JP2000065986A - Method and device for treating radioactive organic waste - Google Patents
Method and device for treating radioactive organic wasteInfo
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- JP2000065986A JP2000065986A JP10237675A JP23767598A JP2000065986A JP 2000065986 A JP2000065986 A JP 2000065986A JP 10237675 A JP10237675 A JP 10237675A JP 23767598 A JP23767598 A JP 23767598A JP 2000065986 A JP2000065986 A JP 2000065986A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、放射性有機廃棄物
の処理方法、とくに原子力発電所で行なう水処理に伴っ
て発生する使用済イオン交換樹脂やフィルタースラッ
ジ、あるいは除染作業の結果発生する除染廃液を酸化分
解して処理する方法に関する。 本発明はまた、この酸
化分解処理に使用する装置にも関する。[0001] The present invention relates to a method for treating radioactive organic waste, and more particularly to a method for treating waste water generated in a nuclear power plant, including used ion exchange resin and filter sludge, and decontamination generated as a result of decontamination work. The present invention relates to a method for oxidatively decomposing and treating a dye waste liquid. The present invention also relates to an apparatus used for this oxidative decomposition treatment.
【０００２】[0002]
【従来の技術】原子力発電所において放射性核種を含有
する排水の処理に使用したフィルタースラッジおよび使
用済イオン交換樹脂の処理法として、出願人は、触媒と
しての鉄イオンの存在下に過酸化水素を作用させる湿式
酸化法を提案した（特公昭６１−９５９９）。 この種
の湿式酸化法に関してはさまざまな技術が開発されてお
り、触媒としての銅イオンの使用（特開昭５９−４４７
００、特開昭６０−６１６９７）、鉄触媒に対する助触
媒としてのニッケルの使用（特開昭６１−１５７５３
９）、クエン酸の添加（特開昭６３−１５８４９７）、
酢酸塩の添加（特開平１−３１３７９９）、しゅう酸塩
の添加（特開平１−３１３８００）などが提案されてい
る。2. Description of the Related Art As a method for treating filter sludge and spent ion exchange resin used for treating wastewater containing radionuclides in a nuclear power plant, the applicant has proposed hydrogen peroxide in the presence of iron ions as a catalyst. We have proposed a wet oxidation method to act (Japanese Patent Publication No. 61-9599). Various techniques have been developed for this type of wet oxidation method, and the use of copper ions as a catalyst (Japanese Patent Application Laid-Open No. 59-474)
00, JP-A-60-61697), and the use of nickel as a cocatalyst for an iron catalyst (JP-A-61-15753).
9), addition of citric acid (JP-A-63-158497),
Addition of acetate (JP-A-1-313799), addition of oxalate (JP-A-1-313800), and the like have been proposed.
【０００３】過酸化水素を用いた湿式酸化分解は、核燃
料再処理工場から出るリン酸トリブチル（ＴＢＰ）を主
成分とする廃溶媒の処理にも適用される（特開昭６２−
２９７７９２）が、ここではオゾンを併用する。[0003] The wet oxidative decomposition using hydrogen peroxide is also applied to the treatment of a waste solvent containing tributyl phosphate (TBP) as a main component, which is discharged from a nuclear fuel reprocessing plant.
297792), but ozone is used here.
【０００４】湿式酸化分解の生成物を最終的にどう処理
するかについて、出願人は、廃液を濃縮し中和して固化
処理することを提案した（特開平２−６３５９５）。
湿式酸化分解反応は、通常は常圧下に、ほぼ沸騰状態で
実施するので、高分子有機物がまだ完全に酸化分解され
ていない段階、すなわちＣＯ2やＨ2Ｏにまで分解される
途上にある低分子量の有機酸、たとえばギ酸や酢酸が、
反応液から揮発して来る。 フィルタースラッジの材料
にアクリル繊維を用いた場合は、酸化分解によりシアン
化合物が生成する。 酸化分解により生成したアミン
類、アンモニアは、酸性の反応液中では固定されている
が、反応の最終段階において、反応液を中和したとき放
出される。 ＴＢＰの湿式酸化処理の場合は、ｎ−ドデ
カンが生成する。Regarding the final treatment of the product of wet oxidative decomposition, the applicant has proposed that the waste liquid is concentrated, neutralized and solidified (Japanese Patent Laid-Open No. 2-63595).
Since the wet oxidative decomposition reaction is usually carried out under normal pressure and almost in a boiling state, a high-molecular organic substance is not completely oxidatively decomposed, that is, a low-molecular-weight organic compound is being decomposed into CO 2 and H 2 O. Organic acids of molecular weight, such as formic acid and acetic acid,
Volatilizes from the reaction solution. When acrylic fiber is used as a material for the filter sludge, a cyanide compound is generated by oxidative decomposition. The amines and ammonia formed by the oxidative decomposition are fixed in the acidic reaction solution, but are released when the reaction solution is neutralized in the final stage of the reaction. In the case of wet oxidation treatment of TBP, n-dodecane is generated.
【０００５】揮発したこれらの中間生成物の一部は、発
生する水蒸気とともにコンデンサーにおいて凝縮され、
凝縮水のＴＯＣ（有機炭素含有量）やＣＯＤを高くす
る。したがって、凝縮水を再利用したり放出したりする
ためには、二次的な処理が必要である。 非凝縮性の物
質は排ガスの側に出るから、放出に先立って除去しなけ
ればならない。Some of these volatilized intermediate products are condensed in the condenser together with the generated steam,
Increase the TOC (organic carbon content) and COD of condensed water. Therefore, in order to reuse or discharge the condensed water, a secondary treatment is required. Non-condensable materials exit the exhaust gas side and must be removed prior to release.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、放射
性核種が共存する有機物質を過酸化水素を用いた湿式酸
化により処理する方法において、酸化分解反応の中間生
成物が、プロセスの結果生じる凝縮水に入って来ること
を防ぎ、二次処理の必要なく凝縮水の再利用または放出
をすることができるようにした処理方法を提供すること
にある。 この方法の実施に使用する装置を提供するこ
ともまた、本発明の目的に含まれる。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for treating an organic substance coexisting with a radionuclide by wet oxidation using hydrogen peroxide, wherein an intermediate product of the oxidative decomposition reaction is produced as a result of the process. It is an object of the present invention to provide a processing method capable of preventing the condensed water from entering and allowing the condensed water to be reused or discharged without the need for a secondary treatment. It is also an object of the present invention to provide an apparatus for use in performing this method.
【０００７】[0007]
【課題を解決するための手段】本発明の放射性有機廃棄
物の処理方法は、水性媒体中で鉄イオンおよび（また
は）銅イオンの存在下に放射性有機廃棄物に過酸化水素
を作用させて酸化分解することを本質的な工程とする放
射性有機廃棄物の処理方法において、酸化分解反応の結
果生成した、低分子量の有機酸、アミン類、アンモニ
ア、シアン化合物および炭化水素の少なくとも１種を含
有する中間生成物と水蒸気との混合物を、酸化反応槽か
ら取り出して加熱し、温度を高めてから、酸化触媒をそ
なえた触媒燃焼装置に導き、そこで酸素を供給して中間
生成物を二次的に酸化分解したのち冷却し、ＴＯＣを実
質上含まない凝縮水と、無害無臭の排ガスとを得ること
からなる。According to the present invention, there is provided a method for treating radioactive organic waste, comprising the steps of oxidizing a radioactive organic waste with hydrogen peroxide in the presence of iron ions and / or copper ions in an aqueous medium. A method for treating radioactive organic waste in which the decomposition is an essential step, the method comprising at least one of low molecular weight organic acids, amines, ammonia, cyanide, and hydrocarbons generated as a result of the oxidative decomposition reaction. The mixture of the intermediate product and water vapor is taken out of the oxidation reaction tank, heated, heated, and then led to a catalytic combustion device equipped with an oxidation catalyst, where oxygen is supplied to convert the intermediate product to secondary gas. After oxidative decomposition, cooling is performed to obtain condensed water substantially free of TOC and harmless and odorless exhaust gas.
【０００８】本発明の放射性有機廃棄物の処理装置は、
図１に全体の構成を示すように、放射性有機廃棄物に過
酸化水素を作用させて湿式酸化分解するための、撹拌機
をそなえた反応槽（２）、反応槽への過酸化水素、触媒
溶液およびｐＨ調整用の酸・アルカリの供給タンク（２
１〜２５）、反応槽から揮発してくる酸化分解反応の中
間生成物および水蒸気の混合物を受け入れて、中間生成
物を二次的に酸化させるための、酸化触媒をそなえた触
媒燃焼装置（３）、触媒燃焼装置への酸素供給手段
（４）、触媒燃焼装置からの排ガスを冷却して凝縮水を
得るためのコンデンサー（５）、ならびに、触媒燃焼装
置からの排ガスの熱で混合ガスを加熱するための熱交換
器（６）から本質的に構成される。 図１において、符
号（１）は処理すべき放射性有機廃棄物のタンクを、ま
た符号（７）は凝縮水を受けるタンクを、それぞれ示
す。[0008] The apparatus for treating radioactive organic waste of the present invention comprises:
As shown in FIG. 1, a reactor (2) equipped with a stirrer, hydrogen peroxide to the reactor, and a catalyst for wet oxidative decomposition of hydrogenated radioactive waste by the action of hydrogen peroxide. Acid and alkali supply tanks for solution and pH adjustment (2
1 to 25), a catalytic combustion device provided with an oxidation catalyst for receiving a mixture of the intermediate product of the oxidative decomposition reaction and water vapor volatilized from the reaction tank and secondary oxidizing the intermediate product (3). ), Means for supplying oxygen to the catalytic combustion device (4), a condenser (5) for cooling the exhaust gas from the catalytic combustion device to obtain condensed water, and heating the mixed gas by the heat of the exhaust gas from the catalytic combustion device Essentially consisting of a heat exchanger (6). In FIG. 1, reference numeral (1) indicates a tank for radioactive organic waste to be treated, and reference numeral (7) indicates a tank for receiving condensed water.
【０００９】[0009]
【発明の実施の形態】本発明の方法で処理する放射性有
機廃棄物は、原子力発電所で発生する使用済の粒状また
は粉末状のイオン交換樹脂がその代表であるが、濾過助
材のフィルタースラッジも同様な処理の対象となる。
フィルタスラッジは、セルロース系のものはもちろん、
アクリル繊維系のものも処理できる。 核燃料再処理工
場から発生する廃溶媒も、処理の対象に含まれる。 本
発明の方法はまた、クエン酸、シュウ酸、ＥＤＴＡを含
む除染廃液の処理にも適用できる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The radioactive organic waste to be treated by the method of the present invention is typically a used granular or powdered ion exchange resin generated in a nuclear power plant. Are subject to similar processing.
Filter sludge is of course cellulosic,
Acrylic fibers can also be processed. Waste solvents generated from nuclear fuel reprocessing plants are also included in the scope of treatment. The method of the present invention is also applicable to the treatment of decontamination waste liquors containing citric acid, oxalic acid and EDTA.
【００１０】触媒燃焼装置は、Ｎｉ−Ｃｒ系、ＳｉＯ2
−Ａｌ2Ｏ3−ＭｇＯ系あるいはγ−Ａｌ2Ｏ3などの酸化
触媒をそなえたものであって、スポンジ状、球状、ハニ
カム体など種々の形状のものがあり、任意に選択使用で
きる。 圧力損失を小さくするという観点からは、Ｎｉ
−Ｃｒ系発泡金属触媒が好適である。 触媒燃焼装置
は、塗装や印刷の業界で、有機溶剤を含有する雰囲気を
浄化するために実用されている。 本発明においては、
溶剤蒸気含有空気と違って、多量の水蒸気が共存する条
件下の使用であるが、既存の装置を本発明の処理方法に
おいても利用できることを確認してある。[0010] The catalytic combustion device is a Ni-Cr type, SiO 2
It is provided with an oxidation catalyst such as —Al 2 O 3 —MgO or γ-Al 2 O 3, and has various shapes such as sponge, sphere and honeycomb, and can be arbitrarily selected and used. From the viewpoint of reducing pressure loss, Ni
-Cr-based foamed metal catalysts are preferred. Catalytic combustion devices are used in the painting and printing industries to purify atmospheres containing organic solvents. In the present invention,
Unlike air containing solvent vapor, which is used under conditions where a large amount of water vapor coexists, it has been confirmed that existing equipment can be used in the treatment method of the present invention.
【００１１】可燃性のガスを含有する気体を、上記のよ
うな酸化触媒に接触させてその表面で酸化を行なうと
き、一般に、２００℃以上、好ましくは３００℃以上で
酸化反応が盛んに起こり、触媒の温度が上昇する。 温
度上昇の度合いは、もちろん供給される可燃物の濃度に
よって異なるが、しばしば１００℃またはそれ以上に達
する。 触媒床に入るガスの温度を３００〜３５０℃に
高めておけば、触媒床を出る排ガスの温度は４００〜５
００℃に達する。When a gas containing a flammable gas is brought into contact with an oxidation catalyst as described above to oxidize the surface thereof, the oxidation reaction generally occurs actively at 200 ° C. or higher, preferably 300 ° C. or higher, The temperature of the catalyst increases. The degree of temperature rise will of course depend on the concentration of combustibles supplied, but often reaches 100 ° C. or more. If the temperature of the gas entering the catalyst bed is raised to 300-350 ° C., the temperature of the exhaust gas exiting the catalyst bed will be 400-5
Reach 00 ° C.
【００１２】二次的な酸化反応により、有機酸は完全に
酸化されてＣＯ2およびＨ2Ｏに変化し、アミン・アンモ
ニアの類は、Ｎ2およびＨ2Ｏになる。 このようにし
て、ＴＯＣが実質上ゼロといってよい（１〜２ppm）凝
縮水が得られる。[0012] By the secondary oxidation reaction, the organic acid is completely oxidized and changed into CO 2 and H 2 O, and the kind of amine ammonia becomes N 2 and H 2 O. In this way, condensed water having a TOC of substantially zero (1-2 ppm) is obtained.
【００１３】酸化分解反応の中間生成物と水蒸気との混
合物の加熱は、必要であれば、燃焼ガスの導入により実
施することができる。 燃焼装置からの排ガスのもつ熱
を、中間生成物と水蒸気との混合物と熱交換することが
好ましい。The heating of the mixture of the intermediate product of the oxidative decomposition reaction and steam can be carried out by introducing a combustion gas, if necessary. It is preferred that the heat of the exhaust gas from the combustion device be exchanged with the mixture of the intermediate product and steam.
【００１４】湿式酸化分解は、連続式に行なってもバッ
チ式に行なってもよいが、後記する実施例にみるような
セミバッチ式が有利である。 すなわち、処理すべき放
射性有機廃棄物の一部をあらかじめ反応槽に装入してお
いて酸化分解反応を開始し、反応の進行に伴って廃棄物
を補給して行き、所定の量を投入し終わったのちも過酸
化水素の供給を続け、酸化分解をほぼ完全に進めてから
停止するという手順に従う方式である。The wet oxidative decomposition may be carried out either continuously or batchwise, but a semi-batch type as described in Examples described later is advantageous. That is, a part of the radioactive organic waste to be treated is previously charged into the reaction tank to start the oxidative decomposition reaction, and the waste is replenished as the reaction proceeds, and a predetermined amount is charged. After this, the supply of hydrogen peroxide is continued, and the oxidative decomposition is almost completely advanced before stopping.
【００１５】過酸化水素による湿式酸化は、水性媒体が
酸性のときによく進行するから、反応の開始に当たっ
て、硫酸などの酸を添加する。 すると、アンモニアや
アミン類は、反応中は液中に固定されていて揮発せず、
反応終了後、苛性ソーダなどのアルカリを加えて液を中
和すると、放出される。 したがって、その段階で揮発
してきた中間生成物を触媒燃焼装置に送って、二次酸化
して完全に分解する。Since the wet oxidation with hydrogen peroxide proceeds well when the aqueous medium is acidic, an acid such as sulfuric acid is added at the start of the reaction. Then, ammonia and amines are fixed in the liquid during the reaction and do not evaporate,
After completion of the reaction, the solution is released when the solution is neutralized by adding an alkali such as caustic soda. Therefore, the intermediate product volatilized at that stage is sent to the catalytic combustion device, and is secondary-oxidized and completely decomposed.
【００１６】[0016]
【実施例】［実施例１］図１に示す構成の、放射性有機
廃棄物処理装置を組み立てた。 反応槽（２）は、容量
２５０リットルで、ジャケットおよび撹拌機つきのもの
である。 使用済イオン交換樹脂を模擬したものとし
て、下記２種の粒状イオン交換樹脂 ＩＲ−１２０Ｂ：１５．０ｋｇ ＩＲＡ−４００：３０．０ｋｇ の混合物を、廃棄物の供給タンク（１）に入れ、１０重
量％水スラリーとした。EXAMPLE 1 An apparatus for treating radioactive organic waste having the structure shown in FIG. 1 was assembled. The reactor (2) has a capacity of 250 liters and is equipped with a jacket and a stirrer. As a simulated used ion exchange resin, a mixture of the following two types of granular ion exchange resins IR-120B: 15.0 kg IRA-400: 30.0 kg was put into a waste supply tank (1), and 10 wt. % Water slurry.
【００１７】イオン交換樹脂スラリーの７５リットルを
反応槽に移し、蒸留水を加えて容量を倍の１５０リット
ルとした。 酸供給タンク（２４）から硫酸を添加して
ｐＨを１〜３に調節した。 ジャケットにスチームを通
して加熱し、内容を沸騰状態にしたのち、触媒として、
触媒溶液タンク（２２、２３）から、硫酸第一鉄および
硫酸銅を濃厚溶液としてほぼ等量ずつ、あわせて３モル
を添加した。 この状態で、模擬廃棄物スラリーを３０
リットル／時の供給速度で、また３５％過酸化水素水を
２７リットル／時の供給速度で、反応槽に供給した。
反応槽内部は、スチーム加熱と反応熱により沸騰状態が
継続し、液量がほぼ一定に保たれた。75 liters of the ion exchange resin slurry was transferred to a reaction tank, and distilled water was added to double the volume to 150 liters. Sulfuric acid was added from the acid supply tank (24) to adjust the pH to 1-3. After heating the jacket through steam to bring the contents to a boil, as a catalyst,
From the catalyst solution tanks (22, 23), ferrous sulfate and copper sulfate were added as concentrated solutions in almost equal amounts, each in a total amount of 3 mol. In this state, the simulated waste slurry was
A 35% aqueous hydrogen peroxide solution was supplied to the reaction tank at a supply rate of 1 liter / hour and a supply rate of 27 liter / hour.
Inside the reaction tank, the boiling state continued due to the steam heating and the reaction heat, and the liquid volume was kept almost constant.
【００１８】反応層から発生する水蒸気と酸化分解の中
間生成物との混合物は、約９０Ｎm3／時の速度で触媒燃
焼装置（３）に通し、空気１０Ｎm3／時を供給して、中
間生成物を燃焼させた。 この燃焼装置は、Ｎｉ−Ｃｒ
系の発泡金属からなる触媒床を備えている。 定常状態
における触媒床の温度は、約３２０℃であった。 燃焼
装置からの排ガスは、熱交換器（５）で熱交換の後、コ
ンデンサー（６）で冷却し、非凝縮ガスと分離して、凝
縮水を凝縮水タンク（７）に受けた。The mixture of the steam generated from the reaction layer and the intermediate product of the oxidative decomposition is passed through a catalytic combustion device (3) at a speed of about 90 Nm 3 / hour, and 10 Nm 3 / hour of air is supplied to the intermediate product. Burned things. This combustion device uses Ni-Cr
A catalyst bed made of a metal foam is provided. The catalyst bed temperature at steady state was about 320 ° C. Exhaust gas from the combustion device was heat-exchanged in a heat exchanger (5), cooled in a condenser (6), separated from non-condensable gas, and received condensed water in a condensed water tank (7).
【００１９】模擬廃棄物の供給を４時間で止め、その後
は過酸化水素水のみを供給したまま反応を５時間継続
し、その時点で反応を停止した。 定常状態の４時間の
うち反応開始後１時間おき、および模擬廃棄物の供給を
停止して１時間後の凝縮水について、ＴＯＣを測定し
た。 結果を図２の下段に示す。The supply of the simulated waste was stopped in 4 hours, and thereafter the reaction was continued for 5 hours while supplying only the hydrogen peroxide solution, at which point the reaction was stopped. The TOC was measured for the condensed water every one hour after the start of the reaction and one hour after the supply of the simulated waste was stopped among the four hours in the steady state. The results are shown in the lower part of FIG.
【００２０】反応停止後、アルカリ供給タンク（２５）
から苛性ソーダ溶液を添加して、酸性の反応後の液を中
和した。 すると、液中に固定されていたアミン類やア
ンモニアが分離揮発してきたので、このガスも触媒燃焼
装置に送って酸化させ、ついでコンデンサーに導いた。
このとき、コンデンサーで分離された非凝縮性のガス
の中には、アミン類もアンモニアも検出されなかった。After stopping the reaction, an alkali supply tank (25)
, A solution after the acidic reaction was neutralized by adding a sodium hydroxide solution. Then, the amines and ammonia fixed in the liquid were separated and volatilized. This gas was also sent to the catalytic combustion device to be oxidized, and then led to the condenser.
At this time, neither amines nor ammonia was detected in the non-condensable gas separated by the condenser.
【００２１】［比較例１］実施例１において、触媒燃焼
装置による中間生成物の二次酸化分解を省略した工程を
実施した。 凝縮水のＴＯＣの時間変化は、図２の上段
に示すとおりであって、６２０〜８３０ppm、平均６８
８ppmであった。 有機炭素の成分を調べたところ、ギ
酸、酢酸、プロピオン酸などであった。 反応後、アル
カリによる中和を行なうと、コンデンサーの非凝縮ガス
出口からアンモニアに似た臭気がしたので、ガスを採取
してガスクロマトグラフで分析したところ、悪臭物質は
主としてトリメチルアミンであることがわかった。[Comparative Example 1] In Example 1, a step was performed in which the secondary oxidative decomposition of the intermediate product by the catalytic combustion device was omitted. The time change of the TOC of the condensed water is as shown in the upper part of FIG.
It was 8 ppm. When the components of the organic carbon were examined, they were formic acid, acetic acid, propionic acid and the like. After the reaction, when neutralization with alkali was performed, an odor similar to ammonia was emitted from the non-condensed gas outlet of the condenser. .
【００２２】［実施例２］実施例１で用いた装置によ
り、下記２種の粉末状イオン交換樹脂 ＰＣＨ：７．５ｋｇ ＰＡＯ：７．５ｋｇ の混合物を、実施例１と同様な条件で湿式酸化分解によ
り処理した。Example 2 A mixture of the following two kinds of powdery ion-exchange resins PCH: 7.5 kg PAO: 7.5 kg was wet-oxidized under the same conditions as in Example 1 by using the apparatus used in Example 1. Treated by decomposition.
【００２３】凝縮水について、ＴＯＣを測定した結果
を、図３の下段に示す。 コンデンサーで分離された非
凝縮性のガスの中には、実施例１と同様、アミン類もア
ンモニアも検出されなかった。The result of measuring the TOC of the condensed water is shown in the lower part of FIG. As in Example 1, no amines or ammonia was detected in the non-condensable gas separated by the condenser.
【００２４】［比較例２］比較例１と同じ装置を使用
し、実施例２の工程を、触媒燃焼装置による中間生成物
の二次酸化分解を省略して実施した。 凝縮水のＴＯＣ
の時間変化は、図３の上段に示すとおり、４２０〜１３
５０ppm、平均９４３ppmであった。 有機炭素成分は、
比較例１と同様であった。 反応後、アルカリによる中
和を行なったとき発生した非凝縮ガスも、比較例１と同
様、悪臭物質は主としてトリメチルアミンであった。Comparative Example 2 The same apparatus as in Comparative Example 1 was used, and the process of Example 2 was performed without the secondary oxidative decomposition of the intermediate product by the catalytic combustion device. TOC of condensed water
The time change of 420 to 13 as shown in the upper part of FIG.
50 ppm, average 943 ppm. Organic carbon components are
It was the same as Comparative Example 1. As in Comparative Example 1, the non-condensable gas generated when neutralization with an alkali was performed after the reaction was mainly trimethylamine.
【００２５】［実施例３］実施例１で用いた装置におい
て、セルロースを濃度１０重量％のスラリーにして、実
施例１と同様な条件で湿式酸化分解により処理した。
凝縮水についてＴＯＣを測定したところ、４時間の反応
時間とその後の１時間を通じて、１ppm 前後であった。Example 3 In the apparatus used in Example 1, a slurry having a cellulose concentration of 10% by weight was processed by wet oxidative decomposition under the same conditions as in Example 1.
The TOC of the condensed water was measured and found to be around 1 ppm over a reaction time of 4 hours and thereafter for 1 hour.
【００２６】［比較例３］比較例１と同じ装置を使用
し、実施例３の工程を、触媒燃焼装置による中間生成物
の二次酸化分解を省略して実施した。 凝縮水のＴＯＣ
は、４時間の反応時間とその後の１時間を通じて、２６
〜２６３ppm、平均１２５ppmであった。 有機炭素成分
は、ギ酸および酢酸であった。Comparative Example 3 The same apparatus as that of Comparative Example 1 was used, and the process of Example 3 was carried out without the secondary oxidative decomposition of the intermediate product by the catalytic combustion device. TOC of condensed water
Is 26 hours over a 4 hour reaction time followed by 1 hour
２６263 ppm, average 125 ppm. The organic carbon components were formic acid and acetic acid.
【００２７】［実施例４］実施例１で用いた装置によ
り、下記の濾過助材の混合物 ＤＦＫ−１０：３ｋｇ ＤＦＡ−１０：６ｋｇ Ｌ−１０ ：５ｋｇ を濃度１０重量％のスラリーにして、実施例１と同様な
条件で湿式酸化分解により処理した。 凝縮水について
ＴＯＣを測定したところ、４時間の反応時間とその後の
１時間を通じて、１ppm 前後であった。 非凝縮ガスの
中に、有害な成分や悪臭をもつ成分は検出されなかっ
た。Example 4 The following filter aid mixture DFK-10: 3 kg DFA-10: 6 kg L-10: 5 kg was converted into a slurry having a concentration of 10% by weight using the apparatus used in Example 1 Treated by wet oxidative decomposition under the same conditions as in Example 1. The TOC of the condensed water was measured and found to be around 1 ppm over a reaction time of 4 hours and thereafter for 1 hour. No harmful or odorous components were detected in the non-condensable gas.
【００２８】［比較例４］比較例１と同じ装置を使用
し、実施例４の工程を、触媒燃焼装置による中間生成物
の二次酸化分解を省略して実施した。 凝縮水中のＴＯ
Ｃは、比較例２と同じような傾向を示した。 シアン化
合物の生成が予測されたので、吸収液中に非凝縮ガスを
通過させたところ、吸収液１００ml中のシアン濃度は８
６．１ppm であった。 反応液の中にもシアンが残存し
ており、その濃度は０．３６ppm と測定された。Comparative Example 4 The same apparatus as in Comparative Example 1 was used, and the process of Example 4 was carried out without the secondary oxidative decomposition of the intermediate product by the catalytic combustion device. TO in condensed water
C showed the same tendency as Comparative Example 2. Since the generation of a cyanide compound was predicted, when a non-condensed gas was passed through the absorbing solution, the cyan concentration in 100 ml of the absorbing solution was 8
It was 6.1 ppm. Cyan remained in the reaction solution, and its concentration was measured to be 0.36 ppm.
【００２９】［実施例５］実施例１で用いた装置によ
り、下記の粒状イオン交換樹脂と濾過助材の混合物 ＩＲ−１２０Ｂ： ５ｋｇ ＩＲＡ−４００：１０ｋｇ ＤＦＫ−１０： ６ｋｇ ＤＦＡ−１０： １２ｋｇ Ｌ−１０ ： １０ｋｇ を濃度１０重量％のスラリーにして、実施例１と同様な
条件で湿式酸化分解により処理した。 凝縮水について
ＴＯＣを測定したところ、４時間の反応時間とその後の
１時間を通じて、１ppm 前後であった。 非凝縮ガスの
中に、有害な成分や悪臭をもつ成分は検出されなかっ
た。Example 5 The following mixture of a granular ion exchange resin and a filter aid was used in the apparatus used in Example 1 IR-120B: 5 kg IRA-400: 10 kg DFK-10: 6 kg DFA-10: 12 kg L -10: 10 kg was made into a slurry having a concentration of 10% by weight, and treated by wet oxidative decomposition under the same conditions as in Example 1. The TOC of the condensed water was measured and found to be around 1 ppm over a reaction time of 4 hours and thereafter for 1 hour. No harmful or odorous components were detected in the non-condensable gas.
【００３０】[0030]
【発明の効果】本発明の方法によれば、放射性有機廃棄
物を過酸化水素を用いた湿式酸化分解により処理したと
きに発生する酸化反応の中間生成物、すなわち低分子量
の有機酸、アミン類、アンモニア、シアン化合物、炭化
水素などを、コンデンサーに至る前に二次的に燃焼分解
することによって、凝縮水や排気に混入することを防止
できる。 その結果、ＴＯＣが実質上ゼロである凝縮水
を得て、再利用したり放出したりすることができるし、
排ガスは無臭かつ無害である。According to the method of the present invention, intermediate products of an oxidation reaction generated when a radioactive organic waste is treated by wet oxidative decomposition using hydrogen peroxide, that is, low molecular weight organic acids and amines , Ammonia, cyanide, hydrocarbons and the like are secondarily burned and decomposed before reaching the condenser, so that they can be prevented from being mixed into condensed water and exhaust gas. As a result, condensed water having a TOC of substantially zero can be obtained, reused and discharged,
The exhaust gas is odorless and harmless.
【００３１】この処理方法に使用する装置は、在来の湿
式酸化分解の装置に対し、溶剤蒸気を含む雰囲気の浄化
に使用されている触媒燃焼装置と熱交換器を付加しただ
けで構成できるから、設備費の増大はさして問題ず、Ｔ
ＯＣの高い凝縮水の二次処理のための設備を設けるよ
り、はるかに有利である。The apparatus used in this treatment method can be constituted by simply adding a catalytic combustion apparatus and a heat exchanger used for purifying an atmosphere containing solvent vapor to a conventional wet oxidative decomposition apparatus. , The increase in equipment costs is no problem.
It is much more advantageous than providing equipment for secondary treatment of high OC condensed water.
【図１】 本発明の放射性有機廃棄物の処理装置の全体
の構成を示すフローチャート。FIG. 1 is a flowchart showing the overall configuration of the radioactive organic waste treatment apparatus of the present invention.
【図２】 本発明の実施例１および比較例１の結果を示
す図であって、コンデンサーからの凝縮水のＴＯＣの時
間変化を示す。 上段のグラフは比較例１のデータであ
り、下段のグラフは実施例１のデータである。FIG. 2 is a diagram showing the results of Example 1 and Comparative Example 1 of the present invention, showing a time change of TOC of condensed water from a condenser. The upper graph is the data of Comparative Example 1, and the lower graph is the data of Example 1.
【図３】 本発明の実施例２および比較例２の結果を示
す図であって、コンデンサーからの凝縮水のＴＯＣの時
間変化を示す。 上段のグラフは比較例２のデータであ
り、下段のグラフは実施例２のデータである。FIG. 3 is a diagram showing the results of Example 2 and Comparative Example 2 of the present invention, showing the time change of the TOC of the condensed water from the condenser. The upper graph is the data of Comparative Example 2, and the lower graph is the data of Example 2.
１ 放射性有機廃棄物のタンク ２ 湿式酸化分解の反応槽 ２１ 過酸化水素の供給タンク ２２ 触媒（硫酸第一鉄）溶液の供給タンク ２３ 触媒（硫酸銅）溶液の供給タンク ２４ 酸の供給タンク ２５ アルカリの供給タンク ３ 触媒燃焼装置 ４ 酸素供給手段 ５ コンデンサー ６ 熱交換器 ７ 凝縮水を受けるタンク REFERENCE SIGNS LIST 1 Radioactive organic waste tank 2 Wet oxidative decomposition reaction tank 21 Hydrogen peroxide supply tank 22 Catalyst (ferrous sulfate) solution supply tank 23 Catalyst (copper sulfate) solution supply tank 24 Acid supply tank 25 Alkali Supply tank 3 catalytic combustion device 4 oxygen supply means 5 condenser 6 heat exchanger 7 tank for receiving condensed water
Claims (6)
よび（または）銅イオンの存在下に放射性有機廃棄物に
過酸化水素を作用させて湿式酸化分解することを本質的
な工程とする放射性有機廃棄物の処理方法において、酸
化分解反応の結果生成した、低分子量の有機酸、炭化水
素、アンモニア、アミンおよびシアン化合物の少なくと
も１種を含有する中間生成物と水蒸気との混合物を、酸
化反応槽から取り出して加熱し、温度を高めてから酸化
触媒をそなえた触媒燃焼装置に導き、そこで酸素を供給
して中間生成物を二次的に酸化分解したのち冷却し、Ｔ
ＯＣを実質上含まない凝縮水と無害無臭の排ガスとを得
ることからなる放射性有機廃棄物の処理方法。1. A radioactive method comprising the step of subjecting a radioactive organic waste to hydrogen peroxide in an aqueous medium in the presence of iron ions and / or copper ions as a catalyst to perform wet oxidative decomposition. In a method for treating organic waste, a mixture of steam and an intermediate product containing at least one of low molecular weight organic acids, hydrocarbons, ammonia, amines and cyanides, which is generated as a result of an oxidative decomposition reaction, is subjected to an oxidation reaction. After being taken out of the tank and heated, the temperature is raised and then led to a catalytic combustion device equipped with an oxidation catalyst, where oxygen is supplied to secondarily oxidize and decompose the intermediate product and then cooled.
A method for treating radioactive organic waste, comprising obtaining condensed water substantially free of OC and harmless and odorless exhaust gas.
チ式に行ない、まず反応媒体に酸を加えて低いｐＨとし
て過酸化水素を作用させ、反応停止後、反応液にアルカ
リを加えてほぼ中性のｐＨとし、その結果放出されるア
ンモニアおよび（または）アミン類を触媒燃焼装置で二
次的に酸化分解する操業方式で実施する請求項１の処理
方法。2. A wet oxidative decomposition is carried out in a batch or semi-batch system. First, an acid is added to the reaction medium to lower the pH to hydrogen peroxide, and after the reaction is stopped, an alkali is added to the reaction solution to make it almost neutral. The treatment method according to claim 1, wherein the treatment method is carried out in an operation system in which the pH is adjusted and ammonia and / or amines released as a result are secondarily oxidatively decomposed in a catalytic combustion device.
生する使用済イオン交換樹脂、フィルタースラッジもし
くは除染廃液、または核燃料再処理工場から発生する廃
溶媒のいずれかである請求項１または２の処理方法。3. The radioactive organic waste is one of a spent ion exchange resin generated at a nuclear power plant, a filter sludge or a decontamination waste liquid, and a waste solvent generated from a nuclear fuel reprocessing plant. Processing method.
混合物の加熱を、燃焼ガスの導入により実施する請求項
１または２の処理方法。4. The treatment method according to claim 1, wherein the heating of the mixture of the intermediate product of the oxidative decomposition reaction and steam is carried out by introducing a combustion gas.
生成物と水蒸気との混合物と熱交換することにより利用
する請求項１または２の処理方法。5. The method according to claim 1, wherein heat of the exhaust gas from the combustion device is utilized by exchanging heat with a mixture of an intermediate product and steam.
せて湿式酸化分解するための、撹拌機をそなえた反応槽
（２）、反応槽への過酸化水素、触媒溶液およびｐＨ調
整用の酸・アルカリの供給タンク（２１〜２５）、反応
槽から揮発してくる酸化分解反応の中間生成物および水
蒸気の混合物を受け入れて、中間生成物を二次的に酸化
させるための、酸化触媒をそなえた触媒燃焼装置
（３）、触媒燃焼装置への酸素供給手段（４）、触媒燃
焼装置からの排ガスを冷却して凝縮水を得るためのコン
デンサー（５）、ならびに、触媒燃焼装置からの排ガス
の熱で混合ガスを加熱するための熱交換器（６）から本
質的に構成される放射性有機廃棄物の処理装置。6. A reaction tank (2) provided with a stirrer for reacting radioactive organic waste with hydrogen peroxide to perform wet oxidative decomposition, a hydrogen peroxide to the reaction tank, a catalyst solution, and a pH adjuster. An acid / alkali supply tank (21 to 25), an oxidation catalyst for receiving a mixture of the intermediate product of the oxidative decomposition reaction and water vapor volatilized from the reaction tank and secondary oxidation of the intermediate product, Provided catalytic combustion device (3), means for supplying oxygen to the catalytic combustion device (4), condenser (5) for cooling the exhaust gas from the catalytic combustion device to obtain condensed water, and exhaust gas from the catalytic combustion device An apparatus for treating radioactive organic waste, consisting essentially of a heat exchanger (6) for heating a gas mixture with the heat of
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| JP23767598A JP4224631B2 (en) | 1998-08-24 | 1998-08-24 | Method and apparatus for treating radioactive organic waste |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23767598A JP4224631B2 (en) | 1998-08-24 | 1998-08-24 | Method and apparatus for treating radioactive organic waste |
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