JP2003299941A - Hydrothermal oxidative reaction treatment apparatus and method using the same - Google Patents

Hydrothermal oxidative reaction treatment apparatus and method using the same

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Publication number
JP2003299941A
JP2003299941A JP2002102540A JP2002102540A JP2003299941A JP 2003299941 A JP2003299941 A JP 2003299941A JP 2002102540 A JP2002102540 A JP 2002102540A JP 2002102540 A JP2002102540 A JP 2002102540A JP 2003299941 A JP2003299941 A JP 2003299941A
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JP
Japan
Prior art keywords
organic polymer
molecular weight
hydrothermal
polymer compound
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2002102540A
Other languages
Japanese (ja)
Inventor
Masaaki Wakita
正明 脇田
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.)
Komatsu Ltd
Kurita Water Industries Ltd
Original Assignee
Komatsu Ltd
Kurita Water Industries Ltd
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 Komatsu Ltd, Kurita Water Industries Ltd filed Critical Komatsu Ltd
Priority to JP2002102540A priority Critical patent/JP2003299941A/en
Publication of JP2003299941A publication Critical patent/JP2003299941A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Processing Of Solid Wastes (AREA)
  • Physical Water Treatments (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrothermal oxidative reaction treatment apparatus capable of performing hydrothermal reaction simply and efficiently while suppressing the formation of char. <P>SOLUTION: A substance to be treated in a storage tank 1 for the substance to be treated is introduced into a chemical treatment tank 2, while an oxidation- reduction chemical agent is added to the chemical treatment tank 2 from a chemical agent supply passage 13 to convert an organic high-molecular compound in the substance to be treated to a low-molecular compound. The low- molecular substance to be treated is sent to the supply device 15 of a hydrothermal reactor 4 by a high pressure pump 17, and mixed with an oxidizing agent sent from an oxidizing agent tank 5. The mixed stream is supplied to the hydrothermal reactor 4 as a descending flow, and held to a supercritical or sub-critical state to be subjected to hydrothermal reaction. <P>COPYRIGHT: (C)2004,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は有機高分子化合物を
水の超臨界または亜臨界状態で水熱反応により酸化分解
する水熱酸化反応処理装置および方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a hydrothermal oxidation reaction treatment apparatus and method for oxidatively decomposing an organic polymer compound by hydrothermal reaction in a supercritical or subcritical state of water.

【０００２】[0002]

【従来の技術】被処理物を処理して酸化分解や加水分解
を行うことにより、廃棄物を処理したり、エネルギーを
生成したり、化学物質を製造したりする水熱反応処理は
３０年以上にわたって研究され、利用されている。特
に、近年、水の超臨界または亜臨界状態で、被処理物と
酸化剤を含んだ水とを水熱反応器で反応させることによ
り、燃焼を含む酸化反応（以下、単に反応という場合が
ある）を生じさせ、被処理物中の有機物を短時間でほぼ
完全に分解する水熱酸化反応（以下、単に水熱反応とい
う場合がある）処理が注目されている。2. Description of the Related Art Hydrothermal reaction treatment for treating wastes, generating energy, or producing chemical substances by treating an object to be treated and oxidatively decomposing or hydrolyzing it is more than 30 years. Has been studied and used for. In particular, in recent years, in a supercritical or subcritical state of water, by reacting an object to be treated with water containing an oxidant in a hydrothermal reactor, an oxidation reaction including combustion (hereinafter, may be simply referred to as a reaction ) Is generated, and a hydrothermal oxidation reaction (hereinafter sometimes simply referred to as a hydrothermal reaction) treatment for decomposing an organic substance in an object to be treated almost completely in a short time is drawing attention.

【０００３】水熱反応により被処理物を酸化分解する場
合、被処理物、酸化剤、水を加圧、加熱し水熱反応器へ
供給して酸化反応させる。反応の結果、有機物は酸化分
解され、水と二酸化炭素からなる高温高圧の液体と、乾
燥またはスラリー状態の灰分や塩類等の固体を含む反応
生成物が得られる。しかし、被処理物の種類や反応条件
などにより水熱反応器や予熱器ですす状物質（チャー）
が生成する場合が有り、弁などが閉塞したり、処理水中
に流出するなどの問題が生じる場合がある。When an object to be treated is oxidatively decomposed by a hydrothermal reaction, the object to be treated, an oxidant and water are pressurized and heated and supplied to a hydrothermal reactor to cause an oxidation reaction. As a result of the reaction, the organic matter is oxidatively decomposed to obtain a reaction product containing a high-temperature and high-pressure liquid composed of water and carbon dioxide and a solid such as ash and salts in a dried or slurry state. However, depending on the type of material to be treated and reaction conditions, soot-like substances (chars) in hydrothermal reactors and preheaters
May be generated, which may cause problems such as blockage of valves and the like, and leakage into treated water.

【０００４】とろこで特開２０００−６１４２３号に
は、有機廃棄物と水を超臨界状態で低分子量化し、その
生成物と酸化剤を混合し亜臨界状態で酸化する廃棄物処
理方法が記載されている。この方法は有機廃棄物に含ま
れる無機物が水熱反応器表面に析出して水熱反応器を閉
塞してしまう問題を解決するための方法であり、有機廃
棄物を低分子量化する工程を含んでいるが、超臨界状態
で低分子量化を行っているので、チャーの生成を防止す
ることはできない。In Japanese Patent Laid-Open No. 2000-61423, there is described a waste treatment method in which organic waste and water are made to have a low molecular weight in a supercritical state, and the product and an oxidizing agent are mixed and oxidized in a subcritical state. Has been done. This method is a method for solving the problem that the inorganic substances contained in the organic waste deposit on the surface of the hydrothermal reactor and block the hydrothermal reactor, and include a step of reducing the molecular weight of the organic waste. However, since the molecular weight is lowered in the supercritical state, it is not possible to prevent the formation of char.

【０００５】[0005]

【発明が解決しようとする課題】本発明の課題は、チャ
ーの生成を抑制して、簡単に効率よく水熱反応を行うこ
とができる水熱酸化反応処理装置および方法を提案する
ことである。SUMMARY OF THE INVENTION An object of the present invention is to propose a hydrothermal oxidation reaction treatment apparatus and method capable of suppressing the production of char and performing a hydrothermal reaction simply and efficiently.

【０００６】[0006]

【課題を解決するための手段】本発明は次の水熱酸化反
応処理装置および方法である。 （１） 有機高分子化合物を含む被処理物を水の超臨界
または亜臨界状態で水熱酸化反応により処理する水熱酸
化反応処理装置において、有機高分子化合物を低分子化
する低分子化装置と、低分子化した有機高分子化合物を
含む被処理物を水の超臨界または亜臨界状態で水熱酸化
反応により処理する水熱反応器とを有する水熱酸化反応
処理装置。 （２） 低分子化装置が、有機高分子化合物に薬剤を接
触させて低分子化する薬剤処理装置、有機高分子化合物
に超音波を照射して低分子化する超音波照射装置、有機
高分子化合物に光を照射して低分子化する光照射装置、
有機高分子化合物にオゾンを接触させて低分子化するオ
ゾン処理装置、有機高分子化合物を電気分解する電気分
解装置、またはこれらを組み合せた装置である上記
（１）記載の装置。 （３） 有機高分子化合物が合成有機高分子である上記
（１）または（２）記載の装置。 （４） 有機高分子化合物を含む被処理物を水の超臨界
または亜臨界状態で水熱酸化反応により処理する水熱酸
化反応処理方法において、有機高分子化合物を低分子化
する低分子化工程と、低分子化した有機高分子化合物を
含む被処理物を水の超臨界または亜臨界状態で水熱酸化
反応により処理する水熱反応工程とを有する水熱酸化反
応処理方法。 （５） 低分子化工程が、有機高分子化合物に薬剤を接
触させて低分子化する薬剤処理、有機高分子化合物に超
音波を照射して低分子化する超音波照射、有機高分子化
合物に光を照射して低分子化する光照射、有機高分子化
合物にオゾンを接触させて低分子化するオゾン処理、有
機高分子化合物を電気分解する電気分解、またはこれら
を組み合せて行う工程である上記（４）記載の方法。 （６） 有機高分子化合物が合成有機高分子である上記
（４）または（５）記載の方法。The present invention provides the following hydrothermal oxidation reaction treatment apparatus and method. (1) In a hydrothermal oxidation reaction treatment device for treating an object to be treated containing an organic polymer compound by a hydrothermal oxidation reaction in a supercritical or subcritical state of water, a molecular weight reduction device for lowering the molecular weight of the organic polymer compound And a hydrothermal reactor for treating an object to be treated containing a low molecular weight organic polymer compound in a supercritical or subcritical state of water by a hydrothermal oxidation reaction. (2) A low molecular weight device is a drug treatment device that lowers the molecular weight by contacting a drug with an organic polymer compound, an ultrasonic irradiation device that irradiates an organic high molecular compound with ultrasonic waves to lower the molecular weight, and an organic polymer A light irradiation device that irradiates a compound with light to reduce its molecular weight,
The apparatus according to (1) above, which is an ozone treatment apparatus for bringing an organic polymer compound into contact with ozone to lower the molecular weight thereof, an electrolysis apparatus for electrolyzing an organic polymer compound, or an apparatus combining these. (3) The device according to (1) or (2) above, wherein the organic polymer compound is a synthetic organic polymer. (4) In a hydrothermal oxidation reaction treatment method of treating an object to be treated containing an organic polymer compound by a hydrothermal oxidation reaction in a supercritical or subcritical state of water, a molecular weight reduction step of lowering the molecular weight of the organic polymer compound And a hydrothermal reaction step of treating an object to be treated containing a low molecular weight organic polymer compound by a hydrothermal oxidation reaction in a supercritical or subcritical state of water. (5) The process of lowering the molecular weight is to treat the organic polymer compound with a drug to lower the molecular weight thereof, to irradiate the organic polymer compound with ultrasonic waves to lower the molecular weight of the organic polymer compound. It is a step of performing light irradiation for lowering the molecular weight by irradiating light, ozone treatment for contacting ozone with an organic polymer compound to lower the molecular weight, electrolysis for electrolyzing the organic polymer compound, or a combination thereof. (4) The method described. (6) The method according to (4) or (5) above, wherein the organic polymer compound is a synthetic organic polymer.

【０００７】本発明で水熱酸化反応に供する被処理物は
有機高分子化合物を含む被処理物であり、樹脂、ゴム、
繊維、塗料、インキ、接着剤、電子製品や分離剤等の高
機能性材料などを製造したり使用している工場などから
排出される廃棄物や廃液などがあげられる。上記有機高
分子化合物の分子量は通常１０，０００〜１０，００
０，０００程度である。有機高分子化合物の具体的なも
のとしては、セルロース、デンプン、タンパク質等の天
然高分子またはそれらを改質したもの；ポリスチレンス
ルホン酸ナトリウム、ポリアクリル酸、ポリメタクリル
酸、ポリビニルアルコール、これらの誘導体等の水に可
溶の合成有機高分子；ポリエチレン、ポリプロピレン、
ポリスチレン、ナイロン、ポリブタジエン、ポリ塩化ビ
ニル、ポリ酢酸ビニル、これらの誘導体等の水に不溶ま
たは難溶の合成有機高分子などがあげられる。前記分子
量の合成有機高分子はチャーが生成しやすいので、本発
明の装置および方法は合成有機高分子、特に水に溶解し
ている合成有機高分子を含む被処理物の処理に適してい
る。有機高分子化合物は成形体であってもよく、この場
合は粉砕して処理に供することができる。被処理物中に
は有機高分子化合物以外のものが含まれていてもよい。The object to be treated in the present invention, which is subjected to the hydrothermal oxidation reaction, is an object containing an organic polymer compound, such as resin, rubber,
Examples include wastes and waste liquids discharged from factories that manufacture and use highly functional materials such as fibers, paints, inks, adhesives, electronic products and separating agents. The molecular weight of the organic polymer compound is usually 10,000 to 10,000.
It is about 10,000. Specific examples of the organic polymer compound include natural polymers such as cellulose, starch, and proteins, or those modified from them; sodium polystyrene sulfonate, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, derivatives thereof, and the like. Water soluble synthetic organic polymers; polyethylene, polypropylene,
Examples thereof include synthetic organic polymers insoluble or sparingly soluble in water such as polystyrene, nylon, polybutadiene, polyvinyl chloride, polyvinyl acetate, and their derivatives. Since the synthetic organic polymer having the above-mentioned molecular weight tends to generate char, the apparatus and method of the present invention are suitable for treating an object to be treated containing a synthetic organic polymer, particularly a synthetic organic polymer dissolved in water. The organic polymer compound may be a molded product, and in this case, it can be crushed and subjected to treatment. The object to be treated may contain a substance other than the organic polymer compound.

【０００８】本発明で使用する低分子化装置としては、
有機高分子化合物に薬剤を接触させて低分子化する薬剤
処理装置、有機高分子化合物に超音波を照射して低分子
化する超音波照射装置、有機高分子化合物に光を照射し
て低分子化する光照射装置、有機高分子化合物にオゾン
を接触させて低分子化するオゾン処理装置、有機高分子
化合物を電気分解する電気分解装置などが使用でき、こ
れらを組み合せて使用することもできる。The molecular weight reducing device used in the present invention is as follows:
Drug treatment device that lowers the molecular weight by contacting a drug with an organic polymer compound, ultrasonic irradiation device that irradiates an organic polymer compound with ultrasonic waves to lower the molecular weight, and irradiates light to an organic polymer compound to lower the molecular weight It is possible to use a light irradiating device for converting the organic polymer compound, an ozone treatment device for bringing the organic polymer compound into contact with ozone to lower the molecular weight thereof, an electrolyzer for electrolyzing the organic polymer compound, and the like, or a combination thereof.

【０００９】前記薬剤処理装置では、被処理物に薬剤を
接触させ、酸化還元反応または加水分解反応などにより
有機高分子化合物の主鎖を切断して低分子化する。薬剤
処理装置としては、被処理物と薬剤とを混合して反応さ
せる反応槽などが使用できる。薬剤として使用する酸化
または還元薬剤としては、過酸化水素、次亜塩素酸、過
ヨウ素酸、過マンガン酸、クロム酸、アスコルビン酸、
エリソルビン酸、これらの塩、また金属との組み合せな
どがあげられる。In the chemical treatment apparatus, a chemical is brought into contact with an object to be treated, and the main chain of the organic polymer compound is cut by an oxidation-reduction reaction or a hydrolysis reaction to lower the molecular weight. As the chemical treatment device, a reaction tank or the like that mixes the substance to be treated and the chemical to cause a reaction can be used. Examples of the oxidizing or reducing agents used as drugs include hydrogen peroxide, hypochlorous acid, periodate, permanganate, chromic acid, ascorbic acid,
Examples include erythorbic acid, salts thereof, and combinations with metals.

【００１０】被処理物の有機高分子化合物が水溶性であ
る場合、有機高分子化合物が溶解している被処理物に酸
化または還元薬剤を添加し、攪拌下に反応を行って低分
子化する。このとき加熱、酸素の吹き込みは反応促進の
点から好ましい。被処理物の有機高分子化合物が水に溶
解しない場合、固体を粉砕して、または粉砕することな
く水に分散させ、有機高分子化合物が分散した被処理物
に酸化または還元薬剤を添加し、攪拌下に反応を行って
低分子化する。固体の場合、反応が遅いので、加熱、酸
素の吹き込みなどの条件を過酷にするのが好ましい。When the organic polymer compound of the object to be treated is water-soluble, an oxidizing or reducing agent is added to the object to be treated in which the organic polymer compound is dissolved, and the reaction is carried out with stirring to lower the molecular weight. . At this time, heating and blowing oxygen are preferable from the viewpoint of accelerating the reaction. If the organic polymer compound of the object to be treated is not dissolved in water, the solid is crushed or dispersed in water without crushing, and an oxidizing or reducing agent is added to the object to be treated in which the organic polymer compound is dispersed, The reaction is carried out with stirring to lower the molecular weight. In the case of a solid, since the reaction is slow, it is preferable to make the conditions such as heating and blowing of oxygen severe.

【００１１】また加水分解反応により低分子化するに
は、有機高分子化合物に酸またはアルカリを接触させて
低分子化する。この場合、加熱するのが好ましい。また
有機高分子化合物がタンパク質、多糖類などの場合、酵
素と接触させ酵素反応により低分子化することができ
る。In order to lower the molecular weight by the hydrolysis reaction, the organic polymer compound is brought into contact with acid or alkali to lower the molecular weight. In this case, it is preferable to heat. Further, when the organic polymer compound is a protein, a polysaccharide or the like, it can be made into a low molecular weight compound by bringing it into contact with an enzyme to cause an enzymatic reaction.

【００１２】前記超音波照射装置では、被処理物に超音
波を照射して有機高分子化合物を低分子化する。この
時、加熱したり、酸化剤を添加することもできる。前記
光照射装置では、被処理物に高圧〜低圧水銀ランプで発
生させた光を照射し、有機高分子化合物を低分子化す
る。この時、酸素、空気の吹き込みは好ましい。また、
過酸化水素などのラジカルを発生する薬剤を併用すると
効果的である。In the ultrasonic irradiation device, ultrasonic waves are applied to the object to be processed to lower the molecular weight of the organic polymer compound. At this time, it is possible to heat or add an oxidant. In the light irradiation device, the object to be processed is irradiated with light generated by a high-pressure to low-pressure mercury lamp to lower the molecular weight of the organic polymer compound. At this time, blowing of oxygen and air is preferable. Also,
It is effective to use a drug that generates radicals such as hydrogen peroxide together.

【００１３】前記オゾン処理装置では、市販のオゾナイ
ザーなどを利用して、被処理物にオゾンまたはオゾン含
有ガスを接触させ、有機高分子化合物を低分子化する。
この時光照射を併用することもできる。接触方法は限定
されず、例えば被処理物が液状の場合はオゾンまたはオ
ゾン含有ガスを被処理液に吹き込む方法などが採用でき
る。前記電気分解装置では、液状の被処理物に電気エネ
ルギーを与えて電解反応により有機高分子化合物を電気
分解させて低分子化する。In the ozone treatment apparatus, a commercially available ozonizer or the like is used to bring ozone or an ozone-containing gas into contact with the object to be treated to lower the molecular weight of the organic polymer compound.
At this time, light irradiation can be used together. The contact method is not limited. For example, when the object to be processed is liquid, a method of blowing ozone or an ozone-containing gas into the liquid to be processed can be adopted. In the electrolyzer, electric energy is applied to a liquid object to be electrolyzed to electrolyze an organic polymer compound to lower its molecular weight.

【００１４】本発明で使用する低分子化装置としては、
反応速度が速く、しかも誘導期間が存在しないかまたは
短く、かつ装置が小型化できるので、前記薬剤処理装置
が好ましい。上記低分子化装置では、有機高分子化合物
の分子量が通常１０，０００未満になるように低分子量
化する。The molecular weight reducing device used in the present invention is as follows:
The drug treatment device is preferable because the reaction rate is high, the induction period does not exist or is short, and the device can be downsized. In the above-mentioned molecular weight lowering device, the molecular weight of the organic polymer compound is usually lowered to less than 10,000.

【００１５】本発明で使用する水熱反応器としては従来
から水熱反応器として使用されているものが制限なく使
用できる。本発明では、前記低分子化装置により被処理
物中の有機高分子化合物を低分子化した後、この被処理
物を水熱反応器に導入し、水熱酸化反応を行う。水熱反
応は、従来と同じ方法で行うことができる。As the hydrothermal reactor used in the present invention, those conventionally used as hydrothermal reactors can be used without limitation. In the present invention, the organic polymer compound in the material to be treated is reduced in molecular weight by the molecular weight reduction device, and then the material to be treated is introduced into a hydrothermal reactor to carry out a hydrothermal oxidation reaction. The hydrothermal reaction can be carried out in the same manner as conventional methods.

【００１６】ここで水熱反応とは、超臨界または亜臨界
状態の高温高圧の水および酸化剤の存在下に有機物を酸
化反応により酸化分解する反応である。超臨界状態とは
３７４℃以上、２２ＭＰａ以上の状態である。また亜臨
界状態とは例えば３７４℃以上、２．５ＭＰａ以上２２
ＭＰａ未満あるいは３７４℃未満、２２ＭＰａ以上の状
態、あるいは３７４℃以下、２２ＭＰａ未満であっても
臨界点に近い高温高圧状態をいう。The hydrothermal reaction is a reaction of oxidatively decomposing an organic substance by an oxidative reaction in the presence of water at high temperature and high pressure in a supercritical or subcritical state and an oxidizing agent. The supercritical state is a state of 374 ° C. or higher and 22 MPa or higher. The subcritical state is, for example, 374 ° C. or higher and 2.5 MPa or higher 22
A state of less than MPa, less than 374 ° C., 22 MPa or more, or a temperature of 374 ° C. or less, less than 22 MPa is a high temperature / high pressure state close to the critical point.

【００１７】このような水熱反応は低分子化された有機
高分子化合物が水および酸化剤と混合した状態で水熱反
応器において行われ、これらの混合物が水熱反応器内部
で水熱反応を受ける。酸化剤としては、空気、酸素、液
体酸素、過酸化水素水、硝酸、亜硝酸、硝酸塩、亜硝酸
塩等を用いることができる。酸化剤は、被処理物と混合
されて供給されてもよいし、供給口を二重管ノズルにし
て複層流として供給してもよい。また必要により触媒や
中和剤等が添加される場合があるが、これらは被処理物
と混合して、あるいは別々に水熱反応器に供給すること
ができる。Such a hydrothermal reaction is carried out in a hydrothermal reactor in a state in which a low molecular weight organic polymer compound is mixed with water and an oxidant, and the mixture thereof is hydrothermally reacted inside the hydrothermal reactor. Receive. As the oxidizing agent, air, oxygen, liquid oxygen, hydrogen peroxide solution, nitric acid, nitrous acid, nitrate, nitrite or the like can be used. The oxidant may be mixed with the material to be treated and supplied, or may be supplied as a multi-layered flow with a double-tube nozzle as the supply port. If necessary, a catalyst, a neutralizing agent, etc. may be added, and these can be supplied to the hydrothermal reactor either as a mixture with the object to be treated or separately.

【００１８】水熱反応において被処理物の熱量が不足す
る場合は、補助燃料を水熱反応器に供給して反応を行う
ことができる。補助燃料としては、灯油、ケロシン、イ
ソプロピルアルコール、メタノール、アセトン等をあげ
ることができる。補助燃料は純物質である必要はなく、
例えば他の有機物、無機物、水分などを含有する廃溶媒
であってもよい。When the amount of heat of the object to be treated is insufficient in the hydrothermal reaction, the auxiliary fuel can be supplied to the hydrothermal reactor to carry out the reaction. Examples of auxiliary fuels include kerosene, kerosene, isopropyl alcohol, methanol, acetone and the like. The auxiliary fuel does not have to be a pure substance,
For example, it may be a waste solvent containing other organic substances, inorganic substances, water and the like.

【００１９】本発明で用いられる水熱反応器は超臨界ま
たは亜臨界状態で水熱反応を行うように、耐熱、耐圧材
料により、実質的に垂直方向に配置した筒状水熱反応器
で形成される。反応熱だけでは超臨界または亜臨界状態
に達しない場合には外部加熱手段を設けることができ
る。水熱反応器の形状は円筒、だ円筒、多角筒のものを
用いることができ、下端部はコーン状とすることができ
る。このような水熱反応器により超臨界または亜臨界状
態で水熱反応を行うと、有機物は酸化剤により酸化され
て最終的に水と二酸化炭素に分解され、あるいは加水分
解により低分子化し、無機物は固体あるいは溶融状態で
分離する。反応生成物はそのまま、または固形物を分離
後、冷却、減圧、固液分離等の操作により、ガス分、液
分、固形分に分離される。The hydrothermal reactor used in the present invention is formed of a tubular hydrothermal reactor which is arranged in a substantially vertical direction by a heat resistant and pressure resistant material so that the hydrothermal reaction is carried out in a supercritical or subcritical state. To be done. If the reaction heat alone does not reach the supercritical or subcritical state, an external heating means can be provided. The hydrothermal reactor may have a cylindrical shape, an elliptic shape, or a polygonal shape, and the lower end portion may have a cone shape. When a hydrothermal reaction is carried out in a supercritical or subcritical state by such a hydrothermal reactor, organic substances are oxidized by an oxidant and finally decomposed into water and carbon dioxide, or hydrolyzed to lower molecular weight, and inorganic substances Separates in the solid or molten state. The reaction product is separated as it is, or after solid matter is separated, it is separated into a gas content, a liquid content, and a solid content by operations such as cooling, pressure reduction, and solid-liquid separation.

【００２０】水熱反応器としては特開平１１−１５６１
８６号に示されているように、上部に逆流を伴う混合反
応域、下部に栓状流反応域を形成する実質的に垂直な水
熱反応器に、さらに上部に設けられた供給装置から被処
理物と酸化剤の混合流を下向流で供給して上部の混合反
応域で逆流を伴う混合流を形成して水熱反応を行い、下
部の栓状流反応域で平行な下向栓流を形成して追加の水
熱反応を行う構造のものが好ましい。As a hydrothermal reactor, JP-A-11-1561
As shown in No. 86, a substantially vertical hydrothermal reactor which forms a mixed reaction zone with backflow in the upper part and a plug flow reaction zone in the lower part is connected to a feed device provided on the upper part. A mixed flow of the treated product and the oxidant is supplied in a downward flow to form a mixed flow with a backflow in the upper mixing reaction zone to perform hydrothermal reaction, and a parallel downward plug in the lower plug flow reaction zone. A structure in which a stream is formed to carry out an additional hydrothermal reaction is preferable.

【００２１】水熱反応器の材質は制限されないが、ハス
テロイ、インコネル、ステンレス等の耐食性の材質が好
ましい。水熱反応器には耐腐食性ライナーを設けるのが
好ましい。耐腐食性ライナーは特に限定されず、特開平
１１−１５６１８６号に開示されたような耐腐食性ライ
ナーと圧力負荷壁との間に間隙が存在するような耐腐食
性ライナーを用いることができる。The material of the hydrothermal reactor is not limited, but is preferably a corrosion resistant material such as Hastelloy, Inconel or stainless steel. The hydrothermal reactor is preferably provided with a corrosion resistant liner. The corrosion-resistant liner is not particularly limited, and a corrosion-resistant liner having a gap between the corrosion-resistant liner and the pressure load wall as disclosed in JP-A-11-156186 can be used.

【００２２】水熱反応器には反応混合物を排出口から排
出する前に冷却するための冷却手段を設けることができ
る。冷却手段は特に限定されないが、水熱反応器内に水
を導入して冷却し、無機塩を溶解してその排出を促進す
ることができる。また、水熱反応器内に酸やアルカリを
含む水を導入して冷却し、アルカリや酸の中和を行うこ
とができる。固体の粘着性が著しい場合には、水熱反応
器の内壁に付着した固体を除去するための機械的除去装
置を設けることができる。固体除去のための機械的除去
装置は特に限定されないが、特開平１１−１５６１８６
号で開示された切欠窓部分を含む実質的に円筒状のスク
レーパが好適である。The hydrothermal reactor may be provided with cooling means for cooling the reaction mixture before it is discharged from the outlet. The cooling means is not particularly limited, but water can be introduced into the hydrothermal reactor to be cooled, and the inorganic salt can be dissolved to accelerate the discharge thereof. In addition, water containing an acid or an alkali can be introduced into the hydrothermal reactor and cooled to neutralize the alkali or the acid. A mechanical removal device for removing solids adhering to the inner wall of the hydrothermal reactor can be provided when the solids are extremely sticky. The mechanical removing device for removing solids is not particularly limited, but is disclosed in Japanese Patent Application Laid-Open No. 11-156186.
A substantially cylindrical scraper including a notched window portion as disclosed in US Pat.

【００２３】水熱反応の進行に伴って、水熱反応器内で
中和塩が堆積する場合は、水熱反応器内における塩の堆
積防止手段や排出手段の併用が望ましい。具体的な方法
としては、水熱反応器下部に水層を設けて塩を溶解、排
出する手段（特許２７２６２９３）や機械的に塩を掻き
取る手段（ＵＳＰ５，１００，５６０、特開平１０−１
５５６６号、特開平１１−２５３７８６号）、水熱反応
器表面から流体を噴出させて付着を防止する手段（特開
平９−２９９９６６号）など、公知の方法を採用するこ
とができる。When the neutral salt deposits in the hydrothermal reactor as the hydrothermal reaction progresses, it is desirable to use a salt deposition preventing means and a discharging means in the hydrothermal reactor. As a specific method, means for dissolving and discharging salt by providing a water layer in the lower part of the hydrothermal reactor (patent 2726293) and means for mechanically scraping salt (USP 5,100,560, JP-A-10-1)
5566, JP-A No. 11-253786), and means for ejecting a fluid from the surface of the hydrothermal reactor to prevent adhesion (JP-A No. 9-299966) can be used.

【００２４】水熱反応器から排出される反応流体中の固
形物を分離する分離手段を設けることができる。特に、
超臨界状態の反応流体中では無機塩類が溶解せずに固体
として含まれているため、不溶化している無機物を分離
することにより、処理水の再利用が容易になる。固形物
分離手段は特に限定されず、水熱反応器から反応流体を
導入する流入口および固体を除去した流体を排出する流
出口を備えた容器と、容器内に配設されて前記反応流体
に含まれている前記固体を除去し、排出する手段とを備
えたものが使用できる。また、冷却、減圧の工程で、気
液分離や固液分離の手段を設けることもできる。Separation means may be provided for separating solids in the reaction fluid discharged from the hydrothermal reactor. In particular,
Inorganic salts are not dissolved in the reaction fluid in the supercritical state but are contained as a solid, so that the treated water can be easily reused by separating the insolubilized inorganic substances. The solid matter separating means is not particularly limited, and a container having an inlet for introducing the reaction fluid from the hydrothermal reactor and an outlet for discharging the fluid from which the solid has been removed, and the reaction fluid disposed in the container to the reaction fluid. A means provided with a means for removing and discharging the contained solid can be used. Further, means for gas-liquid separation or solid-liquid separation can be provided in the steps of cooling and depressurizing.

【００２５】水熱反応器による反応開始の手段は特に制
限されない。通常、水熱反応器は反応開始にあたって所
定の反応温度付近に予熱される。予熱は加熱装置を水熱
反応器に設けるか、あるいは被処理物および／または酸
化剤供給路に設けて加熱された水や空気を導入して実施
することができる。通常、所定の温度、圧力に調整され
た後、被処理物を含む流体を供給して水熱反応を開始す
る。水熱反応によって有機物が分解され、反応熱が発生
する。水熱反応器上部に逆流を伴う混合反応域を設けた
場合、ここで逆流を伴う混合作用で有機物、酸化剤およ
び水熱反応器内容物などが十分に混合されるため、流体
の温度が上昇する。これにより供給される有機物は速や
かに水熱反応を開始し、安定した反応が継続されること
になる。反応流体は水熱反応器内を下向きに移動し、栓
状流反応域で継続反応した後、排出口から排出される。
水熱反応器の長さ：直径の比は１：１〜１００：１が好
ましい。The means for starting the reaction by the hydrothermal reactor is not particularly limited. Usually, the hydrothermal reactor is preheated to around a predetermined reaction temperature when starting the reaction. The preheating can be performed by providing a heating device in the hydrothermal reactor or by introducing heated water or air provided in the object to be treated and / or the oxidant supply passage. Usually, after being adjusted to a predetermined temperature and pressure, a fluid containing an object to be treated is supplied to start a hydrothermal reaction. Organic substances are decomposed by the hydrothermal reaction, and heat of reaction is generated. When a mixing reaction zone involving backflow is provided above the hydrothermal reactor, the temperature of the fluid rises because organic substances, oxidants, hydrothermal reactor contents, etc. are sufficiently mixed by the mixing action involving backflow. To do. As a result, the supplied organic substance promptly starts the hydrothermal reaction, and the stable reaction is continued. The reaction fluid moves downward in the hydrothermal reactor, continuously reacts in the plug flow reaction region, and is then discharged from the discharge port.
The length: diameter ratio of the hydrothermal reactor is preferably 1: 1 to 100: 1.

【００２６】水熱反応器を出た反応流体はそのまま、ま
たは固体を分離した後、冷却して減圧され気液分離され
る。水熱反応器内で冷却して液体が生成している場合は
水熱反応器を出た段階で固体とともに液体を分離し、必
要によりさらに冷却、気液分離および固液分離を行うこ
とができる。最終的に生成した水、気体、固体は、その
まま、エネルギー回収されたり、物質として再利用され
たり、そのままあるいは追加処理されて廃棄される。The reaction fluid leaving the hydrothermal reactor is used as it is, or after separating solids, it is cooled and decompressed to be separated into gas and liquid. When liquid is produced by cooling in the hydrothermal reactor, the liquid can be separated together with the solid at the stage of leaving the hydrothermal reactor, and further cooling, gas-liquid separation and solid-liquid separation can be performed if necessary. . The finally produced water, gas, and solid are directly recovered as energy, reused as a substance, or directly or additionally treated and disposed of.

【００２７】有機高分子化合物を低分子化した後水熱反
応することによりチャーの生成が防止できる理由は明確
ではないが、次のように推測される。すなわち、チャー
の生成は有機高分子化合物が水熱反応器で蒸発、酸化反
応する前に熱分解してしまうために起こると考えられる
が、有機高分子化合物を低分子化した後水熱反応するこ
とにより、被処理液の粘度が低下して反応器に注入され
る液滴が微細化するとともに、有機物の沸点が低下して
蒸発しやすくなって、熱分解することなく酸化反応し、
これによりチャーの生成が防止できるものと推測され
る。The reason why the formation of char can be prevented by hydrothermally reacting the organic polymer compound after lowering its molecular weight is not clear, but it is presumed as follows. That is, it is considered that the formation of char occurs because the organic polymer compound is thermally decomposed before being evaporated and oxidized in the hydrothermal reactor, but the organic polymer compound is hydrolyzed after lowering the molecular weight of the organic polymer compound. As a result, the viscosity of the liquid to be treated decreases and the droplets injected into the reactor become finer, and the boiling point of the organic substance decreases to facilitate evaporation, causing an oxidation reaction without thermal decomposition,
It is speculated that this can prevent the generation of char.

【００２８】[0028]

【発明の効果】本発明の水熱酸化反応処理装置は、被処
理物中の有機高分子化合物を低分子化する低分子化装置
を備えているので、チャーの生成を抑制して、簡単に効
率よく水熱反応を行うことができる。本発明の水熱酸化
反応処理方法は、被処理物中の有機高分子化合物を低分
子化する低分子化工程を含んでいるので、チャーの生成
を抑制して、簡単に効率よく水熱反応を行うことができ
る。EFFECT OF THE INVENTION Since the hydrothermal oxidation reaction treatment apparatus of the present invention is provided with a low molecular weight reducing apparatus for lowering the molecular weight of the organic polymer compound in the object to be treated, the generation of char can be suppressed to easily The hydrothermal reaction can be performed efficiently. The hydrothermal oxidation reaction treatment method of the present invention includes a step of lowering the molecular weight of the organic polymer compound in the object to be treated, so that the generation of char is suppressed, and the hydrothermal reaction is easily and efficiently performed. It can be performed.

【００２９】[0029]

【発明の実施の形態】以下、本発明の実施の形態を図面
により説明する。図１は実施形態の水熱反応処理装置の
系統図である。図１において、１は被処理物貯槽、２は
低分子化装置としての薬剤処理槽、３は熱交換器、４は
水熱反応器、５は酸化剤槽、６は気液分離器である。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a system diagram of the hydrothermal reaction treatment apparatus of the embodiment. In FIG. 1, 1 is an object storage tank, 2 is a chemical treatment tank as a molecular weight lowering device, 3 is a heat exchanger, 4 is a hydrothermal reactor, 5 is an oxidizer tank, and 6 is a gas-liquid separator. .

【００３０】被処理物貯槽１には被処理物を導入する被
処理物導入路１１が連絡している。薬剤処理槽２には被
処理物貯槽１から被処理物を導入する系路１２、および
薬剤を添加する薬剤供給路１３が連絡している。薬剤処
理槽２は被処理物貯槽１から被処理物を導入し、薬剤供
給路１３から酸化還元薬剤を添加し、槽内で混合して被
処理物中の有機高分子化合物を低分子化するように構成
されている。An object introduction path 11 for introducing an object is connected to the object storage tank 1. The chemical treatment tank 2 is connected to a system passage 12 for introducing the treatment object from the treatment object storage tank 1 and a chemical supply passage 13 for adding the chemical. The chemical treatment tank 2 introduces the treatment object from the treatment object storage tank 1, adds an oxidation-reduction agent from the chemical supply path 13, and mixes in the vessel to lower the molecular weight of the organic polymer compound in the treatment object. Is configured.

【００３１】薬剤処理槽２から、水熱反応器４の上部に
設けられた供給装置１５に系路１６が連絡している。こ
の系路１６には、有機高分子化合物を低分子化した被処
理物を供給する高圧ポンプ１７、および熱交換器３が設
けられている。供給装置１５には酸化剤を供給する酸化
剤槽５から高圧ポンプ１８を有する系路１９が連絡して
いる。この供給装置１５は酸化剤と被処理物の混合流を
水熱反応器４に下向流として供給するように取付けられ
ている。A system path 16 is connected from the chemical treatment tank 2 to a supply device 15 provided above the hydrothermal reactor 4. The system 16 is provided with a high-pressure pump 17 for supplying an object to be treated in which an organic polymer compound has a low molecular weight, and a heat exchanger 3. A line 19 having a high-pressure pump 18 communicates with the supply device 15 from the oxidant tank 5 for supplying the oxidant. The supply device 15 is installed so as to supply the mixed flow of the oxidant and the object to be treated to the hydrothermal reactor 4 as a downward flow.

【００３２】水熱反応器４は中空の反応器の上部に逆流
を伴う混合反応域、下部に栓状流反応域が形成されるよ
うになっている。水熱反応器４には必要により加熱装置
が設けられる。水熱反応器４の下部から系路２１が熱交
換器３に連絡し、熱交換器３から系路２２が気液分離器
６に連絡している。気液分離器６から減圧弁２３を有す
る気体排出路２４および減圧弁２５を有する液体排出路
２６が系外に連絡している。なお上記の装置においてポ
ンプ、弁等が必要であるが、省略して図示されている。The hydrothermal reactor 4 has a hollow reactor having a mixed reaction region accompanied by backflow at the upper part thereof and a plug flow reaction region at the lower part thereof. If necessary, the hydrothermal reactor 4 is provided with a heating device. A passage 21 communicates with the heat exchanger 3 from the lower part of the hydrothermal reactor 4, and a passage 22 communicates with the gas-liquid separator 6 from the heat exchanger 3. A gas discharge passage 24 having a pressure reducing valve 23 and a liquid discharge passage 26 having a pressure reducing valve 25 communicate with the outside of the system from the gas-liquid separator 6. Although a pump, a valve and the like are required in the above device, they are omitted in the drawing.

【００３３】上記の装置における処理は以下のように行
われる。まず被処理物導入路１１から有機高分子化合物
を含む被処理物、好ましくは有機高分子化合物が溶解し
ている被処理物を被処理物貯槽１に導入し、一時的に貯
留する。被処理物貯槽１内の被処理物は系路１２を通し
て薬剤処理槽２に導入するとともに薬剤供給路１３から
酸化還元薬剤を添加し、有機高分子化合物と薬剤とを接
触させ、有機高分子化合物を低分子化する。The processing in the above apparatus is performed as follows. First, an object to be processed containing an organic polymer compound, preferably an object to be processed in which an organic polymer compound is dissolved, is introduced from the object introduction path 11 into the object storage tank 1 and temporarily stored. The material to be processed in the material storage tank 1 is introduced into the chemical treatment tank 2 through the system path 12 and the redox chemical is added from the chemical supply path 13 to bring the organic polymer compound and the chemical into contact with each other. To lower the molecule.

【００３４】低分子化した被処理物は高圧ポンプ１７に
より系路１６から熱交換器３に導入して予熱したのち、
水熱反応器４の供給装置１５に送る。ここで酸化剤槽５
から高圧ポンプ１８により系路１９を通して送られる酸
化剤（例えば空気、過酸化水素水）と混合し、混合流を
水熱反応器４に下向流で供給して水熱反応を行う。水熱
反応器４では水の超臨界または亜臨界状態に保って水熱
反応を行う。The low molecular weight object to be treated is introduced into the heat exchanger 3 from the system passage 16 by the high pressure pump 17 and preheated,
It is sent to the supply device 15 of the hydrothermal reactor 4. Oxidizer tank 5 here
Is mixed with an oxidant (for example, air, hydrogen peroxide solution) sent from the high pressure pump 18 through the system line 19, and the mixed flow is supplied to the hydrothermal reactor 4 in a downward flow to perform the hydrothermal reaction. In the hydrothermal reactor 4, the hydrothermal reaction is carried out while keeping the water in a supercritical or subcritical state.

【００３５】供給装置１５から供給される混合流は水熱
反応器４の上部では逆流を伴う混合反応域を形成して酸
化分解が行われ、下部では乱流は解消して栓状流反応域
を形成して追加反応が行われる。The mixed flow supplied from the supply device 15 forms a mixed reaction zone accompanied by a backflow in the upper part of the hydrothermal reactor 4 to undergo oxidative decomposition, and the turbulent flow is eliminated in the lower part to form a plug flow reaction zone. To form an additional reaction.

【００３６】水熱反応器４の反応物は系路２１から熱交
換器３に導入して被処理物を加熱することにより自身は
冷却され、続いて気液分離器６で気液分離し、気体排出
路２４から気体を排出し、液体排出路２６から処理水を
排出する。The reaction product of the hydrothermal reactor 4 is introduced into the heat exchanger 3 from the system passage 21 to heat the object to be processed, thereby cooling itself, and subsequently, gas-liquid separation is carried out by the gas-liquid separator 6, The gas is discharged from the gas discharge passage 24, and the treated water is discharged from the liquid discharge passage 26.

【００３７】上記のように、有機高分子化合物を低分子
化した後水熱反応を行うことにより、水熱反応器４での
チャーの生成を防止することができる。このため、弁の
閉塞や、処理水へのチャーの混入が防止できる。As described above, the formation of char in the hydrothermal reactor 4 can be prevented by performing the hydrothermal reaction after lowering the molecular weight of the organic polymer compound. Therefore, it is possible to prevent the valve from closing and the char from mixing into the treated water.

【００３８】図１の装置では、必要に応じて、薬剤処理
槽２にｐＨ調整剤を添加するｐＨ調整剤供給路を接続
し、有機高分子化合物の低分子化に適したｐＨに調整す
ることもできる。また必要に応じて、加熱することもで
きる。また水熱反応は補助燃料を添加して行うこともで
きる。In the apparatus shown in FIG. 1, if necessary, a pH adjusting agent supply path for adding a pH adjusting agent to the chemical treatment tank 2 is connected to adjust the pH suitable for lowering the molecular weight of the organic polymer compound. You can also Further, if necessary, heating can be performed. The hydrothermal reaction can also be carried out by adding an auxiliary fuel.

【００３９】[0039]

【実施例】実施例１ 有機高分子化合物としてポリスチレンスルホン酸ナトリ
ウム（分子量２００万、蒸発残分９２重量％）を用い、
下記の方法により低分子化した後、水熱反応を行った。Example 1 Sodium polystyrene sulfonate (molecular weight 2,000,000, evaporation residue 92% by weight) was used as an organic polymer compound,
After lowering the molecular weight by the following method, hydrothermal reaction was performed.

【００４０】・低分子化工程 ２）ポリスチレンスルホン酸ナトリウムを水に溶解し、
濃度２．８重量％の水溶液とした。この水溶液に過酸化
水素を１Ｍ、ＦｅＳＯ4を鉄として０．０３Ｍとなるよ
うに添加し、硫酸でｐＨを３に調整した。その後、６０
℃で３時間攪拌し、ポリスチレンスルホン酸ナトリウム
を低分子化した。低分子化後の反応液をゲルろ過法で測
定したところ、分子量は約２０００まで低下していた。
ＮａＯＨでｐＨを５に調整した後、被処理液として水熱
反応工程に供した。-Low molecular weight step 2) Sodium polystyrene sulfonate is dissolved in water,
An aqueous solution having a concentration of 2.8% by weight was prepared. Hydrogen peroxide was added to this aqueous solution as 1 M and FeSO 4 as iron so as to be 0.03 M, and the pH was adjusted to 3 with sulfuric acid. Then 60
The mixture was stirred at 0 ° C for 3 hours to reduce the molecular weight of sodium polystyrene sulfonate. When the reaction liquid after the molecular weight reduction was measured by the gel filtration method, the molecular weight was reduced to about 2000.
After adjusting the pH to 5 with NaOH, it was subjected to a hydrothermal reaction step as a liquid to be treated.

【００４１】・水熱反応工程 内径９．４５ｍｍ、高さ３００ｍｍのステンレス管を水
熱反応器とし、水熱反応を行った。上記被処理液は高圧
ポンプで送液し、水熱反応器に設けた注入口から圧入し
た（２ｍｌ／ｍｉｎ）。また酸化剤として過酸化水素水
を使用し、配管部で外部熱源により３７０℃に予熱し、
注入口直前の配管で被処理液と混合して水熱反応器へ圧
入した（１ｍｌ／ｍｉｎ）。水熱反応器はセラミックヒ
ーターと内部に設けた熱伝対を使って、反応流体の温度
が６５０℃となるようにした。反応流体は二重冷却管式
冷却器で冷却した。圧力は出口に設けた調圧弁で２４Ｍ
Ｐａに調整した。水熱反応が安定して継続した（２時間
まで確認した）。得られた処理液は無色透明で、ＴＯＣ
は１０ｐｐｍであり、有機物はほぼ完全に分解できた。Hydrothermal reaction step A stainless tube having an inner diameter of 9.45 mm and a height of 300 mm was used as a hydrothermal reactor to carry out hydrothermal reaction. The liquid to be treated was sent by a high-pressure pump, and was injected under pressure from an injection port provided in the hydrothermal reactor (2 ml / min). Also, using hydrogen peroxide water as an oxidizer, preheat to 370 ° C. with an external heat source in the piping section,
It mixed with the to-be-processed liquid in the pipe | tube just before an injection port, and pressure-inserted into the hydrothermal reactor (1 ml / min). The hydrothermal reactor used a ceramic heater and a thermocouple provided inside so that the temperature of the reaction fluid was 650 ° C. The reaction fluid was cooled by a double cooling tube cooler. The pressure is 24M with the pressure regulating valve installed at the outlet.
It was adjusted to Pa. The hydrothermal reaction continued stably (confirmed up to 2 hours). The resulting treatment liquid is colorless and transparent and has TOC
Was 10 ppm, and the organic matter could be decomposed almost completely.

【００４２】比較例１ 低分子化工程を省略し、ポリスチレンスルホン酸ナトリ
ウムをそのまま用いて水熱反応を行った。すなわち、分
子量２００万のポリスチレンスルホン酸ナトリウムを水
に溶解し、濃度２．８重量％の水溶液を調製し、ＮａＯ
ＨでｐＨを５に調整した後、被処理液として水熱反応工
程に供し、実施例１と同じ方法で水熱反応を行った。こ
の処理液は黒色のＳＳを含む懸濁液で、有機臭がしたた
め水熱反応を中止した。Comparative Example 1 A hydrothermal reaction was carried out by omitting the step of lowering the molecular weight and using sodium polystyrene sulfonate as it was. That is, sodium polystyrenesulfonate having a molecular weight of 2,000,000 was dissolved in water to prepare an aqueous solution having a concentration of 2.8% by weight, and NaO was added.
After adjusting the pH to 5 with H, the liquid to be treated was subjected to the hydrothermal reaction step, and the hydrothermal reaction was carried out in the same manner as in Example 1. The treatment liquid was a suspension containing black SS, and the hydrothermal reaction was stopped because an organic odor was generated.

【図面の簡単な説明】[Brief description of drawings]

【図１】実施形態の水熱反応処理装置の系統図である。FIG. 1 is a system diagram of a hydrothermal reaction treatment device of an embodiment.

【符号の説明】[Explanation of symbols]

１ 被処理物貯槽 ２ 薬剤処理槽 ３ 熱交換器 ４ 水熱反応器 ５ 酸化剤槽 ６ 気液分離器 １１ 被処理物導入路 １２、１６、１９、２１、２２ 系路 １３ 薬剤供給路 １５ 供給装置 １７、１８ 高圧ポンプ ２３、２５ 減圧弁 ２４ 気体排出路 ２６ 液体排出路 1 Processing object storage tank 2 Chemical treatment tank 3 heat exchanger 4 Hydrothermal reactor 5 oxidizer tank 6 gas-liquid separator 11 Processing object introduction path 12, 16, 19, 21, 22 route 13 Drug supply route 15 Supply device 17, 18 High pressure pump 23, 25 Pressure reducing valve 24 gas exhaust path 26 Liquid discharge path

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０２Ｆ 1/30 Ｃ０２Ｆ 1/36 1/36 1/70 Ｚ 1/461 1/72 Ｚ 1/70 1/74 １０１ 1/72 ＺＡＢ 1/74 １０１ 1/76 Ｚ ＺＡＢ 1/78 1/76 1/46 １０１Ｃ 1/78 Ｂ０９Ｂ 3/00 ３０４Ｐ Ｆターム(参考） 4D004 AA06 AA07 AC05 CA36 CA37 CA39 CA43 CA44 CA50 CC02 CC11 CC15 4D037 AA11 AB17 BA16 BA26 CA12 4D050 AA13 AB23 AB24 AB25 AB26 AB27 BA12 BB01 BB02 BB03 BB06 BB08 BB09 BB11 BC01 BC02 BC09 CA07 CA10 CA13 4D061 DA08 DB19 DC11 DC12 EA03 EA04 FA01 FA07 FA20 4G075 AA15 AA22 AA37 BA05 BA06 CA20 CA23 CA33 CA57 CA65 CA66 DA01 EB31 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C02F 1/30 C02F 1/36 1/36 1/70 Z 1/461 1/72 Z 1/70 1 / 74 101 1/72 ZAB 1/74 101 1/76 Z ZAB 1/78 1/76 1/46 101C 1/78 B09B 3/00 304P F term (reference) 4D004 AA06 AA07 AC05 CA36 CA37 CA39 CA43 CA44 CA50 CC02 CC11 CC15 4D037 AA11 AB17 BA16 BA26 CA12 4D050 AA13 AB23 AB24 AB25 AB26 AB27 BA12 BB01 BB02 BB03 BB06 BB08 BB09 BB11 BC01 BC02 BC09 CA07 CA10 CA13 4D061 DA08 DB19 DC11 DC12 EA03 EA04 FA01 FA07 BA20 BA05 A20 FA20 A05A20A20A20A20A20 DA01 EB31

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 有機高分子化合物を含む被処理物を水の
超臨界または亜臨界状態で水熱酸化反応により処理する
水熱酸化反応処理装置において、 有機高分子化合物を低分子化する低分子化装置と、 低分子化した有機高分子化合物を含む被処理物を水の超
臨界または亜臨界状態で水熱酸化反応により処理する水
熱反応器とを有する水熱酸化反応処理装置。1. A hydrothermal oxidation reaction treatment apparatus for treating an object to be treated containing an organic polymer compound by a hydrothermal oxidation reaction in a supercritical or subcritical state of water, wherein a low molecule for lowering the molecular weight of the organic polymer compound is used. A hydrothermal oxidation reaction treatment apparatus having a hydrothermal oxidation apparatus and a hydrothermal reactor for treating an object containing a low molecular weight organic polymer compound in a supercritical or subcritical state of water by a hydrothermal oxidation reaction. 【請求項２】 低分子化装置が、有機高分子化合物に薬
剤を接触させて低分子化する薬剤処理装置、有機高分子
化合物に超音波を照射して低分子化する超音波照射装
置、有機高分子化合物に光を照射して低分子化する光照
射装置、有機高分子化合物にオゾンを接触させて低分子
化するオゾン処理装置、有機高分子化合物を電気分解す
る電気分解装置、またはこれらを組み合せた装置である
請求項１記載の装置。2. A low-molecular-weight device for treating a low-molecular weight compound by bringing a drug into contact with an organic polymer compound, an ultrasonic irradiation device for irradiating an organic high-molecular compound with ultrasonic waves to lower the molecular weight, and an organic substance. A light irradiation device for irradiating a high molecular compound with light to lower the molecular weight, an ozone treatment device for contacting an organic high molecular compound with ozone to lower the molecular weight, an electrolysis device for electrolyzing an organic high molecular compound, or these The device of claim 1 which is a combined device. 【請求項３】 有機高分子化合物が合成有機高分子であ
る請求項１または２記載の装置。3. The device according to claim 1, wherein the organic polymer compound is a synthetic organic polymer. 【請求項４】 有機高分子化合物を含む被処理物を水の
超臨界または亜臨界状態で水熱酸化反応により処理する
水熱酸化反応処理方法において、 有機高分子化合物を低分子化する低分子化工程と、 低分子化した有機高分子化合物を含む被処理物を水の超
臨界または亜臨界状態で水熱酸化反応により処理する水
熱反応工程とを有する水熱酸化反応処理方法。4. A hydrothermal oxidation reaction treatment method for treating an object to be treated containing an organic polymer compound by a hydrothermal oxidation reaction in a supercritical or subcritical state of water, wherein a low molecule for lowering the molecular weight of the organic polymer compound is used. And a hydrothermal reaction step of treating an object containing a low molecular weight organic polymer compound by a hydrothermal oxidation reaction in a supercritical or subcritical state of water. 【請求項５】 低分子化工程が、有機高分子化合物に薬
剤を接触させて低分子化する薬剤処理、有機高分子化合
物に超音波を照射して低分子化する超音波照射、有機高
分子化合物に光を照射して低分子化する光照射、有機高
分子化合物にオゾンを接触させて低分子化するオゾン処
理、有機高分子化合物を電気分解する電気分解、または
これらを組み合せて行う工程である請求項４記載の方
法。5. The treatment for lowering the molecular weight is carried out by treating the organic polymer compound with a drug to lower the molecular weight thereof, ultrasonic irradiation of irradiating the organic polymer compound with ultrasonic waves to lower the molecular weight, and organic polymer. In the process of performing light irradiation to irradiate a compound to lower the molecular weight, ozone treatment to bring ozone into contact with an organic polymer compound to lower the molecular weight, electrolysis to electrolyze an organic polymer compound, or a combination thereof. 5. The method of claim 4, wherein: 【請求項６】 有機高分子化合物が合成有機高分子であ
る請求項４または５記載の方法。6. The method according to claim 4, wherein the organic polymer compound is a synthetic organic polymer.
JP2002102540A 2002-04-04 2002-04-04 Hydrothermal oxidative reaction treatment apparatus and method using the same Pending JP2003299941A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005007578A2 (en) * 2003-06-19 2005-01-27 Kansai Paint Co., Ltd. Method for clarifying waste water containing organic material
JP2005138099A (en) * 2003-06-19 2005-06-02 Kansai Paint Co Ltd Method for cleaning wastewater containing organic substance
WO2006040943A1 (en) * 2004-10-14 2006-04-20 Matsushita Electric Industrial Co., Ltd. Method of liquefying solid organic substance and liquefier for solid organic substance
JP2012522635A (en) * 2009-04-01 2012-09-27 アース・リニューアル・グループ，エルエルシー Improved aqueous phase oxidation process
JP2013534857A (en) * 2010-05-24 2013-09-09 ザイレコ，インコーポレイテッド Chemical processing
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005007578A2 (en) * 2003-06-19 2005-01-27 Kansai Paint Co., Ltd. Method for clarifying waste water containing organic material
WO2005007578A3 (en) * 2003-06-19 2005-05-12 Kansai Paint Co Ltd Method for clarifying waste water containing organic material
JP2005138099A (en) * 2003-06-19 2005-06-02 Kansai Paint Co Ltd Method for cleaning wastewater containing organic substance
US7431850B2 (en) 2003-06-19 2008-10-07 Kansai Paint Co., Ltd. Process for purification treatment of wastewater containing organic substance
JP4541776B2 (en) * 2003-06-19 2010-09-08 関西ペイント株式会社 Purification method for wastewater containing organic substances
WO2006040943A1 (en) * 2004-10-14 2006-04-20 Matsushita Electric Industrial Co., Ltd. Method of liquefying solid organic substance and liquefier for solid organic substance
JP2012522635A (en) * 2009-04-01 2012-09-27 アース・リニューアル・グループ，エルエルシー Improved aqueous phase oxidation process
JP2014144452A (en) * 2009-04-01 2014-08-14 Earth Renewal Group Llc Improved aqueous phase oxidation process
US9272936B2 (en) 2009-04-01 2016-03-01 Earth Renewal Group, Llc Waste treatment process
US9611158B2 (en) 2009-04-01 2017-04-04 Earth Renewal Group, Llc Waste treatment process
US9902632B2 (en) 2009-04-01 2018-02-27 Earth Renewal Group, Llc Waste treatment method
JP2013534857A (en) * 2010-05-24 2013-09-09 ザイレコ，インコーポレイテッド Chemical processing
CN103755400A (en) * 2014-01-10 2014-04-30 傅剑锋 Method for preparing mineral organic fertilizer by using surplus sludge in municipal sewage plants
CN114790029A (en) * 2022-04-29 2022-07-26 西安交通大学 Pollutant harmless regulation and control system and method based on supercritical water oxidation technology
CN114790029B (en) * 2022-04-29 2024-02-06 西安交通大学 Pollutant harmless regulation and control system and method based on supercritical water oxidation technology

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