulsified hybrid material reaches the specified value in the electric resistance measuring unit 9, the closed solenoid valves VI, V4, and V5 are opened, and the pump 1 and the port are opened. One tally kiln 3 rotates and returns to normal operation.
電気抵抗式溶融炉 5からの排気は、 排気管 2 4に設けてある排気用ファ ン F 1で排気用チェンパ 7に送られ、 排気用チェンバ 7の内部にある排気 ガス処理フィルタと触媒で、 できるだけ環境を汚染しない排気ガスとして、 煙突 1 2から空間に排気される。  Exhaust gas from the electric resistance melting furnace 5 is sent to an exhaust chamber 7 by an exhaust fan F1 provided in an exhaust pipe 24, and is exhausted by an exhaust gas treatment filter and a catalyst inside the exhaust chamber 7, and The exhaust gas is exhausted from the chimney 12 into the space as exhaust gas that does not pollute the environment as much as possible.
排気管 2 5に設けたセンサ群 6は、 排気用チェンパ 7から排気に含まれ ている有害なガス類を検出、 基準値以上の場合は自動制御部 1 3が作動し て、 ファン F 1を停止、 電磁弁 V 7、 V 8を閉めてお^気チェンパ 7内の 気を停止して任意時間、 排気用チェンパ 7の内部に保留し、 排気ガス処理 フィルタと触媒により脱有害ガス化して、 センサ群 6での値が基準値以下 になれば、 自動制御部 1 3で電磁弁 V 7、 V 8が開いて、 排気用ファン F 1が作動して、 通常の排気を行う。 図面の簡単な説明 A sensor group 6 provided in the exhaust pipe 25 detects harmful gases contained in the exhaust gas from the exhaust chamber 7, and when the gas exceeds the reference value, the automatic control unit 13 operates to activate the fan F 1. Stop, close the solenoid valves V7 and V8, stop the air inside the air chamber 7 and hold it inside the exhaust chamber 7 for an arbitrary period of time. When the value of the sensor group 6 becomes equal to or less than the reference value, the solenoid valves V7 and V8 are opened by the automatic control unit 13, and the exhaust fan F1 operates to perform normal exhaust. BRIEF DESCRIPTION OF THE FIGURES
図 1は本発明のポリ塩化ビフエニールの無害化装置の 1実施形態を示す 構成図である。  FIG. 1 is a configuration diagram showing one embodiment of a polychlorinated biphenyl detoxifying apparatus of the present invention.
図 2は本発明に係わる電気抵抗式溶融炉の例を示し、図（A)縦断面図、 図 （B) は図 （A) の B— B線に沿う断面図、 図 （C) は電気回路を示す 図である。  FIG. 2 shows an example of an electric resistance melting furnace according to the present invention. FIG. 2 (A) is a longitudinal sectional view, FIG. 2 (B) is a sectional view taken along line BB of FIG. 2 (A), and FIG. FIG. 3 is a diagram showing a circuit.
図 1の電気抵抗式溶融炉 5の例を示し、 図 （A) は縦断面図、 図 （B) は図 （A) の B— B線に沿う断面図、図 （C) は電気回路を示す図である。 図 （A) およぴ図 （B) において、 乳化混成材 30の下部に在るメタル 溶融体 31は、 乳化混成材 30が溶融される以前に金属類の廃材を溶融し たものであり、 このメタル溶融体 31の上面に乳化混成材 30を堆積させ る。  Fig. 1 shows an example of the electric resistance type melting furnace 5 of Fig. 1; Fig. 1 (A) is a longitudinal sectional view, Fig. 1 (B) is a sectional view taken along line BB of Fig. 1 (A), and Fig. 1 (C) shows an electric circuit. FIG. In FIGS. (A) and (B), the metal melt 31 below the emulsified hybrid 30 is obtained by melting metal waste before the emulsified hybrid 30 is melted. The emulsified hybrid material 30 is deposited on the upper surface of the metal melt 31.
溶融炉 5の天井部 32には、 2本の断面四角形状の黒鉛電極 33 a、 33 bが天井部 32を貫通して昇降可能に配設され、 黒鉛電極 33 a、 33 bの外周面はモリブデン部材 Mで被覆されており、 先端はメタル溶融 体 31中に埋没され、 メタル溶融体 31上乳化混成材 30が投下されてい る。  On the ceiling 32 of the melting furnace 5, two graphite electrodes 33a, 33b having a rectangular cross section are arranged so as to be able to move up and down through the ceiling 32, and the outer peripheral surfaces of the graphite electrodes 33a, 33b are The tip is buried in a metal melt 31, and the emulsified hybrid material 30 is dropped on the metal melt 31.
黒口、電極 33 a、 33bには電力供給ケープノレ 34 a, 34bが接続 されている。  A power supply cape notch 34a, 34b is connected to the black mouth and the electrodes 33a, 33b.
図 1 (C) に示すように、 電力供給ケープノレ 34 a, 34 bは、 電源変 圧器 35の 2次側単相の電力供給端子 35 b. 35 cに接続され、 電源変 圧器 35の 1次側 35 aの接続用端子 U， B， Wは 3相電源に接続されて いる。  As shown in Fig. 1 (C), the power supply cape clamps 34a and 34b are connected to the single-phase power supply terminal 35b.35c on the secondary side of the power transformer 35, and are connected to the primary side of the power transformer 35. The connection terminals U, B, and W on the side 35a are connected to a three-phase power supply.
本例による電極は、 黒鉛材の外周面をモリブデン Mで被覆することによ り、 各電極の構造的に強度が増大し、 また、 温度的に約 2600 まで使 用できる利点があるので、 乳化混成材または廃棄金属片が電極に当たって も電極が破損することが少なくなり、 その分だけ処理コストを低減させる ことができる。 そして、 溶融した乳化混成材 30は、 無害のガラス状にな つて外部に排出され、 溶融炉 5に投入された有無害の金属類は、 溶融され て合金材となり外部に排出される。  The electrode according to this example has the advantage of increasing the structural strength of each electrode by covering the outer peripheral surface of graphite material with molybdenum M, and has the advantage that it can be used up to about 2600 in terms of temperature. Even if the hybrid material or the waste metal piece hits the electrode, the electrode is less likely to be damaged, and the processing cost can be reduced accordingly. Then, the melted emulsified hybrid material 30 is formed into a harmless glass and discharged to the outside, and the harmless metals introduced into the melting furnace 5 are melted to form an alloy material and discharged to the outside.
1…ポリ塩化ビフエニール液貯蔵タンク 2·'·超音波乳化器  1… polychlorinated biphenyl liquid storage tank 2 ··· ultrasonic emulsifier
3 ···ロータリーキルン 4·''酸化アルミナ'二酸化ケイ素貯蔵タンク 3 Rotary kiln 4 `` Alumina oxide '' silicon dioxide storage tank
5···電気抵抗式溶融炉 8…監視部 9···電気抵抗測定 5 Electric resistance melting furnace 8 Monitoring section 9 Electric resistance measurement
10···自動制御部 22…フィードバック管 産業上の利用可能性 10 Automatic control unit 22 Feedback tube Industrial applicability
以上の説明から明らかなように、 本発明によれば、 超音波乳化器におい てポリ塩化ビフェニール液は、 酸化アルミナ ·二酸化ケィ素の粉体材と混合、 乳化混成されて、 一種の粘土状となり、 この乳化混成材を電気抵抗式溶融 炉の高温下で瞬時に溶融するので、 乳化混成材は、 酸化アルミナ ·二酸化ケ ィ素でガラス状になるため、 有害ガスの発生は極めて微小であり、 お気用 チェンバ内部のフィルタと触媒等で排気中の有害ガス成分は基準以下とな る。  As is clear from the above description, according to the present invention, in an ultrasonic emulsifier, a polychlorinated biphenyl liquid is mixed with a powder material of alumina oxide / silicon dioxide, emulsified and mixed to form a kind of clay. Since this emulsified hybrid material is instantaneously melted at a high temperature in an electric resistance melting furnace, the emulsified hybrid material becomes glassy with alumina oxide and silicon dioxide. The harmful gas components in the exhaust gas will be below the standard due to the filter and catalyst inside the safety chamber.
また、 ガラス状材は化学的に安定であり、 無害化されているので、 路材 等に使用することができる。  In addition, the glassy material is chemically stable and detoxified, so that it can be used for road materials and the like.

Claims

請求の範囲 ポリ塩ィ匕ビフェニール液と酸化アルミナぉよび二酸化ケィ素を超音波 乳化器に混入、 乳化させ、 乳化された乳化混成材を電気抵抗式溶融炉内の 溶融メタル上に投下し、 1 5 0 0 °Cないし 2 0 0 0での温度で溶融、 ガラ ス状に処理してなることを特徴とするポリ塩ィ匕ビフエニールの無害化方法。 超音波乳化器に接続されたポリ塩化ビフェニール液貯蔵タンクと、 超音 波乳化器にロータリーキルンを介して接続された酸化アルミナ '二酸化ケ ィ素貯蔵タンクと、 超音波乳化器に監視部および電気抵抗測定部を介して 接続された電気抵抗式溶融炉と、 超音波乳化器により得られた乳化混成材 を超音波乳化器にフィードパックさせるフィードパック管と、 前記電気抵 抗測定部により乳化混成材の乳ィ匕状態を測定し不完全の乳化混成材をフィ 一ドパック管を介して超音波乳化器にフィードパックさせる自動制御部と を備えたことを特徴とするポリ塩化ビフエニールの無害化装置。 Claims: Polychlorinated biphenyl liquid, alumina oxide and silicon dioxide are mixed and emulsified in an ultrasonic emulsifier, and the emulsified mixed material is dropped on molten metal in an electric resistance melting furnace. A method for detoxifying polychloride biphenyl, which is obtained by melting at a temperature of 500 ° C. to 2000 and processing it into a glass. Polychlorinated biphenyl liquid storage tank connected to ultrasonic emulsifier, alumina oxide silicon dioxide storage tank connected to ultrasonic emulsifier via rotary kiln, monitoring unit and electric resistance in ultrasonic emulsifier An electric resistance melting furnace connected via a measuring unit, a feed pack tube for feeding the emulsified hybrid material obtained by the ultrasonic emulsifier to the ultrasonic emulsifier, and an emulsified hybrid material by the electric resistance measuring unit An automatic control unit for measuring the state of the mulching and feeding the incomplete emulsified hybrid material to an ultrasonic emulsifier via a feed pack tube.
PCT/JP2001/008172 2001-09-20 2001-09-20 Method and apparatus for rendering polychlorinated biphenyl harmless WO2003026745A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7211038B2 (en) * 2001-09-25 2007-05-01 Geosafe Corporation Methods for melting of materials to be treated

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Publication number Priority date Publication date Assignee Title
JPH04166172A (en) * 1990-10-31 1992-06-12 Taiho Sangyo Kk Treatment of container for liquefied organic halide
US6061383A (en) * 1999-07-26 2000-05-09 Setsu Anzai Method and apparatus for tuning polychlorinated biphenyl to harmless
JP2001104512A (en) * 1999-10-05 2001-04-17 Yamada Sangyo Kk Decomposition treatment method for halogen compound
JP2001293104A (en) * 2000-03-02 2001-10-23 Ryoji Watabe Method of turning polychlorinated biphenyl oil to resource

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04166172A (en) * 1990-10-31 1992-06-12 Taiho Sangyo Kk Treatment of container for liquefied organic halide
US6061383A (en) * 1999-07-26 2000-05-09 Setsu Anzai Method and apparatus for tuning polychlorinated biphenyl to harmless
JP2001104512A (en) * 1999-10-05 2001-04-17 Yamada Sangyo Kk Decomposition treatment method for halogen compound
JP2001293104A (en) * 2000-03-02 2001-10-23 Ryoji Watabe Method of turning polychlorinated biphenyl oil to resource

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7211038B2 (en) * 2001-09-25 2007-05-01 Geosafe Corporation Methods for melting of materials to be treated
US7429239B2 (en) 2001-09-25 2008-09-30 Geosafe Corporation Methods for melting of materials to be treated

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