JPS5976593A - Treatment of chemical washing waste liquor containing edta - Google Patents
Treatment of chemical washing waste liquor containing edtaInfo
- Publication number
- JPS5976593A JPS5976593A JP18524282A JP18524282A JPS5976593A JP S5976593 A JPS5976593 A JP S5976593A JP 18524282 A JP18524282 A JP 18524282A JP 18524282 A JP18524282 A JP 18524282A JP S5976593 A JPS5976593 A JP S5976593A
- Authority
- JP
- Japan
- Prior art keywords
- edta
- crystals
- cod
- liquid
- separated
- 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.)
- Granted
Links
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002699 waste material Substances 0.000 title claims abstract description 29
- 239000000126 substance Substances 0.000 title claims abstract description 12
- 238000005406 washing Methods 0.000 title abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 239000013078 crystal Substances 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- -1 iron ions Chemical class 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- GOLXRNDWAUTYKT-UHFFFAOYSA-N 3-(1H-indol-3-yl)propanoic acid Chemical compound C1=CC=C2C(CCC(=O)O)=CNC2=C1 GOLXRNDWAUTYKT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は化学洗浄廃液の処理方法、特にエチレンジアミ
ン四酢酸（以下、ｒＥＤＴＡＪと略す。）と結合した重
金属イオンを含む化学洗浄廃液の処理方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating chemical cleaning waste liquid, and particularly to a method for treating chemical cleaning waste liquid containing heavy metal ions combined with ethylenediaminetetraacetic acid (hereinafter abbreviated as rEDTAJ).
ＥＤＴＡはキレート洗浄剤としてボイラ、熱交換器、配
管等のスケール除去に広く用いられている。EDTA is widely used as a chelate cleaning agent to remove scale from boilers, heat exchangers, piping, etc.
この洗浄廃液中ばは洗浄過程でＥＤＴＡと結合した多量
の重金属イオンと高濃度のＣＯＤを含み、従来から効率
的な廃液処理方法の開発が求められていた。This cleaning waste liquid contains a large amount of heavy metal ions combined with EDTA during the cleaning process and a high concentration of COD, and there has been a demand for the development of an efficient waste liquid treatment method.
本発明者は鋭意研究の結果、廃液中からＥＤＴＡを回収
して再利用を図ると共に、廃液中のＣＯＤを低減させる
効率的な廃液処理を見い出したものである。As a result of intensive research, the inventor of the present invention has discovered an efficient waste liquid treatment that recovers and reuses EDTA from waste liquid and reduces COD in the waste liquid.
即ち、本発明はＦＪＤＴＡと結合した重金属イオンを含
む化学洗浄廃液の処理方法において１．該廃液にアルカ
リを添加してｐ）〜１１０以上で重金属イオンを沈殿分
離させる第１工程、前記第１工程の分離液に酸を添加し
てＥｌ）ＴＡの結晶を生成させ、該結晶を分離、回収す
る第２工程、および前記結晶を分離した分離液に酸化剤
を添加してＣＯＤを低減化させる第３工程とからなるこ
とを特徴とするＥＤＴＡを含む化学洗浄廃液の処理方法
である。That is, the present invention provides a method for treating chemical cleaning waste liquid containing heavy metal ions combined with FJDTA. A first step of adding an alkali to the waste liquid to precipitate and separate heavy metal ions at p) ~ 110 or higher, adding an acid to the separated liquid of the first step to generate El) TA crystals, and separating the crystals. , a second step of recovering the crystals, and a third step of adding an oxidizing agent to the separated liquid from which the crystals have been separated to reduce COD.
以下に本発明の処理方法について詳述する。The processing method of the present invention will be explained in detail below.
本発明の処理方法は、まず、廃液にアルカリを添加して
ＥＤＴＡとキレートしている重金属イオン−ｉ ＥＩ）
ＴＡから分離させる。該分離工程においては、苛性ソー
ダなどのアルカリ剤を注入して液のｐＨを１０以上にす
る必要があるが銘イオン、ニッケルイオンを含有する場
合にはｐ＋（１２以上、望ましく（ｌｉｐｌ−１１２，
５にする。また鉄（１）イオンを含有する場合は空気な
どで曝気することにより酸化し鉄（ｎ）イオンにするこ
とが好ましい。これは鉄（１）イオンであればｐＨ１２
，５以上にすることを要するが、予め鉄（［１）イオン
にしておけばｐＨ１２でよく、つ−まり加えるアルカリ
剤の量が少な（てすみ経済的であるからである。In the treatment method of the present invention, first, an alkali is added to the waste liquid to chelate heavy metal ions with EDTA (EI).
Separate from TA. In the separation process, it is necessary to inject an alkaline agent such as caustic soda to make the pH of the liquid 10 or more, but if it contains nickel ions, p+ (12 or more, preferably (lipl-112,
Make it 5. Further, when iron (1) ions are contained, it is preferable to oxidize them into iron (n) ions by aeration with air or the like. If this is iron(1) ion, the pH is 12.
, 5 or more, but if the iron ([1) ion is made in advance, the pH can be set to 12, which means that the amount of alkali agent added is small (this is because it is economical).
なお、鉄（■）イオンを酸化する手段ｄ：どのような方
法でも適用可能（例えば酸化剤を用いる等）であるが、
空気を用いて曝気するのが簡便であり経済的である。Note that the means d for oxidizing iron (■) ions: Any method can be applied (for example, using an oxidizing agent), but
Aeration using air is simple and economical.
廃液にアンモニアを包む場合には、銅イオンやニッケル
イオンはｐｉ（１２，５でも解離できない。これを解離
させるにはｐＨ１４以上にしなければならない。When enclosing ammonia in waste liquid, copper ions and nickel ions cannot be dissociated even at pi(12.5). To dissociate them, the pH must be 14 or higher.
従って、銅イオンについてはアルカリとして硫化ソータ
゛、硫化アンモンなどの硫化アルカリを銅イオンの１．
０〜１６５当量加えることにより硫化銅として分離する
ことができる。この場合の液のｐＨはアルカリ性であれ
ばよいから使用するアルカリ剤の隼が節約でき経済的で
ある。Therefore, for copper ions, sulfide alkalis such as sulfide sorter and ammonium sulfide are used as alkalis.
By adding 0 to 165 equivalents, it can be separated as copper sulfide. In this case, the pH of the solution only needs to be alkaline, so the amount of alkaline agent used can be saved and it is economical.
なお、アルカリの種類としては苛性ソーダ、硫化アルカ
リの他に消石灰、苛性カリなどでも使用可能である。As for the type of alkali, in addition to caustic soda and alkali sulfide, slaked lime and caustic potash can also be used.
次に、第１工程で重金属イオンを沈殿分離させた分離液
に酸を添加してＥＤＴＡの結晶を生成させ該結晶を分離
、回収する。該Ｅ Ｄ Ｔ Ａの結晶生成時の液の最適
ｐＨ域はＥＤＴＡの濃度によって幅が認められるが、ｐ
Ｈ３，０〜１．０がよく、好ましくはｐＨ１，８〜１．
４がよい。これはｐＨ３，０以上又はｐＨ１，０以ドで
はＥ ＤＴ Ａの結晶生成速度が遅いからである。Next, an acid is added to the separated liquid in which heavy metal ions have been precipitated and separated in the first step to generate EDTA crystals, and the crystals are separated and recovered. The optimum pH range of the solution during crystal formation of EDTA varies depending on the concentration of EDTA, but
H3.0-1.0 is good, preferably pH1.8-1.0.
4 is good. This is because the crystal formation rate of E DT A is slow at pH 3.0 or higher or pH 1.0 or higher.
なお、この処理工程でＥＤＴＡと重金属イオンがキレー
トしているとＥＤＴＡの結晶生成が起らない。Note that if EDTA and heavy metal ions are chelated in this treatment step, EDTA crystal formation will not occur.
従って、前記第１工程におけるＥＤＴＡと重金属イオン
の分離が不充分であると、それに相当する分だけＥＤＴ
Ａの回収率が低下することになる１、また、一部の重金
属イオンは結晶に取り込まれてしまう。Therefore, if the separation of EDTA and heavy metal ions in the first step is insufficient, EDT will be removed by a corresponding amount.
1, the recovery rate of A will decrease, and some heavy metal ions will be incorporated into the crystals.
特に、銅イオンの場合は、その量の５−〜■０％が結晶
に取り込１れ、回収したＥＤＴＡの純度を著しく低下さ
せ、再利用に際しても不都合である。かよう顛、本発明
においては第−処理工程で重金属イオンの分離を完全に
行う必要がある。In particular, in the case of copper ions, 5-0% of the amount is incorporated into the crystals, which significantly reduces the purity of the recovered EDTA and is inconvenient for reuse. Therefore, in the present invention, it is necessary to completely separate heavy metal ions in the first treatment step.
結晶反応槽では結晶生成のだめに所定の滞留時間を要す
るが、その時間は１０分以上が好′ましい。In the crystal reaction tank, a predetermined residence time is required for crystal formation to occur, and this time is preferably 10 minutes or more.
これは反応時間即ち液の滞留時間と結晶生成率の関係を
調べてみると反応時間５分では回収率８０〜８５％、反
応時間１０分では回収率９０〜９５チであり、反応時間
１０分程度壕では回収率が直線的に高するが、これを越
えると回収率の増加はゆるやかとなシ実用的でなくなる
からである。しかし、ＥＤＴＡの回収率を更に高めるこ
とが要求される場合には、液の滞留時間を長くすればよ
いととは云うまでもない。This is because when we examine the relationship between the reaction time, that is, the residence time of the liquid, and the crystal formation rate, we find that with a reaction time of 5 minutes, the recovery rate is 80-85%, and with a reaction time of 10 minutes, the recovery rate is 90-95%. This is because the recovery rate increases linearly in a deep trench, but beyond this point the increase in recovery rate becomes too gradual and becomes impractical. However, if it is required to further increase the recovery rate of EDTA, it goes without saying that it is sufficient to lengthen the residence time of the liquid.
また、ＥＤＴＡはＣＯＤ成分の一つであることから、後
段の第３工程でのＣＯＤ酸化工程での負相を軽減するた
めに、ＥＤＴＡの結晶分離装置内で３０〜６０分の滞留
時間を与えることによって結晶化を促進させるとより効
果的である。In addition, since EDTA is one of the COD components, in order to reduce the negative phase in the COD oxidation step in the third step, EDTA is given a residence time of 30 to 60 minutes in the crystal separation device. It is more effective to promote crystallization by
以ドに本発明の一実施態様を図面に従って説明する。An embodiment of the present invention will be described below with reference to the drawings.
廃液１′を重金属イオン分離処理槽］に受は人、れだの
ち、重金属分離薬品として苛性ソーダなどのア四ノ）ｌ
）剤５を注入し空気などによりよく攪拌してｐＨＩＱ以
−に、重重しくけｐＨ１２以上にする。１次に、アイモ
ニアを含有している廃液で銅イオンを含む場合には、硫
化アルカリを銅の量の１〜１．５倍当量を加え、銅イメ
ンを分離する。また鉄（１）（オン含有の廃液について
は、予め空気などで攪拌、酸化し鉄（１１）イオンにす
る。ここで分離される重金属イオンは水酸化物あるいは
硫化物のような不溶性のものとなり沈でんするが、この
場合、高分子凝集剤等の助剤を添加することは分離効果
を助長する。The waste liquid 1' is transferred to a heavy metal ion separation treatment tank] for human and human life, and for heavy metal separation chemicals such as caustic soda.
) Agent 5 is injected, stirred well with air, etc., and made to a pH of 12 or higher using a heavy weight. First, when the waste liquid contains copper ions, an alkali sulfide equivalent of 1 to 1.5 times the amount of copper is added to separate copper ions. In addition, waste liquid containing iron (1) (on) is stirred and oxidized with air in advance to form iron (11) ions.The heavy metal ions separated here are insoluble ones such as hydroxides or sulfides. However, in this case, adding an auxiliary agent such as a polymer flocculant promotes the separation effect.
沈でん分離後、移送ポンプ１１で移送管８を経由してＥ
ｌ）ＴＡ結晶反応槽２へ、さらに移送管９を通じて５′
Ｊ離装置３へ、移送管１０を通じて酸化分解槽４へと連
続的に移送し、分離処理槽１の分離液を処Ｊ！ｌする。After sediment separation, the transfer pump 11 passes the transfer pipe 8 to E.
l) 5′ to the TA crystal reaction tank 2 and further through the transfer pipe 9
The separated liquid in the separation treatment tank 1 is continuously transferred to the J! I do it.
まだ、分離処理槽１で発生する沈でん物は、脱水器等に
より処理し、その脱離液も同じルートで結晶を回収す乙
。However, the sediment generated in separation treatment tank 1 will be treated with a dehydrator, etc., and the crystals will be recovered from the separated liquid using the same route.
結晶反応槽２から酸化分解槽４までのフローは高低差を
与えることによる自然流下法で行うことも可能で、ポン
プ等の動力を節約することができる。The flow from the crystal reaction tank 2 to the oxidation decomposition tank 4 can also be carried out by a gravity flow method by providing a difference in height, and the power of pumps and the like can be saved.
移送管８による移送の途中で、液中の盾濁物（以下、Ｓ
Ｓと言う）を除去するためｊツ過槽を設置することも良
い。寸た、廃液１′中に暦食抑制剤などの他の吸着性の
有機物質が含１れている場合には、ｆ材を兼ねて活性炭
カラムを設置することにより、回収ＥＤＴＡの汚染や、
第３工程の酸化分解工程の薬品量の低減化、処理時間の
短縮もＨ＋Ｊ能となる。During the transfer through the transfer pipe 8, shield turbidity (hereinafter referred to as S) in the liquid
It is also a good idea to install a filter tank to remove S. In addition, if the waste liquid 1' contains other adsorbent organic substances such as eclipse inhibitors, installing an activated carbon column that also serves as an f material will prevent contamination of the recovered EDTA.
Reducing the amount of chemicals and shortening the treatment time in the third oxidative decomposition step also contributes to H+J performance.
結晶反応槽２では攪拌を与えなから酸６を加えｐＨ３，
０〜１．０の範囲になるよってするが、ｐＨ１，８〜１
．４ が望ましい。ここに用いる酸は硫酸、塩酸などの
無機酸である。結晶反応槽２での反応時間は１５分程度
でも良いが、３０分〜６０分間の滞留時間を設けること
が望ましい。In crystallization reactor 2, without stirring, add acid 6 to pH 3.
It depends on the range of 0 to 1.0, but the pH is 1.8 to 1.
．． 4 is desirable. The acid used here is an inorganic acid such as sulfuric acid or hydrochloric acid. The reaction time in the crystal reaction tank 2 may be about 15 minutes, but it is desirable to provide a residence time of 30 to 60 minutes.
分離装置３でＥ ＤＴ Ａの結晶を分１ｉｉ［ｆシ、、
分離液は移送管１０を通して酸化分解槽４へ移送するが
、分離装置３で３０分以上の滞留を与えることで結晶は
さらに成長し、溶解しているＥＤ’Ｉ’Ａの濃度を低「
させることができる。Separator 3 separates the crystals of EDT A into 1ii[f].
The separated liquid is transferred to the oxidation decomposition tank 4 through the transfer pipe 10, but by allowing it to stay in the separation device 3 for 30 minutes or more, the crystals grow further, reducing the concentration of dissolved ED'I'A.
can be done.
酸化分解槽４では、適正なｐＨにて酸化剤７を加えてＣ
ＯＩ）処理を行い低減化する。ここで消費する酸化剤７
の量は溶解しているＥｌ）’Ｉ’Ａなどの濃度に比例す
る。In the oxidation decomposition tank 4, an oxidizing agent 7 is added at an appropriate pH and C
OI) processing to reduce the amount. Oxidizing agent consumed here7
The amount of is proportional to the concentration of dissolved El)'I'A, etc.
分離装置３で分離されだＥＤ Ｔ Ａの結晶は、水洗に
より夾雑水分除くことによって簡単に純度の高い結晶と
して回収することかできる。Ｅ ＩＪ ’ｌ’ Ａの回
収率、純度については実施例１，２に示す如く充分再利
用＝Ｊ能な良好のものであった。The EDTA crystals separated by the separator 3 can be easily recovered as highly pure crystals by removing contaminant water by washing with water. As shown in Examples 1 and 2, the recovery rate and purity of E IJ 'l' A were good enough to allow sufficient reuse.
以」−のように本発明は、ＥＤＴＡと結合した重金属イ
オンを含む廃液からＥＤＴＡを効率よく回収して、その
ｒ１利用を図ることができると共に、該廃液のＣＯＤを
低減化させることができる効果があり、本発明により化
学洗浄廃液の効率的な処理が可能となった。As described above, the present invention has the effect of efficiently recovering EDTA from a waste liquid containing heavy metal ions combined with EDTA, making it possible to use the r1, and reducing the COD of the waste liquid. The present invention has made it possible to efficiently treat chemical cleaning waste liquid.
次に、本発明の実施例について記す。Next, examples of the present invention will be described.
実施例−１ 被処理液の組成は、次表のとおりである。Example-1 The composition of the liquid to be treated is shown in the following table.
ＥＤＴＡ濃度 ：４０％
□
１゜
ナトリウ馴オフ １ ０７２％□
Ｆｅイオン ６０００１’）Ｉ）ｍＣｕイ
オ” ５０Ｆ’ｊｐｐｍ１）ｆ（１６
，８
ＣＯＤ ｌ ３５００（）ｐｐｍ液量 ：１０
を
上記組成の液を空気で攪拌しながら消石灰を１５０７投
入し充分酸化したところｐＨ１２，２となった。EDTA concentration: 40% □ 1゜ Sodium acclimatization off 1 072% □ Fe ion 60001')I) mCu ion"50F'jppm1) f(16
,8 COD l 3500()ppm Liquid amount: 10
While agitating the solution with air, slaked lime of 150% was added to sufficiently oxidize the solution, resulting in a pH of 12.2.
これて高分子凝集剤１０ ｐｐｍを添加し沈でんを分離
したところ上澄液は無色透明となり、水引は次のとおり
であった。When 10 ppm of a polymer flocculant was added and the precipitate was separated, the supernatant liquid became clear and colorless, and the water content was as follows.
この液を第１工程の処理液とし、３５条の塩酸を比例注
入しながら反応槽で３０分滞留時間を１５え、連続処理
した。このときの液のｐＨは〕７５であり、白色のＩε
Ｄ ｉ’ Ａの結晶が生じ、分離装置でこの結晶を分１
’：！８ Ｌだ。分１ｌｉＢ装置内では３０分間の滞留
時間を与えた○
反応槽出口の液に５Ａの１紙を用いて結晶を完全にｆ１
過し、そのＰ液のＣＯＤを測定したところ、１２００ｐ
ｐｍであった。まだ分離装置出口の液のＣＯＤ値は５２
０ ｐｐｍであった。This solution was used as the treatment solution in the first step, and was continuously treated in a reaction tank for 30 minutes with a residence time of 15 minutes while proportionately injecting 35 portions of hydrochloric acid. The pH of the liquid at this time was 75, and the white Iε
Crystals of D i' A are formed, and these crystals are divided into 1 portion using a separation device.
':! It's 8L. A residence time of 30 minutes was given in the 1liB apparatus. ○ A piece of 5A paper was used to completely remove the crystals from the liquid at the outlet of the reaction tank.
When the COD of the P solution was measured, it was found to be 1200p.
It was pm. The COD value of the liquid at the outlet of the separator is still 52.
It was 0 ppm.
次に鉄イオ７ ’、Ｃ２００ｐｐｍ添加しｐＨ３〜３−
５にて過酸化水素にて酸化分解したところ、ＣＯＤは４
日後に６．２ ｐｐｍとなった。Next, add 200 ppm of iron 7' and C to pH 3-3-
When oxidatively decomposed with hydrogen peroxide in step 5, the COD was 4.
After a few days, it became 6.2 ppm.
ここで分離回収したｇｌ）ＴＡを１．５４の純水（１／
Ａｓ／ｍ）で水洗した３、水洗水の水質は次表に示す値
であったので水洗を止め、Ｅ Ｉ）Ｔ Ａを乾燥してそ
の重量を測定し７たところ、３８９？であった。このＥ
ＤＴＡ中の不純物とｌ＞ Ｉ）Ｔ Ａの純度を測定した
ところ次表のようであった。Here, the separated and collected gl) TA was mixed with 1.54% pure water (1/
The water quality of the washing water was as shown in the table below, so the washing was stopped, E I) T A was dried and its weight was measured, and it was found to be 389? Met. This E
Impurities in DTA and l> I) When the purity of TA was measured, it was as shown in the following table.
この値よシ、ＥＤＴＡの回収車を次の計算式から求める
ことができる。Based on this value, the number of EDTA collection vehicles can be calculated using the following formula.
１０〜Ｘ０．０４０ 実施例−２ 被処理液の組成は次表のとおりである。10~X0.040 Example-2 The composition of the liquid to be treated is shown in the table below.
」１記の液を空気で攪拌酸化を行ｉながら苛性ソーダ７
５０２全投入し攪拌したところ ｐ！−４１２，５とな
った。これに硫化ソーダ５５Ｆを投入し攪拌すると。While stirring and oxidizing the solution in step 1 with air, mix it with caustic soda 7.
When all 502 was added and stirred, p! -412.5. Add 55F of soda sulfide to this and stir.
ｐＬＩ １２．６となり黒色の沈でん物の発生が認めら
れた。pLI was 12.6, and the occurrence of black precipitate was observed.
これに高分子凝集剤１０１）Ｉ）ｍを添加し沈でんを分
離したところ、」−澄液の水質は次のとおりであった。When a polymer flocculant 101)I)m was added to this and the precipitate was separated, the water quality of the clear liquid was as follows.
ｐｒ−ｉ ｉ １２．に
の分ＩＷｔ液を活性炭カラムを通したところ、ＳＳは認
められず、インヒビターに由来する発泡も消失していた
。pr-i i 12. When the IWt solution was passed through an activated carbon column, no SS was observed and the foaming caused by the inhibitor had disappeared.
この液を第１工程の処理液とし、７５チの硫酸を廃液に
比例注入しながら反応槽で３０分滞留時間を力え連続式
に処理した。このときの液のｐＨは１６２であり、白色
の結晶が生じ、分離装置で分離した。This liquid was used as the treatment liquid in the first step, and was continuously treated in a reaction tank for 30 minutes while proportionally injecting 75 sulfuric acid into the waste liquid. The pH of the liquid at this time was 162, and white crystals were formed, which were separated using a separator.
分離装置では３０分間の滞留全力えた。The separator had a retention capacity of 30 minutes.
反応槽出口の液を１紙を用いて結晶を完全に濾過し、そ
の′Ｐ液のＣ０Ｉ）を測定したところ２２００ ｐｐｍ
であった。分離装置出口の液を同様に処Ｊ！＋！、 Ｌ
だｌＨｉ液のＣＯＤば１６００ ｐｐｍであり、これに
硫酸第二鉄を鉄イオンとして５００ ｐｐｍ添加し、ｐ
Ｈ３〜３．５にて過酸化水素にて酸化分解したところ、
ＣＯＤは次第に低ドし５日後にＣＯＤ ８．７ ｐｐｍ
となった。The crystals were completely filtered from the liquid at the outlet of the reaction tank using a piece of paper, and the 'P liquid COI) was measured and found to be 2200 ppm.
Met. Treat the liquid at the outlet of the separator in the same way. +! , L
The COD of the stock solution was 1600 ppm, and 500 ppm of ferric sulfate as iron ions was added to it.
When oxidatively decomposed with hydrogen peroxide at H3-3.5,
COD gradually decreased to 8.7 ppm after 5 days.
It became.
ここで回収されたＥＤＴＡの容積は３ｔであった。The volume of EDTA recovered here was 3 tons.
これを１μｓ／／ｃｒｎの純水で水洗し／こところ、５
１の水洗量で流出水洗水の水質が次表の値を丞し／この
でを測定したところ１１８（ｌであった。このＥ Ｉ）
ｉ’ Ａ中の不純物とＥ Ｄ ＴＡの純度を測定したと
ころ、次のような結果となった。Wash this with pure water of 1μs//crn/Kotokoro, 5
The water quality of the flushing water was lower than the value in the table below at the amount of water washed at 1. When measured, it was 118 (l. This E I)
When the impurities in i'A and the purity of EDTA were measured, the following results were obtained.
Ｎ’ａ−” １１５ ｐｐｍ
この値よりＥＤＴＡの回収率を次の計算式から求めるこ
とができる。N'a-'' 115 ppm From this value, the recovery rate of EDTA can be calculated from the following formula.
図面は、本発明の一実施ｊン駿様を示すフローシートで
ある。
丁・廃液、１・・分Ｘｔｔ処丹槽、２・・・結晶反応槽
、３・・・分ｔ；１１装置、４・・１衰化分解槽、５・
−・アルカリ剤、６・酸、７・・・酸化剤、８，９．１
０・・移送管、１１・・移送ポンプ。The drawing is a flow sheet showing one implementation of the present invention. Waste liquid, 1... min.
-・alkali agent, 6・acid, 7・oxidizing agent, 8,9.1
0...Transfer pipe, 11...Transfer pump.
Claims (1)
Ａ」と略す。）と結合した重金属イオンを含む化学洗浄
廃液の処理方法において、 ａ） 該廃液にアルカリを添加してｐＨ１０以上で重金
属イオンを沈殿分離させる＄１工程、ｂ） 前記第１工
程の分離液に酸を添加してＥｌ）ＴＡの結晶を生成させ
、該結晶を分離、回収する第２工程、 Ｃ） および前記結晶を分離した分離液に酸化剤を添加
してＣＯＤを低減させる第３工程、とからなることを特
徴とするＥＤＴＡを含む化学洗浄廃液の処理方法。 ２ 前記廃液が、ＥＤＴＡと結合した重金属イオンとし
て、少なくとも鉄イオン又は銅イオンを含むものである
特許請求の範囲第１項記載の方法。 ３ 前記鉄イオンが鉄（１）イオンである場合は予め酸
化した後、アルカリを添加する特許請求の範囲第２項記
載の方法。 ４、 前記第１工程で添加されるアルカリが、硫化アル
カリである特許請求の範囲！′３１項記載の方法。 ５、 前記第２工程における前記酸の添加量を、酸添加
後の液のｐＨが３０〜１．０、好ましくは１．８〜１．
４になるように設定する特許請求の範囲第１項記載の方
法。[Claims] C1. Ethylenediaminetetraacetic acid (r-EDT)
Abbreviated as "A". ) A method for treating a chemical cleaning waste solution containing heavy metal ions combined with a chemical cleaning waste solution comprising: a) a $1 step in which an alkali is added to the waste solution to precipitate and separate the heavy metal ions at a pH of 10 or more; b) an acid is added to the separated solution from the first step. C) A second step of adding El) to produce TA crystals, and separating and recovering the crystals; C) A third step of adding an oxidizing agent to the separated liquid from which the crystals have been separated to reduce COD. A method for treating chemical cleaning waste liquid containing EDTA, characterized by comprising: 2. The method according to claim 1, wherein the waste liquid contains at least iron ions or copper ions as heavy metal ions combined with EDTA. 3. The method according to claim 2, wherein when the iron ions are iron(1) ions, they are oxidized in advance and then an alkali is added. 4. The claim that the alkali added in the first step is an alkali sulfide! 'The method described in item 31. 5. The amount of the acid added in the second step is such that the pH of the solution after addition of the acid is 30 to 1.0, preferably 1.8 to 1.0.
4. The method according to claim 1, wherein the method is set to be 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18524282A JPS5976593A (en) | 1982-10-21 | 1982-10-21 | Treatment of chemical washing waste liquor containing edta |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18524282A JPS5976593A (en) | 1982-10-21 | 1982-10-21 | Treatment of chemical washing waste liquor containing edta |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5976593A true JPS5976593A (en) | 1984-05-01 |
| JPS6134875B2 JPS6134875B2 (en) | 1986-08-09 |
Family
ID=16167370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18524282A Granted JPS5976593A (en) | 1982-10-21 | 1982-10-21 | Treatment of chemical washing waste liquor containing edta |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5976593A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000210681A (en) * | 1999-01-21 | 2000-08-02 | United States Enrichment Corp | Method of removing metal from cleaning liquid |
| CN112960829A (en) * | 2021-02-20 | 2021-06-15 | 成都明天高新产业有限责任公司 | Process for treating copper-containing wastewater generated in production of printed circuit boards |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0449902Y2 (en) * | 1989-04-13 | 1992-11-25 | ||
| JPH0379650U (en) * | 1989-12-05 | 1991-08-14 | ||
| JPH0633821Y2 (en) * | 1990-09-03 | 1994-09-07 | タイトン株式会社 | Holder for hanging scallop aquaculture |
| CN104418400B (en) * | 2013-08-20 | 2017-02-08 | 天津大学 | Iron-based nano-alloy and application thereof in adsorption of cesium |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5027310A (en) * | 1973-07-14 | 1975-03-20 | ||
| JPS5067726A (en) * | 1973-10-22 | 1975-06-06 | ||
| JPS5163555A (en) * | 1974-11-29 | 1976-06-02 | Teikoku Hormone Mfg Co Ltd | JUKINZOKUSAKUENSUIYOEKINO SHORIHOHO |
| JPS529941A (en) * | 1975-07-11 | 1977-01-25 | Bii Esu Konkuriito Kk | Holding device for transportation of bridge* etc* |
| JPS5243453A (en) * | 1975-10-02 | 1977-04-05 | Furuno Electric Co Ltd | Ultrasonic detector |
| JPS52135879A (en) * | 1976-05-11 | 1977-11-14 | Kurita Water Ind Ltd | Treatment of chemical washing waste liquid |
-
1982
- 1982-10-21 JP JP18524282A patent/JPS5976593A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5027310A (en) * | 1973-07-14 | 1975-03-20 | ||
| JPS5067726A (en) * | 1973-10-22 | 1975-06-06 | ||
| JPS5163555A (en) * | 1974-11-29 | 1976-06-02 | Teikoku Hormone Mfg Co Ltd | JUKINZOKUSAKUENSUIYOEKINO SHORIHOHO |
| JPS529941A (en) * | 1975-07-11 | 1977-01-25 | Bii Esu Konkuriito Kk | Holding device for transportation of bridge* etc* |
| JPS5243453A (en) * | 1975-10-02 | 1977-04-05 | Furuno Electric Co Ltd | Ultrasonic detector |
| JPS52135879A (en) * | 1976-05-11 | 1977-11-14 | Kurita Water Ind Ltd | Treatment of chemical washing waste liquid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000210681A (en) * | 1999-01-21 | 2000-08-02 | United States Enrichment Corp | Method of removing metal from cleaning liquid |
| CN112960829A (en) * | 2021-02-20 | 2021-06-15 | 成都明天高新产业有限责任公司 | Process for treating copper-containing wastewater generated in production of printed circuit boards |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6134875B2 (en) | 1986-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4947640B2 (en) | Waste acid solution treatment method | |
| WO2012033077A1 (en) | Method of treating copper etching waste liquor | |
| CZ291141B6 (en) | Method for anaerobic removal of a sulfur compound from waste water | |
| JP2012224901A (en) | Method for treating and recovering copper-containing acidic waste liquid and apparatus for the same | |
| JP2506032B2 (en) | Wastewater treatment method | |
| USH1852H (en) | Waste treatment of metal plating solutions | |
| US5451327A (en) | Compound and method for treating water containing metal ions and organic and/or inorganic impurities | |
| JPS5976593A (en) | Treatment of chemical washing waste liquor containing edta | |
| JP3739845B2 (en) | Treatment method of ferric chloride waste liquid | |
| JPS5834197B2 (en) | High speed inosyoriho | |
| JPS6211634B2 (en) | ||
| JP2000153284A (en) | Treatment of cyan by ozone | |
| JPS59222292A (en) | Treatment of waste liquid of chemical cleaning containing ethylenediamine tetraacetate | |
| CN108996752B (en) | Method for recovering low-concentration nickel from nickel extraction waste water | |
| KR19980702743A (en) | Ammonia Metal Solution Recirculation Method | |
| KR19990027070A (en) | Biological denitrification of wastewater and simultaneous treatment of high concentration hydrofluoric acid, lead and nitric acid | |
| KR100206485B1 (en) | Thiocyanide removal form coke oven wash water | |
| JPH0483592A (en) | Treatment of waste chemical washing solution | |
| JP3913843B2 (en) | Coagulation sedimentation processing equipment | |
| JPH0369515A (en) | Method for recovering high-purity iron sulfate from waste sulfuric acid pickling solution for stainless steel | |
| RU2213064C1 (en) | Method of recovering ethylenediaminetetraacetic acid from spent washing solution in power station steam generators | |
| JP3195514B2 (en) | Coagulation settling equipment | |
| US5951954A (en) | Method for manufacturing clear brine fluids from impure zinc feedstock | |
| JP5063975B2 (en) | Organic wastewater treatment method and treatment apparatus | |
| JPS5836695A (en) | Treatment of waste liquid of chemical washing |