JP3390138B2 - Treatment method for ion exchange resin regeneration waste liquid - Google Patents
Treatment method for ion exchange resin regeneration waste liquidInfo
- Publication number
- JP3390138B2 JP3390138B2 JP18559898A JP18559898A JP3390138B2 JP 3390138 B2 JP3390138 B2 JP 3390138B2 JP 18559898 A JP18559898 A JP 18559898A JP 18559898 A JP18559898 A JP 18559898A JP 3390138 B2 JP3390138 B2 JP 3390138B2
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- exchange resin
- test
- ion exchange
- resin regeneration
- 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 - Fee Related
Links
- 239000007788 liquid Substances 0.000 title claims description 41
- 239000002699 waste material Substances 0.000 title 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 title claims description 22
- 239000003456 ion exchange resin Substances 0.000 title claims description 17
- 229920003303 ion-exchange polymer Polymers 0.000 title claims description 17
- 238000011069 regeneration method Methods 0.000 title claims description 14
- 230000008929 regeneration Effects 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 12
- 238000005260 corrosion Methods 0.000 claims description 44
- 230000007797 corrosion Effects 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000003112 inhibitor Substances 0.000 claims description 18
- 150000002506 iron compounds Chemical group 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 239000000463 material Substances 0.000 description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000001978 electrochemical passivation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イオン交換樹脂再
生廃液の処理方法、更に詳しくは、アルカノールアミン
含有酸性廃液であるイオン交換樹脂再生廃液を蒸発せし
めて濃縮減量化するに際し、蒸発装置の金属腐食を抑制
し得て安全化が図れる処理方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating an ion-exchange resin regeneration waste liquid, and more particularly to a method for treating an ion-exchange resin regeneration waste liquid, which is an acidic waste liquid containing alkanolamine, by evaporating the metal of an evaporator. The present invention relates to a treatment method capable of suppressing corrosion and achieving safety.
【０００２】[0002]
【従来の技術】従来、モノエタノールアミン等を吸着し
た陽イオン交換樹脂を鉱酸（塩酸等）で再生処理する際
に発生するアルカノールアミン含有酸性廃液であるイオ
ン交換樹脂再生廃液を蒸発させて濃縮減量化せしめるこ
とは公知である。2. Description of the Related Art Conventionally, an alkanolamine-containing acidic waste liquid that is generated when a cation exchange resin that has adsorbed monoethanolamine or the like is regenerated with a mineral acid (such as hydrochloric acid) is evaporated and concentrated. It is known to reduce the amount.
【０００３】例えば、特開平９−３１４１２８号公報中
の段落［００１６］には、有機アミンを吸着した陽イオ
ン交換樹脂の再生廃液を加熱して水分を蒸発させ、有機
アミンを濃縮する蒸発濃縮を行った後、得られた濃縮液
中の有機アミンを気化させると共に濃縮液中の無機塩類
を固形物として分離し、気化した蒸気を燃焼して有機ア
ミンを燃焼分解することが記載されている。For example, in paragraph [0016] of Japanese Patent Application Laid-Open No. 9-314128, evaporative concentration for condensing an organic amine by heating a recycled waste liquid of a cation exchange resin having adsorbed an organic amine to evaporate water is described. After carrying out, it is described that the organic amine in the obtained concentrated liquid is vaporized, the inorganic salts in the concentrated liquid are separated as solids, and the vaporized vapor is burned to combust and decompose the organic amine.
【０００４】なお、かかるイオン交換樹脂再生廃液は、
アルカノールアミンが有機化合物であることからして高
濃度のＣＯＤが含有されていると共に陽イオン交換樹脂
の再生液として用いられる塩酸等が高濃度に含有されて
いる為、生物処理方法や湿式酸化処理方法等のような他
の一般的なＣＯＤ除去方法では対処し難く、従って、上
述のように蒸発濃縮をせざるを得ない。Incidentally, such an ion exchange resin recycling waste liquid is
Since alkanolamine is an organic compound, it contains a high concentration of COD, and also contains a high concentration of hydrochloric acid used as a regenerating liquid for a cation exchange resin, which makes it a biological treatment method or a wet oxidation treatment. It is difficult to deal with other general COD removal methods such as the method, and therefore, it is necessary to perform evaporation concentration as described above.
【０００５】[0005]
【発明が解決しようとする課題】しかし、その場合にお
いて、前記公報中の段落［００３５］に記載されている
ように、イオン交換樹脂再生廃液に金属腐食性の強い塩
酸等が含有されていることに起因して、その蒸発装置
（例えば、フラッシュ缶型の装置等）を高価な耐腐食性
材（例えば、チタン材等）で構成しなければならない
が、そのような高価な耐腐食性材で構成しても完全に安
全であるとは言い切れない。However, in that case, as described in paragraph [0035] of the above publication, the ion-exchange resin regeneration waste liquid contains hydrochloric acid having a strong metal corrosive property. Due to this, the evaporation device (for example, a flash can type device) must be composed of an expensive corrosion-resistant material (for example, titanium material). It is not completely safe to configure.
【０００６】本発明は、このような欠点に鑑み、それを
解決すべく鋭意検討の結果、かかるイオン交換樹脂再生
廃液に、鉄化合物（例えば、塩化第２鉄）等の適当な金
属腐食抑制剤を添加して処理すれば良いことを見い出
し、本発明を完成したものである。In view of the above-mentioned drawbacks, the present invention has made intensive studies to solve the above-mentioned problems, and as a result, in the waste liquid for recycling the ion-exchange resin, an appropriate metal corrosion inhibitor such as an iron compound (eg, ferric chloride) was added. The present invention has been completed by finding out that it suffices to add and treat.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明に係る
イオン交換樹脂再生廃液の処理方法は、請求項１に記載
するように、アルカノールアミン含有酸性廃液であるイ
オン交換樹脂再生廃液を蒸発せしめて濃縮減量化するに
際し、前記イオン交換樹脂再生廃液に金属腐食抑制剤を
添加することを特徴とするものである。なお、金属腐食
抑制剤は、塩化第２鉄や硫酸第２鉄等の鉄化合物が好ま
しく、また、蒸発濃縮液は、液中燃焼するのが好まし
い。That is, as described in claim 1, the method for treating an ion exchange resin regeneration waste liquid according to the present invention comprises evaporating the ion exchange resin regeneration waste liquid which is an alkanolamine-containing acidic waste liquid. When reducing the concentration, a metal corrosion inhibitor is added to the ion-exchange resin regeneration waste liquid. The metal corrosion inhibitor is preferably an iron compound such as ferric chloride or ferric sulfate, and the evaporated concentrate is preferably burned in the liquid.
【０００８】[0008]
【発明の実施の形態】本発明においては、イオン交換樹
脂再生廃液を処理対象とするが、この再生廃液は、モノ
エタノールアミン等を吸着した陽イオン交換樹脂を塩酸
等の鉱酸で再生処理する際に発生するアルカノールアミ
ン含有酸性廃液である。なお、その濃度や組成は、再生
方法等の諸条件により異なるが、通常、アルカノールア
ミン濃度として１％〜２％、塩酸濃度として３％〜７％
の強酸性廃液である。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an ion exchange resin regenerating waste liquid is treated, and this regenerating waste liquid regenerates a cation exchange resin having adsorbed monoethanolamine or the like with a mineral acid such as hydrochloric acid. It is an alkanolamine-containing acidic waste liquid generated at the time. The concentration and composition will vary depending on various conditions such as the regeneration method, but normally, the alkanolamine concentration is 1% to 2%, and the hydrochloric acid concentration is 3% to 7%.
It is a strongly acidic waste liquid.
【０００９】また、かかる再生廃液に金属腐食抑制剤を
添加するが、これは、イオン交換樹脂再生廃液の発生箇
所や貯留箇所等において適当な混合装置により均一に混
合添加せしめたり、或いは、金属腐食抑制剤を溶解した
水溶液を蒸発装置に入る直前において管内混合器で均一
に混合添加せしめたり、更には、かかる水溶液を蒸発装
置の液循環ラインに定量ポンプで注入せしめたりする
等、いかなる方法で行ってもよい。In addition, a metal corrosion inhibitor is added to the recycled waste liquid, which is added or mixed uniformly by an appropriate mixing device at a place where the recycled waste liquid of the ion exchange resin is generated or a storage place, or metal corrosion. Immediately before entering the evaporation device, the aqueous solution in which the inhibitor is dissolved is mixed and added uniformly in the pipe mixer, and further, such an aqueous solution is injected into the liquid circulation line of the evaporation device with a metering pump. May be.
【００１０】また、その添加量についても、アルカノー
ルアミン及び塩酸等の濃度や添加する金属腐食抑制剤の
種類等の諸条件に対応せしめて所定量を設定することが
できるが、一般には、金属腐食抑制剤の総量として１０
ｐｐｍ〜２％、好ましくは１０ｐｐｍ〜３０００ｐｐｍ
程度を添加すればよい。Regarding the amount of addition, a predetermined amount can be set in accordance with various conditions such as the concentration of alkanolamine and hydrochloric acid and the type of metal corrosion inhibitor to be added. 10 as total amount of inhibitor
ppm to 2%, preferably 10 ppm to 3000 ppm
The degree may be added.
【００１１】また、金属腐食抑制剤として、塩化第１
鉄、塩化第２鉄、硫酸第１鉄、硝酸鉄及び硫酸第２鉄等
の鉄化合物が好適である。何故ならば、例えば、チタン
材の場合において、かかる鉄化合物を添加することによ
り、それの強い酸化性によってチタン材の表面に一種の
酸化被膜である不動態被膜が形成されてチタンのイオン
化（溶出）を防止するといった所謂、電気化学的に不動
態化現象が惹起されるからである。なお、鉄化合物の添
加は、その一種又は複数種のいずれであってもよく、ま
た、鉄化合物以外の他の適当な金属腐食抑制剤を選択し
てもよい。Further, as a metal corrosion inhibitor, first chloride
Iron compounds such as iron, ferric chloride, ferrous sulfate, iron nitrate and ferric sulfate are preferred. This is because, for example, in the case of a titanium material, by adding such an iron compound, a strong passivation film, which is a kind of oxide film, is formed on the surface of the titanium material due to its strong oxidizing property, and the titanium ionization (elution) is performed. This is because a so-called electrochemical passivation phenomenon is induced electrochemically. The iron compound may be added singly or in combination, and an appropriate metal corrosion inhibitor other than the iron compound may be selected.
【００１２】更に、蒸発方法についても、特定方法に限
定されないが、減圧下で蒸発させるのが好ましく、か
つ、その際の温度は減圧度により決定されるが、１００
Ｔｏｒｒ以下の場合においては６０℃〜７０℃、常圧の
場合においては１１０℃〜１３０℃であればよい。Further, the evaporation method is not limited to a specific method, but it is preferable to evaporate under reduced pressure, and the temperature at that time is determined by the degree of reduced pressure.
It may be 60 ° C. to 70 ° C. in the case of Torr or less, and 110 ° C. to 130 ° C. in the case of normal pressure.
【００１３】また、蒸発装置についても特定のものに限
定されない。すなわち、強制循環型、フラッシュ缶型、
流下薄膜型等、いかなる型式のものであってもよい。な
お、それらの蒸発缶や伝熱管、更には、その周辺の構成
部材（液が接触する箇所の構成部材）を、チタン材、タ
ンタル材、ジルコニウム材、ハステロイＣ材等の耐腐食
性材で構成するのが好ましい。Also, the evaporation device is not limited to a specific one. That is, forced circulation type, flash can type,
It may be of any type such as a falling film type. It should be noted that those evaporators, heat transfer tubes, and the surrounding components (components in contact with the liquid) are made of a corrosion-resistant material such as titanium material, tantalum material, zirconium material, and Hastelloy C material. Preferably.
【００１４】何故ならば、それらの耐腐食性材を用いる
こととイオン交換樹脂再生廃液に金属腐食抑制剤を添加
することとの組み合わせにより、金属腐食に対する安全
性がより十分になるからである。なお、濃縮倍率につい
ても、アルカノールアミンの濃度等により種々に選択す
ることができるが、一般に１０倍〜３０倍に設定すれば
よい。This is because the combination of using these corrosion resistant materials and adding the metal corrosion inhibitor to the ion exchange resin regeneration waste liquid makes the safety against metal corrosion more sufficient. The concentration ratio can be variously selected depending on the concentration of alkanolamine and the like, but it is generally set to 10 to 30 times.
【００１５】よって、この処理により、蒸発凝縮水が発
生するが、この凝縮水は、塩酸水溶液であって、アルカ
ノールアミンの含有がＣＯＤ値として１０ｐｐｍ以下で
あるから、中和処理だけを行って放流することができ
る。なお、この中和処理は容易に行うことができる。Therefore, by this treatment, evaporative condensed water is generated. Since this condensed water is an aqueous hydrochloric acid solution and the content of alkanolamine is 10 ppm or less as the COD value, only the neutralizing treatment is performed and the condensed water is discharged. can do. The neutralization treatment can be easily performed.
【００１６】一方、濃縮液には、アルカノールアミン、
塩酸及び金属腐食抑制剤等が高濃度に含有されている。
その為、この液を液中燃焼するのが好ましく、これによ
り、エタノールアミンも燃焼分解せしめることができて
産業廃棄物の発生をほぼ完全に阻止することができる。On the other hand, the concentrated liquid contains alkanolamine,
It contains hydrochloric acid and metal corrosion inhibitors in high concentrations.
Therefore, it is preferable to burn this liquid in the liquid, whereby ethanolamine can also be burned and decomposed, and generation of industrial waste can be almost completely prevented.
【００１７】このように、本発明によると、処理が困難
視されていたイオン交換樹脂再生廃液を、金属腐食に対
する安全性を十分に保ちながら効果的に蒸発処理するこ
とができる。なお、金属の腐食性及び各種の剤の腐食抑
制効果を確認する為に下記のテストを行った。As described above, according to the present invention, it is possible to effectively vaporize the ion-exchange resin regeneration waste liquid, which has been regarded as difficult to treat, while sufficiently maintaining the safety against metal corrosion. The following tests were conducted in order to confirm the corrosiveness of metals and the corrosion inhibiting effect of various agents.
【００１８】［テスト１］…上部にコンデンサを備えた
１０００ｍｌのフラスコに、モノエタノールアミン１．
１％と塩酸３．１％の混合水溶液５００ｍｌを入れると
共に、この中に、チタン−パラジウム合金製試験片（直
径が１９ｍｍ、長さが５０ｍｍ、比重が約４．５）を浸
漬し、窒素でシールした後、マントルヒータで加熱して
８０℃に一定に保ち、１００時間経過した時点で前記試
験片を取り出して重量を計り、試験前の重量に対する変
化量（重量減）を求めて下記式により腐食速度Ｖ（ｍｍ
／年）を計算したところ０．１３ｍｍ／年であった。ま
た、前記試験片表面の光沢が失われ薄茶褐色に変化して
いた。[Test 1] ... In a 1000 ml flask equipped with a condenser on top, 1.
While putting 500 ml of a mixed aqueous solution of 1% and 3.1% hydrochloric acid, a titanium-palladium alloy test piece (diameter: 19 mm, length: 50 mm, specific gravity: about 4.5) was immersed in this, and nitrogen was used. After sealing, it was heated with a mantle heater and kept constant at 80 ° C. After 100 hours, the test piece was taken out and weighed, and the change amount (weight reduction) with respect to the weight before the test was calculated by the following formula. Corrosion rate V (mm
/ Year) was calculated to be 0.13 mm / year. Further, the gloss of the surface of the test piece was lost and the test piece was changed to a light brown color.
【００１９】Ｖ＝８７６００×Ｗ×（１／Ｓ）×（１／
Ｈ）×（１／Ｇ）。なお、Ｗは試験片の重量減（ｇ）、
Ｓは試験片の表面積（ｃｍ2 ）、Ｈは浸漬時間（ｈ
ｒ）、Ｇは試験片の比重（ｇ／ｃｍ3 ）である。V = 87600 × W × (1 / S) × (1 /
H) x (1 / G). In addition, W is the weight reduction (g) of the test piece,
S is the surface area (cm 2 ) of the test piece, H is the immersion time (h
r) and G are the specific gravities (g / cm 3 ) of the test pieces.
【００２０】［テスト２］…混合水溶液に、金属腐食抑
制剤として塩化第２鉄０．１３％を添加したこと以外の
条件は、テスト１と同じ条件でテストしたところ、腐食
速度Ｖは０．０１ｍｍ／年であった。また、その表面状
態はテスト前と同じ（変化なし）であった。[Test 2] ... The test was conducted under the same conditions as Test 1 except that 0.13% of ferric chloride was added to the mixed aqueous solution as a metal corrosion inhibitor. It was 01 mm / year. The surface condition was the same as before the test (no change).
【００２１】［テスト３］…塩化第２鉄に代えて硫酸第
２鉄を添加したこと以外の条件は、テスト２と同じ条件
でテストしたところ、腐食速度Ｖは０．０２ｍｍ／年で
あった。また、その表面状態はテスト前と同じであっ
た。[Test 3] ... When tested under the same conditions as Test 2 except that ferric sulfate was added in place of ferric chloride, the corrosion rate V was 0.02 mm / year. . The surface condition was the same as before the test.
【００２２】［テスト４］…上部にコンデンサを備えた
１０００ｍｌのフラスコに、モノエタノールアミン２０
％、塩酸３１％の混合水溶液５００ｍｌを入れると共
に、この中に、金属腐食抑制剤として硫酸第１鉄８００
ｐｐｍ（ａｓＦｅ）を添加し、そして、これにチタン−
パラジウム合金製試験片（直径が１９ｍｍ、長さが５０
ｍｍ、比重が約４．５）を浸漬し、窒素でシールした
後、マントルヒータで加熱して５０℃に一定に保ち、１
００時間経過した時点で前記試験片を取り出して重量を
計り、試験前の重量に対する変化量（重量減）を求めて
腐食速度Ｖを計算したところ０．０１ｍｍ／年であっ
た。[Test 4]: A monoethanolamine 20 was added to a 1000 ml flask equipped with a condenser at the top.
%, 31% hydrochloric acid mixed aqueous solution (500 ml) was added, and ferrous sulfate 800 was added as a metal corrosion inhibitor.
ppm (asFe) was added, and titanium-
Palladium alloy test piece (diameter 19 mm, length 50
mm, specific gravity of about 4.5), dip and seal with nitrogen, then heat with a mantle heater to keep constant at 50 ° C
After the lapse of 00 hours, the test piece was taken out, weighed, and the change rate (weight reduction) from the weight before the test was calculated to calculate the corrosion rate V, which was 0.01 mm / year.
【００２３】［テスト５］…硫酸第１鉄を添加しないこ
と以外の条件は、テスト４と同一条件でテストしたとこ
ろ、腐食速度Ｖは０．１９ｍｍ／年であった。また、そ
の表面は変色し荒れた状態であった。[Test 5] ... When tested under the same conditions as Test 4 except that ferrous sulfate was not added, the corrosion rate V was 0.19 mm / year. In addition, the surface was discolored and in a rough state.
【００２４】［テスト６］…上部にコンデンサを備えた
１０００ｍｌのフラスコに、モノエタノールアミン２０
％、塩酸３１％の混合水溶液５００ｍｌを入れると共
に、この中に、金属腐食抑制剤として硫酸第２鉄５００
ｐｐｍ（ａｓＦｅ）及び塩化第１鉄５００ｐｐｍ（ａｓ
Ｆｅ）を添加し、そして、これにチタン−パラジウム合
金製試験片（直径が１９ｍｍ、長さが５０ｍｍ、比重が
約４．５）を浸漬し、窒素でシールした後、マントルヒ
ータで加熱して８０℃に一定に保ち、１００時間経過し
た時点で前記試験片を取り出して重量を計り、試験前の
重量に対する変化量（重量減）を求めて腐食速度を計算
したところ０．０３ｍｍ／年であった。また、その表面
状態はテスト前と同じであった。[Test 6] ... In a 1000 ml flask equipped with a condenser at the top, monoethanolamine 20 was added.
%, Hydrochloric acid 31%, and 500 ml of a mixed aqueous solution of ferric sulfate as a metal corrosion inhibitor.
ppm (asFe) and ferrous chloride 500 ppm (as
Fe) was added, and a titanium-palladium alloy test piece (diameter: 19 mm, length: 50 mm, specific gravity: about 4.5) was immersed in this, sealed with nitrogen, and then heated with a mantle heater. When the corrosion rate was calculated by calculating the amount of change (weight loss) with respect to the weight before the test by keeping the temperature constant at 80 ° C. and taking out the weight of the test piece after 100 hours, it was 0.03 mm / year. It was The surface condition was the same as before the test.
【００２５】［テスト７］…硫酸第２鉄及び塩化第１鉄
を添加しないこと以外の条件は、テスト６と同一条件で
テストしたところ、腐食速度Ｖは０．２９ｍｍ／年であ
った。また、その表面の光沢が失われ茶色に変化してい
た。[Test 7] ... When tested under the same conditions as Test 6 except that ferric sulfate and ferrous chloride were not added, the corrosion rate V was 0.29 mm / year. Also, the gloss of the surface was lost and the surface changed to brown.
【００２６】［テスト８］…モノエタノールアミンを不
添加の塩酸３．１％の水溶液を用いたこと以外の条件
は、テスト１と同一条件でテストしたところ、腐食速度
Ｖは、０．０２ｍｍ／年であった。[Test 8] ... When tested under the same conditions as Test 1 except that a 3.1% hydrochloric acid aqueous solution containing no monoethanolamine was used, the corrosion rate V was 0.02 mm / Was the year.
【００２７】［テスト９］…塩酸水溶液に塩化第２鉄
０．１３％を添加したこと以外の条件は、テスト８と同
一条件でテストしたところ、腐食速度Ｖは０．０２ｍｍ
／年であった。[Test 9] ... When tested under the same conditions as Test 8 except that 0.13% of ferric chloride was added to the hydrochloric acid aqueous solution, the corrosion rate V was 0.02 mm.
/ It was a year.
【００２８】［テスト１０］…塩化第２鉄に代えて塩化
第２銅を添加したこと以外の条件は、テスト２と同一条
件でテストしたところ、腐食速度Ｖは、０．０８ｍｍ／
年であった。また、その表面が薄茶褐色に変色してい
た。[Test 10] ... When tested under the same conditions as Test 2 except that cupric chloride was added in place of ferric chloride, the corrosion rate V was 0.08 mm /
Was the year. In addition, the surface was discolored to light brown.
【００２９】上述のテスト１〜７において、金属腐食抑
制剤としての鉄化合物を添加しているテスト２，３，
４，６における腐食速度Ｖと、それを添加していないテ
スト１，５，７における腐食速度Ｖとを対比して見た場
合、前者の腐食速度Ｖの方がいずれも著しく小さいか
ら、これの方が有利であることがわかる。In the above Tests 1 to 7, Tests 2 and 3 in which an iron compound was added as a metal corrosion inhibitor.
When the corrosion rate V in Nos. 4 and 6 is compared with the corrosion rate V in Tests 1, 5 and 7 in which it is not added, both of the former corrosion rates V are significantly smaller. It turns out that it is more advantageous.
【００３０】また、上述のテスト１０における腐食速度
Ｖと、それを添加していないテスト１，５，７における
腐食速度Ｖとを対比して見た場合、前者の腐食速度Ｖの
方が小さいから、これの方が有利であることがわかる。When the corrosion rate V in the above-mentioned test 10 is compared with the corrosion rate V in the tests 1, 5 and 7 in which it is not added, the former corrosion rate V is smaller. It turns out that this is more advantageous.
【００３１】また、上述のテスト１０における腐食速度
Ｖと、テスト２，３，４，６における腐食速度Ｖとを対
比して見た場合、前者の腐食速度Ｖは、後者のそれに比
して著しく大きいから、銅化合物は、金属腐食抑制剤と
して不適当であることがわかる。When the corrosion rate V in the above-mentioned test 10 is compared with the corrosion rate V in the tests 2, 3, 4, 6 the corrosion rate V of the former is remarkably higher than that of the latter. The large size indicates that the copper compound is unsuitable as a metal corrosion inhibitor.
【００３２】また、上述のテスト８，９からして、鉄化
合物は、モノエタノールアミンを含有していない液に対
しては金属腐食抑制効果を有していないことがわかる。Further, from the above-mentioned tests 8 and 9, it is understood that the iron compound has no metal corrosion inhibiting effect on the liquid containing no monoethanolamine.
【００３３】[0033]
【発明の効果】上述のように、本発明によると、モノエ
タノールアミン等を吸着した陽イオン交換樹脂を鉱酸
（塩酸等）で再生処理する際に発生するアルカノールア
ミン含有酸性廃液であるイオン交換樹脂再生廃液を蒸発
せしめて濃縮減量化するに際し、蒸発装置の腐食を抑制
し得て安全化が図れると共に産業廃棄物の発生をほぼ完
全に阻止することができる。As described above, according to the present invention, ion exchange is an alkanolamine-containing acidic waste liquid generated when a cation exchange resin having adsorbed monoethanolamine or the like is regenerated with a mineral acid (hydrochloric acid or the like). When the resin recycling waste liquid is evaporated to reduce its concentration and weight, it is possible to suppress the corrosion of the evaporation device to achieve safety and to prevent generation of industrial waste almost completely.
フロントページの続き (56)参考文献 特開 平９−314128（ＪＰ，Ａ) 特開 平11−128756（ＪＰ，Ａ) 特開 平６−306652（ＪＰ，Ａ) 特開 昭61−183481（ＪＰ，Ａ) 特開 昭58−39998（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C02F 1/04 B01J 49/00 Continuation of the front page (56) Reference JP-A-9-314128 (JP, A) JP-A-11-128756 (JP, A) JP-A-6-306652 (JP, A) JP-A-61-183481 (JP , A) JP-A-58-39998 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C02F 1/04 B01J 49/00
Claims (3)
イオン交換樹脂再生廃液を蒸発せしめて濃縮減量化する
に際し、前記イオン交換樹脂再生廃液に金属腐食抑制剤
を添加することを特徴とするイオン交換樹脂再生廃液の
処理方法。1. A metal corrosion inhibitor is added to the ion exchange resin regeneration waste liquid when the ion exchange resin regeneration waste liquid, which is an acidic waste liquid containing an alkanolamine, is evaporated to reduce the concentration. Waste liquid treatment method.
特徴とする請求項１に記載のイオン交換樹脂再生廃液の
処理方法。2. The method for treating an ion exchange resin regeneration waste liquid according to claim 1, wherein the metal corrosion inhibitor is an iron compound.
する請求項１又は２に記載のイオン交換樹脂再生廃液の
処理方法。3. The method for treating ion exchange resin regeneration waste liquid according to claim 1, wherein the evaporated concentrated liquid is combusted in liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18559898A JP3390138B2 (en) | 1998-06-15 | 1998-06-15 | Treatment method for ion exchange resin regeneration waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18559898A JP3390138B2 (en) | 1998-06-15 | 1998-06-15 | Treatment method for ion exchange resin regeneration waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000000558A JP2000000558A (en) | 2000-01-07 |
| JP3390138B2 true JP3390138B2 (en) | 2003-03-24 |
Family
ID=16173611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18559898A Expired - Fee Related JP3390138B2 (en) | 1998-06-15 | 1998-06-15 | Treatment method for ion exchange resin regeneration waste liquid |
Country Status (1)
| Country | Link |
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| JP (1) | JP3390138B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5839998A (en) * | 1981-09-03 | 1983-03-08 | 石川島播磨重工業株式会社 | Method of protecting scale adhesion.corrosion in radioactive liquid waste condensation system |
| JPS61183481A (en) * | 1985-02-07 | 1986-08-16 | Kubota Ltd | Treatment of waste liquor produced by pretreatment of metal before coating |
| JPH06306652A (en) * | 1993-04-28 | 1994-11-01 | Japan Organo Co Ltd | Corrosion inhibitor for metal and corrosion inhibiting method for metal |
| JPH09314128A (en) * | 1996-03-27 | 1997-12-09 | Japan Organo Co Ltd | Method for treating regeneration waste liquid of cation exchange resin adsorbed of organic amine |
| JP3083504B2 (en) * | 1997-10-29 | 2000-09-04 | 東レエンジニアリング株式会社 | Treatment method for ion exchange resin regeneration waste liquid |
-
1998
- 1998-06-15 JP JP18559898A patent/JP3390138B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000000558A (en) | 2000-01-07 |
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