JPH0143592B2 - - Google Patents
Info
- Publication number
- JPH0143592B2 JPH0143592B2 JP3382383A JP3382383A JPH0143592B2 JP H0143592 B2 JPH0143592 B2 JP H0143592B2 JP 3382383 A JP3382383 A JP 3382383A JP 3382383 A JP3382383 A JP 3382383A JP H0143592 B2 JPH0143592 B2 JP H0143592B2
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- copper
- thiourea
- waste liquid
- acidic cation
- 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.)
- Expired
Links
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 64
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 29
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002699 waste material Substances 0.000 claims description 22
- 239000003729 cation exchange resin Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 14
- 239000003456 ion exchange resin Substances 0.000 claims description 8
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 8
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005202 decontamination Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003588 decontaminative effect Effects 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009390 chemical decontamination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- LROWILPKXRHMNL-UHFFFAOYSA-N copper;thiourea Chemical compound [Cu].NC(N)=S LROWILPKXRHMNL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Description
本発明は、チオ尿素を含有した廃液の処理方法
に関し、特に火力および原子力発電プラントにお
いて配管および機器を化学洗浄した廃液からチオ
尿素を除去する方法に関するものである。
火力発電プラントにおいてはボイラ、熱交換器
等の保守のためクエン酸、シユウ酸、ギ酸等の有
機酸を主とする酸洗浄やエチレンジアミン四酢酸
（以下、EDTAと称す）等のキレート剤を主とし
たキレート洗浄が行われており、必要に応じ、こ
れ等薬品に腐食抑制剤を添加する場合もある。洗
浄の対象となるスケール成分は被洗浄体の種類等
により異なるが鉄の酸化物、銅の酸化物および金
属銅が主である。このスケールを効果的に溶解除
去するために上記薬品を１〜10％の高濃度で使用
する場合が多い。チオ尿素は銅イオン封鎖剤とし
て特に銅成分の多いスケールの洗浄用又は腐食抑
制剤として上記薬品との併用でよく使用される。
これ等薬品は高濃度で使用されるので、洗浄廃液
は非常にCOD濃度が高く、またスケール溶解に
由来する鉄、銅等の金属濃度も高い。
例えば、第１表に示す洗浄廃液はCODが20000
mg／にもなり、何らかの処理をしなければ放流
することは難しい。
The present invention relates to a method for treating waste liquid containing thiourea, and more particularly to a method for removing thiourea from waste liquid obtained by chemically cleaning piping and equipment in thermal and nuclear power plants. In thermal power plants, acid cleaning mainly uses organic acids such as citric acid, oxalic acid, and formic acid, and chelating agents such as ethylenediaminetetraacetic acid (hereinafter referred to as EDTA) are mainly used for maintenance of boilers, heat exchangers, etc. Chelate cleaning is carried out, and if necessary, corrosion inhibitors may be added to these chemicals. The scale components to be cleaned vary depending on the type of object to be cleaned, but mainly include iron oxides, copper oxides, and metallic copper. In order to effectively dissolve and remove this scale, the above chemicals are often used at a high concentration of 1 to 10%. Thiourea is often used as a copper ion sequestering agent, particularly for cleaning copper-rich scales, or as a corrosion inhibitor in combination with the above chemicals.
Since these chemicals are used in high concentrations, the cleaning waste liquid has a very high concentration of COD, and also has a high concentration of metals such as iron and copper derived from scale dissolution. For example, the cleaning waste shown in Table 1 has a COD of 20,000.
mg/, making it difficult to release without some kind of treatment.
【表】
＊ 水洗水を含んだ分析値である。
処理目標値は公害防止対策上COD10mg／以
下が必要であるが、第１表に示すような廃水の
CODを10mg／以下にするのは非常に難しい。
一方、第２表は第１表に示す廃液を過酸化水素
（H2O2）にて酸化処理し、さらにその廃液を活性
炭吸着、次亜塩素酸処理を行つた例である。[Table] *Analysis values include washing water.
The treatment target value must be COD 10mg/or less for pollution prevention measures, but the wastewater as shown in Table 1
It is very difficult to reduce COD to 10mg/or less. On the other hand, Table 2 shows an example in which the waste liquid shown in Table 1 was oxidized with hydrogen peroxide (H 2 O 2 ), and the waste liquid was then adsorbed with activated carbon and treated with hypochlorous acid.
【表】
の上澄液に対する過酸化水素処理
＊2 強塩基性アニオン樹脂による処理
第２表から明らかなようにCODは過酸化水素
処理で100〜200mg／まで低下するが、それ以降
はあまり低下しない。イオン交換処理を行うとあ
る程度除去される場合があるが、CODが50mg／
以上残留し目標値の達成は無理である。本発明
者等は、イオン交換処理してもさらに残留してい
るCOD成分のうち、多くがチオ尿素に由来する
ことを見出した。
チオ尿素は化学的に安定であり、非常に高濃度
のオゾンまたは過酸化水素と長期間接触させても
完全に分解するのは困難である。また、チオ尿素
を過剰の銅イオンと反応させチオ尿素銅の沈殿と
して固液分離する方法も知られているが、100
mg／以下にするのは困難である。さらに、チオ
尿素の分子量は76と小さいので膜分離するのも難
しい。
本発明者等は、チオ尿素除去に関しさらに鋭意
研究を進めた結果、本発明を完成するに至つた。
本発明は、銅型の強酸性カチオン交換樹脂また
は銅型の弱酸性カチオン交換樹脂にチオ尿素含有
廃液を通液し、チオ尿素を選択的に吸着除去する
ことを特徴としている。これによつてチオ尿素は
数mg／となり、CODを10mg／以下にするこ
とが可能となつた。
銅型のイオン交換樹脂でチオ尿素が除去される
機構は明らかではないが、樹脂中の銅とチオ尿素
とのキレート生成によるものと考えられる。しか
し、EDTAのようなキレート剤を高濃度に含む
洗浄廃液を直接銅型のカチオン樹脂層に通液する
と、樹脂中の銅とEDTAがキレートを生成し樹
脂層からリークする。したがつて、銅型のカチオ
ン樹脂に洗浄廃液をそのまま通液するのは好まし
くなく凝集沈殿、酸化処理等の前処理を行い大部
分の金属およびCOD成分を除去しておくのが好
ましい。酸化処理としては過酸化水素処理、オゾ
ン処理、電解などが利用できる。
このような前処理を行つた後、銅型のカチオン
樹脂に通液させる前にさらに強酸性カチオン交換
樹脂（以下、「SAR」と称す）と強塩基性アニオ
ン交換樹脂（以下、「SBR」と称す）とを再生型
で混合した樹脂層に通液し、前処理の後も残留し
ている有機酸、キレート剤等を吸着除去しておく
のが好ましい。チオ尿素は混合樹脂層を通過し、
銅型のカチオン樹脂層で吸着除去される。銅型の
カチオン樹脂層の後、さらにSARとSBRの再生
型よりなる混合層を設け、最初の混合層および銅
型のカチオン樹脂層を通過する微量のCOD成分
をポリツシヤとして除去させるようにしても良い
が、その判断は処理水の用途によつて決めればよ
く、単に放流するだけならばポリツシヤの設置は
必要ない。また、洗浄液が希釈された状態なら
ば、その量にもよるが前処理を省略し直接前記イ
オン交換樹脂に通液してもよい。
銅型のカチオン樹脂およびその上流・下流の混
合樹脂は各々別の塔に充填し順に通液するように
してもよいが、図示の如く一つの塔内に各々の樹
脂層を形成させるべく充填した方がコンパクトで
ある。図中１，３はSAR，SBRの再生型の混合
層、２は銅型カチオン交換樹脂層である。なお、
銅型のカチオン樹脂の調製は市販のSARに
CuCl2，CuSO4等の溶液を通液し水洗するだけで
よい。
以上の操作によりチオ尿素は数mg／となり、
CODを10mg／以下にすることが可能となつた。
洗浄液としてチオ尿素を含有しない液を使用する
場合の洗浄廃液処理は、銅型のカチオン樹脂を使
用する必要はなく、この樹脂を省略するだけで先
に述べた方法はそのまま適用できる。
一方、本発明は原子力発電プラントのシステム
除染にも適用できる。原子力発電プラントをシス
テム除染する方法として化学洗浄は非常に有効な
方法である。ここで、使用する薬品は火力発電所
のように濃厚液を使用する方法も検討されている
が、除染廃液処理および除染後の機器の信頼性等
の問題点から最近は希釈薬剤化学除染法が注目さ
れている。この方法は有機酸等の薬品を１％以下
の低濃度に希釈して使用し、洗浄終了後は混床塔
又は逆浸透膜装置と混床塔の組合せで薬品を分離
除去することを特徴としており除染効果は高濃度
液を使用した場合ほどではないが、腐食が小さい
という利点を有している。しかし、この方法はイ
オン交換反応を利用するので、使用できる薬品の
範囲は限定されている。本発明を希釈薬剤化学除
染法に適用すれば、従来より使用困難であつたチ
オ尿素を使用することが可能となり、さらに効果
的な除染が期待できる。
以上述べたように、本発明は公害防止に寄与す
るばかりでなく、原子力発電プラントにおける作
業員の被曝低減にも寄与し、環境保全および環境
衛生上多大な利益を生ずるものである。
（実施例１および比較例）
強酸性カチオン交換樹脂ダウエツクスHCR―
Ｓ（商品名）300mlと強塩基性アニオン交換樹脂ダ
ウエツクスSBR―Ｐ（商品名）600mlを、それぞ
れ塩酸および水酸化ナトリウムで再生した後、両
者を混合し、そのうち300mlを内径50mm〓のアクリ
ル製カラムに充填した。次いで、その上部に銅型
に調製したダウエツクスHCR―Ｓを300ml充填
し、さらにその上部に前記残りの混合樹脂600ml
を充填した。銅型への調製は別のカラムにHCR
―S300mlを充填しCuCl25％水溶液を３通液し、
次いで純水にて洗浄するという手順で行つた。
さらに、50mm〓のアクリル製カラムをもう１本
用意し、比較のため銅型樹脂を含まない混合樹脂
のみを充填した。
一方、火力発電所におけるボイラの化学洗浄廃
液としてクエン酸、ギ酸およびチオ尿素を含有す
る酸洗廃液を用意した。この廃液には水洗水が含
まれておりPH3.9，COD12000mg／，Fe6300
mg／という水質であつた。
この液を硫酸でPH３に調整したあと、過酸化水
素を１日に１回の割合で15000mg／（０として）
添加し３日間処理したところ、CODは153mg／
、チオ尿素84mg／に低下した。この液を先の
カラム２本にSV5の流速で通液したところ、銅型
樹脂を含む本発明のカラムの処理水CODは3.5
mg／、チオ尿素５mg／になつた。一方、銅型
樹脂を含まない比較例のカラムは処理水CODが
59mg／、チオ尿素84mg／と悪かつた。
（実施例 ２）
弱酸性カチオン交換樹脂ダウエツクスCCR―
２（商品名）300mlに水酸化ナトリウムを通液し洗
浄した後、CuCl25％溶液５通液し銅型とした。
この樹脂を実施例１に示す方法で上下に混合樹脂
層が位置するよう充填した。このカラムに実施例
１の過酸化水素処理した水を通液したところ、処
理水CODは3.7mg／、チオ尿素５mg／になり
実施例１と同様の効果があつた。
（実施例３および比較例）
シユウ酸1000mg／、チオ尿素60mg／を含有
する液を実施例１、比較例の２本のカラムに通液
したところ、実施例のカラムの処理水質は、導電
率0.12μs／cm・at25℃、チオ尿素３mg／、
COD2mg／であつたが比較例のカラムの水質は
導電率0.14μs／cm・at25℃、チオ尿素60mg／、
COD45mg／であつた。[Table] Hydrogen peroxide treatment of supernatant liquid *2 Treatment with strong basic anion resin As is clear from Table 2, COD decreases to 100 to 200 mg/by hydrogen peroxide treatment, but after that it does not decrease much. do not. COD may be removed to some extent by ion exchange treatment, but COD is 50mg/
It is impossible to achieve the target value due to the remaining amount. The present inventors have discovered that most of the COD components that remain even after ion exchange treatment are derived from thiourea. Thiourea is chemically stable and difficult to completely decompose even on prolonged contact with very high concentrations of ozone or hydrogen peroxide. Another known method is to react thiourea with excess copper ions and perform solid-liquid separation to precipitate copper thiourea.
It is difficult to reduce the amount to less than mg/mg. Furthermore, thiourea has a small molecular weight of 76, making it difficult to separate it through membranes. The present inventors further conducted intensive research on thiourea removal, and as a result, completed the present invention. The present invention is characterized in that a thiourea-containing waste liquid is passed through a copper-type strongly acidic cation exchange resin or a copper-type weakly acidic cation exchange resin, and thiourea is selectively adsorbed and removed. This has made it possible to reduce the amount of thiourea to several mg/kg and reduce the COD to less than 10 mg/kg. Although the mechanism by which thiourea is removed by copper-type ion exchange resins is not clear, it is thought to be due to the formation of a chelate between copper and thiourea in the resin. However, when cleaning waste liquid containing a high concentration of a chelating agent such as EDTA is passed directly through a copper-type cationic resin layer, the copper and EDTA in the resin form a chelate, which leaks from the resin layer. Therefore, it is not preferable to pass the cleaning waste liquid through the copper-type cationic resin as it is, but it is preferable to perform pretreatment such as coagulation precipitation and oxidation treatment to remove most of the metal and COD components. As the oxidation treatment, hydrogen peroxide treatment, ozone treatment, electrolysis, etc. can be used. After such pretreatment, a strongly acidic cation exchange resin (hereinafter referred to as "SAR") and a strongly basic anion exchange resin (hereinafter referred to as "SBR") are added before passing the solution through the copper-type cation resin. It is preferable to pass the liquid through a resin layer mixed with the above-mentioned materials in a regenerated form to adsorb and remove organic acids, chelating agents, etc. that remain even after the pretreatment. Thiourea passes through the mixed resin layer,
It is adsorbed and removed by a copper-type cationic resin layer. After the copper-type cationic resin layer, a mixed layer of recycled SAR and SBR is further provided to remove trace amounts of COD components passing through the first mixed layer and the copper-type cationic resin layer as a polisher. However, the decision should be made based on the intended use of the treated water, and if the water is simply being discharged, there is no need to install a polisher. Further, if the cleaning liquid is in a diluted state, the pretreatment may be omitted and the liquid may be directly passed through the ion exchange resin, depending on the amount. The copper-type cationic resin and its upstream and downstream mixed resins may be packed in separate towers and passed through in order, but as shown in the figure, it is possible to fill them in one tower to form their respective resin layers. It is more compact. In the figure, 1 and 3 are regenerated mixed layers of SAR and SBR, and 2 is a copper-type cation exchange resin layer. In addition,
Preparation of copper-type cationic resin is based on commercially available SAR
All you have to do is pass a solution such as CuCl 2 or CuSO 4 through it and wash it with water. Through the above operations, the amount of thiourea will be several mg/
It has become possible to reduce COD to 10mg/or less.
When cleaning waste liquid is treated using a liquid that does not contain thiourea as the cleaning liquid, there is no need to use a copper-type cationic resin, and the method described above can be applied as is by simply omitting this resin. On the other hand, the present invention can also be applied to system decontamination of nuclear power plants. Chemical cleaning is a very effective method for system decontamination of nuclear power plants. The use of concentrated chemicals as used in thermal power plants has been considered, but due to issues such as the treatment of decontamination waste liquid and the reliability of post-decontamination equipment, diluted chemicals have recently been used. Dyeing methods are attracting attention. This method uses chemicals such as organic acids diluted to a low concentration of 1% or less, and after cleaning, the chemicals are separated and removed using a mixed bed column or a combination of a reverse osmosis membrane device and a mixed bed column. Although the decontamination effect is not as great as when using a highly concentrated solution, it has the advantage of less corrosion. However, since this method utilizes an ion exchange reaction, the range of chemicals that can be used is limited. If the present invention is applied to a dilute chemical decontamination method, it becomes possible to use thiourea, which has been difficult to use in the past, and even more effective decontamination can be expected. As described above, the present invention not only contributes to pollution prevention, but also contributes to the reduction of radiation exposure of workers in nuclear power plants, and brings about great benefits in terms of environmental conservation and environmental health. (Example 1 and Comparative Example) Strongly acidic cation exchange resin DOWEX HCR-
After regenerating 300 ml of S (trade name) and 600 ml of strong basic anion exchange resin DOWEX SBR-P (trade name) with hydrochloric acid and sodium hydroxide, the two were mixed, and 300 ml of the mixture was transferred to an acrylic column with an inner diameter of 50 mm. was filled. Next, 300 ml of Dowex HCR-S prepared in a copper mold is filled on top of it, and 600 ml of the remaining mixed resin is added on top of it.
filled with. Preparation to copper type HCR on separate column
-Fill 300ml of S and add CuCl 2 5% aqueous solution three times.
Next, the procedure was to wash with pure water. In addition, another 50 mm acrylic column was prepared, and for comparison, it was filled only with a mixed resin that did not contain copper-type resin. On the other hand, a pickling waste liquid containing citric acid, formic acid, and thiourea was prepared as a chemical cleaning waste liquid of a boiler in a thermal power plant. This waste liquid contains washing water, PH3.9, COD12000mg/, Fe6300
The water quality was mg/mg. After adjusting this solution to PH3 with sulfuric acid, add hydrogen peroxide at a rate of 15,000 mg/(0) once a day.
When added and treated for 3 days, COD was 153mg/
, thiourea decreased to 84 mg/thiourea. When this liquid was passed through the previous two columns at a flow rate of SV5, the COD of the treated water in the column of the present invention containing copper-type resin was 3.5.
mg/, and thiourea 5 mg/. On the other hand, the treated water COD of the comparative example column that does not contain copper-type resin is
It was 59mg/, and thiourea 84mg/. (Example 2) Weakly acidic cation exchange resin DOWEX CCR-
After washing by passing sodium hydroxide through 300 ml of 2 (trade name), five 5% CuCl 2 solutions were passed therethrough to form a copper mold.
This resin was filled by the method shown in Example 1 so that mixed resin layers were located above and below. When the hydrogen peroxide treated water of Example 1 was passed through this column, the COD of the treated water was 3.7 mg/, and the thiourea was 5 mg/, and the same effects as in Example 1 were obtained. (Example 3 and Comparative Example) When a solution containing 1000 mg of oxalic acid and 60 mg of thiourea was passed through the two columns of Example 1 and Comparative Example, the treated water quality of the column of Example was as follows: 0.12μs/cm・at25℃, thiourea 3mg/,
COD was 2mg/, but the water quality of the column in the comparative example was conductivity 0.14μs/cm at 25℃, thiourea 60mg/,
COD was 45mg/.
図面は、本発明の実施に使用されるイオン交換
樹脂塔の一例を示す縦断面図である。
１，３…混合層、２…銅型カチオン交換樹脂
層。
The drawing is a longitudinal cross-sectional view showing an example of an ion exchange resin tower used in carrying out the present invention. 1, 3...mixed layer, 2...copper type cation exchange resin layer.
Claims (1)
酸性カチオン交換樹脂にチオ尿素含有廃液を通液
し、該廃液中のチオ尿素を吸着除去することを特
徴とするチオ尿素含有廃液の処理方法。 ２ 前記チオ尿素含有廃液を、前記銅型の強酸性
カチオン交換樹脂又は銅型の弱酸性カチオン交換
樹脂に通液する前及び／又は後に強酸性カチオン
交換樹脂と強塩基性アニオン交換樹脂との混合樹
脂に通液する特許請求の範囲第１項記載の処理方
法。 ３ 前記チオ尿素含有廃液を、前記銅型の強酸性
カチオン交換樹脂又は銅型の弱酸性カチオン交換
樹脂を充填したイオン交換樹脂塔と、該イオン交
換樹脂塔の上流側及び／又は下流側に配設した、
前記混合樹脂を充填したイオン交換樹脂塔とに通
液する特許請求の範囲第２項記載の処理方法。 ４ 前記チオ尿素含有廃液を、前記銅型の強酸性
カチオン交換樹脂又は銅型の弱酸性カチオン交換
樹脂の上層及び／又は下層に前記混合樹脂を充填
したイオン交換樹脂塔に通液する特許請求の範囲
第２項記載の処理方法。 ５ 前記チオ尿素含有廃液が高濃度の場合は、該
廃液をイオン交換樹脂に通液する前に、あらかじ
め凝集沈殿、酸化処理等の前処理を行う特許請求
の範囲第１項、第２項、第３項又は第４項記載の
処理方法。[Scope of Claims] 1 A thiourea-containing waste liquid is passed through a copper-type strongly acidic cation exchange resin or a copper-type weakly acidic cation exchange resin, and thiourea in the waste liquid is adsorbed and removed. A method for treating urea-containing waste liquid. 2. Mixing a strongly acidic cation exchange resin and a strongly basic anion exchange resin before and/or after passing the thiourea-containing waste liquid through the copper-type strongly acidic cation exchange resin or the copper-type weakly acidic cation exchange resin. The treatment method according to claim 1, wherein a liquid is passed through the resin. 3. The thiourea-containing waste liquid is distributed to an ion exchange resin column filled with the copper-type strongly acidic cation exchange resin or the copper-type weakly acidic cation exchange resin, and to the upstream and/or downstream sides of the ion exchange resin column. established,
3. The treatment method according to claim 2, wherein the mixed resin is passed through an ion exchange resin tower filled with the mixed resin. 4. The thiourea-containing waste liquid is passed through an ion exchange resin tower in which the mixed resin is filled in the upper and/or lower layers of the copper-type strongly acidic cation exchange resin or the copper-type weakly acidic cation exchange resin. The treatment method described in Scope 2. 5. If the thiourea-containing waste liquid has a high concentration, pretreatment such as coagulation and precipitation, oxidation treatment, etc. is performed in advance before passing the waste liquid through an ion exchange resin. The processing method described in item 3 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3382383A JPS59160585A (en) | 1983-03-03 | 1983-03-03 | Process for disposing waste liquid containing thiourea |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3382383A JPS59160585A (en) | 1983-03-03 | 1983-03-03 | Process for disposing waste liquid containing thiourea |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59160585A JPS59160585A (en) | 1984-09-11 |
| JPH0143592B2 true JPH0143592B2 (en) | 1989-09-21 |
Family
ID=12397203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3382383A Granted JPS59160585A (en) | 1983-03-03 | 1983-03-03 | Process for disposing waste liquid containing thiourea |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59160585A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2599912B2 (en) * | 1987-01-09 | 1997-04-16 | 三菱電機株式会社 | Scroll compressor |
| JP5408569B2 (en) * | 2010-02-23 | 2014-02-05 | 栗田工業株式会社 | Method and apparatus for treating thiourea-containing water |
| JP5966514B2 (en) * | 2012-03-29 | 2016-08-10 | 栗田工業株式会社 | Method and apparatus for treating thiourea-containing water |
-
1983
- 1983-03-03 JP JP3382383A patent/JPS59160585A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59160585A (en) | 1984-09-11 |
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