JPH0460717B2 - - Google Patents
Info
- Publication number
- JPH0460717B2 JPH0460717B2 JP14425084A JP14425084A JPH0460717B2 JP H0460717 B2 JPH0460717 B2 JP H0460717B2 JP 14425084 A JP14425084 A JP 14425084A JP 14425084 A JP14425084 A JP 14425084A JP H0460717 B2 JPH0460717 B2 JP H0460717B2
- Authority
- JP
- Japan
- Prior art keywords
- heavy metal
- waste liquid
- sludge
- flocculant
- added
- 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
- 229910001385 heavy metal Inorganic materials 0.000 claims description 45
- 239000002699 waste material Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 27
- 239000010802 sludge Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- 239000013522 chelant Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000005345 coagulation Methods 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 235000011116 calcium hydroxide Nutrition 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 3
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000581017 Oliva Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
Description
〔産業上の利用分野〕
本発明は重金属キレート系廃液の凝集沈澱によ
る処理方法に関するものである。
〔発明の背景〕
プリント基板製造工場などから排出される廃液
は、化学銅めつき液のCu−EDTAなどの重金属
キレート系廃液を含有しているので、この廃液を
そのまゝ河川などに排出すると、環境汚染などの
原因となるおそれがあり、従来からこれら廃液の
処理方法が種々実用化されている。例えば、Cu
−EDTAキレート廃液にカルシウム塩を加え、
PHを12以上に調整し、これに凝集剤を加えて、凝
集沈澱させる消石灰過剰添加法、又Cu−EDTA
を強力な酸化剤を用いて処理する酸化分解法、イ
オン交換樹脂等によるCu−EDTAを処理する吸
着法等が比較的有効な処理方法として知られてい
る。
これらの方法は一応の重金属除去はできるが、
消石灰過剰添加法では、薬品代が高額となる上、
ポンプ、配管へのスケーリング、過機の目詰り
があり、酸化分解法では加熱しても除去率が低
く、充分な除去率を得るには処理に長時間を要す
る。さらに、吸着法では吸着剤の再生費用が高額
となり、効果的なCu除去率の向上は期待できな
い（産業公害vol19，No.６，第76頁〜第87頁）。
〔発明の目的〕
本発明者は重金属キレート系廃液中の重金属除
去率がより一層高く、併せてCOD除去率が高く
フロツクの分離性がよい、廃液の処理方法を得る
ことを目的とし、種々検討した結果、重金属キレ
ート系廃液を先ず、酸性のあるPH域にし、次い
で、この溶液に後に説明する処理工程で生成す
る、重金属とカルシウムを含む汚泥を加えて溶
解、反応させ、次いでアルカリ性のあるPH域で凝
集沈澱することにより、上記目的が達成されるこ
とを知り、本発明を完成した。
〔発明の概要〕
すなわち、本発明の要旨は、重金属キレート系
廃液にPHが４以下となるまで、硫酸を添加し、次
いで二価の鉄、三価の鉄、銅、ニツケル、亜鉛、
三価のクロム等の重金属類とカルシウムを含有す
る汚泥を添加し、遊離のカルシウムイオン、重金
属イオン、重金属キレートを生成、共存させる第
１処理工程と、この工程で得られた溶液にPHが９
以上になるまで、水酸化カルシウムを添加し、生
成する重金属水酸化物をアニオン系高分子凝集剤
で凝集沈澱・分離させる第２処理工程とよりなる
ことを特徴とする重金属キレート系廃液の処理方
法に存する。
本発明をさらに詳細に説明するに、本発明で対
象となる重金属キレート系廃液としては、例えば
プリント基板製造工場、めつき部品製造工場等よ
り排出されるEDTA等ポリアミノカルボン酸、
アミン類、有機酸類とキレート結合している化学
銅めつき廃液、化学ニツケルめつき廃液、金属の
酸洗前処理廃液の濃厚液および水洗水が主なもの
である。また、本発明の第１処理工程で、PH調整
に用いられる酸としては、通常の硫酸が使用され
るが、塩酸でもよい。一方、重金属を含む汚泥と
しては、前述の重金属のうち１種類以上を単独に
含むか、２種類以上を共存するものでよい。通常
はこの処理方法の第２工程で生成する汚泥を一部
返送して用いられるが、他の廃水処理系統例えば
重金属キレート系廃液を含まない重金属イオンを
含む廃液の凝集沈澱処理で生成した汚泥であれば
より好ましい。また、汚泥の添加量は、重金属キ
レート系廃液に含まれる重金属と結合していない
キレート剤の当量以上とすることが望ましいが、
キレート剤の当量以下でも相当する効果が得られ
る。また、汚泥中に含まれるカルシウムは、マグ
ネシウム、アルミニウムであつてもよく、要すれ
ば本発明により生成する汚泥又は通常の重金属含
有廃液の凝集沈澱により生成する汚泥に含まれる
凝集助剤成分でよい。
本発明の第２処理工程で、PH調整に用いられる
アルカリとしては、通常の水酸化カルシウムが使
用されるが、苛性ソーダ、酸化マグネシウムを併
用してもよい。さらに、凝集剤としては、ポリア
クリルアミド系のアニオン系高分子凝集剤が好ま
しいが、カチオン系、ノニオン系のいずれのもの
でもよく、さらにPAC，硫酸バンド、塩化第２
鉄等の無機系凝集剤を併用してもよい。又、凝集
剤添加と同時に、前述の汚泥を返送して添加する
ことを併用するとよい。
本発明では、重金属キレート系廃液をPHの異な
る２段階で処理するが、先ず第１処理工程では、
例えば化学銅廃液に上述の硫酸を加えることによ
り、廃液のPHを４以下好ましくは2.5以下に調整
する。この処理は通常、化学銅廃液を攪拌下、PH
を計測、制御しながら徐々にPH１以下の５％硫酸
を加えながら行なわれる。このPH調整が終ると上
記汚泥を加えるが、汚泥の添加により溶液のPHが
４以上に上昇する場合は、硫酸を添加し、汚泥中
の重金属がイオン化するよう調整するか、汚泥中
に硫酸を添加して、汚泥を重金属を含むPH２〜３
の溶液として廃液に添加する。この汚泥は重金属
キレート廃液中の重金属イオンと結合していない
キレート剤と汚泥中の重金属がキレート結合し、
過剰の重金属イオンが共存するまで添加すればよ
く、通常は溶液中の重金属濃度がキレート剤の２
当量以上が好ましい。第２段階の処理工程では、
第１段階の処理を終つた溶液に先ず、上記の水酸
化カルシウムを加え、PHを９以上好ましくは10〜
11になるようにする。このPH調整が終ると、上記
のポリアクリルアミド系凝集剤を添加して凝集処
理する。この際の凝集剤の添加量は、通常の溶液
に対しては0.5〜10ppm、好ましくは１〜2ppm程
度である。前述のようにこの工程で凝集効果をよ
くするため、汚泥の一部通常５％程度を返送して
処理する時は、凝集剤２〜3ppm程度に増加させ
る。凝集剤は通常0.05〜0.2％の水溶液として添
加され、添加後は攪拌し、２〜10分位放置し、次
いでシツクナ等で濃縮した後、汚泥をオリバ型真
空脱水機等で分離、除去する。
第１処理工程において、PHが４以上であると第
２工程で重金属キレートが残存し、凝集剤を添加
しても良好な沈澱分離ができず、重金属の除去率
が低い。また、第１処理工程で加える汚泥が少な
く、重金属と結合していないキレート剤が残存す
ると、上記の同様、重金属の除去率が低い。
また、第２処理工程において、PHが９未満であ
つたり、カルシウム分が充分でないと、重金属キ
レートが残存したり、再形成されて、重金属の除
去率が低くなる。
〔発明の実施例〕
以下、本発明を実施例により更に詳細に説明す
る。
実施例 １
プリント基板製造工場よりの化学銅廃液
（Cu15ppm含有、EDTA165ppm.COD142ppm含
有）10m3に硫酸をPH2.5になるまで加えた。次い
で、汚泥（含水率98％，Cu1240ppm，
Fe620ppm，Ca15000ppm含有）を廃液に対して
５％の0.5m3を加え、PHを再び2.5に調整し、混合
した。３分間攪拌後10％消石灰を加え、PHを10に
調整した。さらにアニオン系ポリアクリルアミド
凝集剤（栗田工業製クリフロツクEDP351）を溶
液に対し、凝集剤が2ppmとなるよう添加した。
３分間攪拌後５分間放置した後、沈澱した汚泥を
オリバ型真空脱水機により分離した。
得られた上澄液中のCu，Fe及びCODの含有量
を判定し、第１表の結果を得た。
[Industrial Application Field] The present invention relates to a method for treating heavy metal chelate waste liquid by coagulation and precipitation. [Background of the Invention] Waste liquid discharged from printed circuit board manufacturing factories etc. contains heavy metal chelate waste liquid such as Cu-EDTA, a chemical copper plating solution, so if this waste liquid is directly discharged into rivers etc. , there is a risk of causing environmental pollution, etc., and various methods for treating these waste liquids have been put into practical use. For example, Cu
−Add calcium salt to EDTA chelate waste solution,
The slaked lime excess addition method, which adjusts the pH to 12 or more and adds a flocculant to coagulate and precipitate, or Cu-EDTA
The oxidative decomposition method, in which Cu-EDTA is treated with a strong oxidizing agent, and the adsorption method, in which Cu-EDTA is treated with an ion exchange resin, are known as relatively effective treatment methods. Although these methods can remove heavy metals to some extent,
In addition to the excessive slaked lime addition method, the chemical costs are high;
Scaling of pumps and piping and clogging of filters occur, and the removal rate of the oxidative decomposition method is low even when heated, and it takes a long time to obtain a sufficient removal rate. Furthermore, in the adsorption method, the regeneration cost of the adsorbent is high, and an effective improvement in the Cu removal rate cannot be expected (Industrial Pollution Vol. 19, No. 6, pp. 76 to 87). [Purpose of the Invention] The present inventor has conducted various studies with the aim of obtaining a waste liquid treatment method that has an even higher heavy metal removal rate from heavy metal chelate waste liquid, has a high COD removal rate, and has good floc separation properties. As a result, the heavy metal chelate waste liquid was first brought to an acidic pH range, then sludge containing heavy metals and calcium produced in the treatment process explained later was added to dissolve and react, and then the pH was adjusted to an alkaline pH range. The present invention was completed based on the knowledge that the above object can be achieved by coagulation and sedimentation in the region. [Summary of the Invention] That is, the gist of the present invention is to add sulfuric acid to heavy metal chelate waste liquid until the pH becomes 4 or less, and then add divalent iron, trivalent iron, copper, nickel, zinc,
A first treatment step in which sludge containing heavy metals such as trivalent chromium and calcium is added to generate and coexist free calcium ions, heavy metal ions, and heavy metal chelates, and the solution obtained in this step has a pH of 9.
A method for treating heavy metal chelate waste liquid, comprising a second treatment step of adding calcium hydroxide and coagulating and precipitating and separating the produced heavy metal hydroxide with an anionic polymer flocculant until the above is achieved. exists in To explain the present invention in more detail, the heavy metal chelate waste liquid targeted by the present invention includes, for example, polyaminocarboxylic acids such as EDTA discharged from printed circuit board manufacturing factories, plated parts manufacturing factories, etc.
The main sources are chemical copper plating waste liquid that is chelated with amines and organic acids, chemical nickel plating waste liquid, concentrated liquid of metal pickling pretreatment waste liquid, and washing water. Further, in the first treatment step of the present invention, as the acid used for pH adjustment, normal sulfuric acid is used, but hydrochloric acid may also be used. On the other hand, the sludge containing heavy metals may include one or more of the above-mentioned heavy metals alone, or two or more of the heavy metals may coexist. Normally, a part of the sludge produced in the second step of this treatment method is returned and used, but it can be used in other wastewater treatment systems, such as coagulation and sedimentation treatment of wastewater containing heavy metal ions that does not contain heavy metal chelate wastewater. It is more preferable if there is. In addition, it is desirable that the amount of sludge added be equal to or more than the equivalent amount of the chelating agent that is not bound to the heavy metals contained in the heavy metal chelate waste liquid.
A corresponding effect can be obtained even if the amount is less than the equivalent amount of the chelating agent. Further, the calcium contained in the sludge may be magnesium or aluminum, and if necessary, it may be a coagulation aid component contained in the sludge produced by the present invention or the sludge produced by coagulation and sedimentation of ordinary heavy metal-containing waste liquid. . In the second treatment step of the present invention, ordinary calcium hydroxide is used as the alkali used for pH adjustment, but caustic soda and magnesium oxide may also be used in combination. Further, as the flocculant, an anionic polymer flocculant such as polyacrylamide is preferable, but any cationic or nonionic flocculant may be used.
An inorganic flocculant such as iron may be used in combination. Further, it is preferable to add the above-mentioned sludge by returning it at the same time as adding the flocculant. In the present invention, heavy metal chelate waste liquid is treated in two stages with different pH levels. First, in the first treatment step,
For example, by adding the above-mentioned sulfuric acid to a chemical copper waste solution, the pH of the waste solution is adjusted to 4 or less, preferably 2.5 or less. This process usually involves the chemical copper waste solution being stirred and the pH
This is done while gradually adding 5% sulfuric acid with a pH of 1 or less while measuring and controlling the amount of water. After this PH adjustment is completed, the above sludge is added, but if the PH of the solution increases to 4 or more due to the addition of sludge, either add sulfuric acid and adjust so that the heavy metals in the sludge are ionized, or add sulfuric acid to the sludge. Addition of sludge to pH 2-3 containing heavy metals
Add to the waste liquid as a solution. In this sludge, the chelating agent that is not bonded to the heavy metal ions in the heavy metal chelate waste liquid and the heavy metal in the sludge are chelated and bonded.
It is sufficient to add the heavy metal ions until excess heavy metal ions coexist, and usually the heavy metal concentration in the solution is 2 times higher than that of the chelating agent.
An equivalent or more is preferable. In the second stage treatment process,
First, add the above calcium hydroxide to the solution that has been treated in the first stage, and adjust the pH to 9 or more, preferably 10 to 10.
Make it 11. After this pH adjustment is completed, the above-mentioned polyacrylamide flocculant is added to perform flocculation treatment. The amount of flocculant added at this time is about 0.5 to 10 ppm, preferably about 1 to 2 ppm, relative to a normal solution. As mentioned above, in order to improve the coagulation effect in this step, when a portion of the sludge, usually about 5%, is returned for treatment, the flocculant is increased to about 2 to 3 ppm. The flocculant is usually added as a 0.05 to 0.2% aqueous solution, and after addition, it is stirred and left to stand for about 2 to 10 minutes, and then concentrated using a Shitsukuna or the like, and the sludge is separated and removed using an Oliva type vacuum dehydrator or the like. In the first treatment step, if the pH is 4 or higher, heavy metal chelates will remain in the second step, and even if a flocculant is added, good precipitation separation will not be possible, resulting in a low heavy metal removal rate. Furthermore, if the amount of sludge added in the first treatment step is small and chelating agents that are not bonded to heavy metals remain, the removal rate of heavy metals will be low, as described above. Furthermore, in the second treatment step, if the pH is less than 9 or the calcium content is insufficient, heavy metal chelates may remain or be reformed, resulting in a low heavy metal removal rate. [Examples of the Invention] The present invention will now be described in more detail with reference to Examples. Example 1 Sulfuric acid was added to 10 m 3 of a chemical copper waste solution (containing 15 ppm of Cu, 165 ppm of EDTA, and 142 ppm of COD) from a printed circuit board manufacturing factory until the pH reached 2.5. Next, sludge (moisture content 98%, Cu 1240ppm,
0.5 m 3 of 5% (containing 620 ppm Fe and 15000 ppm Ca) was added to the waste liquid, the pH was adjusted to 2.5 again, and the mixture was mixed. After stirring for 3 minutes, 10% slaked lime was added to adjust the pH to 10. Furthermore, an anionic polyacrylamide flocculant (Clifflock EDP351, manufactured by Kurita Industries) was added to the solution so that the flocculant amount was 2 ppm.
After stirring for 3 minutes and leaving for 5 minutes, the precipitated sludge was separated using an Oliva type vacuum dehydrator. The contents of Cu, Fe, and COD in the obtained supernatant were determined, and the results shown in Table 1 were obtained.
【表】
実施例 ２
第１処理工程に使用する汚泥（含水率98％，
Cu370ppm，Fe280ppm，Ni60ppm，Zn160ppm，
Cr15ppm，Ca14000ppm）を第１表のものと変え
た以外は、実施例１と同様な処理を行つた。この
ときに得られた上澄液中の銅、Ni，CODの含有
量を判定し、第２表の結果を得た。[Table] Example 2 Sludge used in the first treatment step (moisture content 98%,
Cu370ppm, Fe280ppm, Ni60ppm, Zn160ppm,
The same treatment as in Example 1 was performed except that Cr15ppm, Ca14000ppm) were changed from those in Table 1. The contents of copper, Ni, and COD in the supernatant liquid obtained at this time were determined, and the results shown in Table 2 were obtained.
【表】
実施例 ３
第２処理工程に使用する凝集剤を2ppmとし、
汚泥を凝集剤と同時に溶液に対して２％（0.2m3）
添加した以外は、実施例１と同様な処理を行つ
た。このときに得られた上澄液中のCu，Fe、及
びCODの含有量を判定し、第３表の結果を得た。[Table] Example 3 The flocculant used in the second treatment step was 2 ppm,
Add sludge to the solution at the same time as flocculant at 2% (0.2m 3 )
The same treatment as in Example 1 was carried out except for the addition of the following. The contents of Cu, Fe, and COD in the supernatant obtained at this time were determined, and the results shown in Table 3 were obtained.
本発明によれば、従来凝集沈澱では効率的な処
理が困難とされていた、重金属キレート系廃液
を、極めて安定な状態で、回分処理および連続処
理で凝集沈澱処理することができ、更に重金属の
除去率が高く、スラツジ発生量も少ないので、工
業的な廃液の処理方法として適している。
According to the present invention, it is possible to treat heavy metal chelate-based waste liquid, which has conventionally been difficult to efficiently treat by coagulation and sedimentation, in an extremely stable state through batch processing and continuous processing, and furthermore, the heavy metal Since the removal rate is high and the amount of sludge generated is small, it is suitable as an industrial waste liquid treatment method.
図は本発明の一実施態様のフローチヤートを示
す図である。
１……廃液貯槽、２……第１処理槽、３……第
２処理槽、４……シツクナ、５……脱水機、P1
〜P4……ポンプ。
The figure is a diagram showing a flowchart of one embodiment of the present invention. 1... Waste liquid storage tank, 2... First treatment tank, 3... Second treatment tank, 4... Shitsukuna, 5... Dehydrator, P 1
~P 4 ...Pump.
Claims (1)
で無機性の酸を添加し、次いで二価の鉄、三価の
鉄、銅、ニツケル、亜鉛、三価のクロム等の重金
属類とカルシウムを含有する汚泥を添加し、遊離
のカルシウムイオン、重金属イオン、重金属キレ
ートを生成、共存させる処理工程と、次いでPHが
９以上になるまで、アルカリを添加し、次いで凝
集剤を添加し、生成する重金属フロツクを分離す
る処理工程よりなることを特徴とする重金属キレ
ート系廃液の処理方法。1 Add inorganic acid to heavy metal chelate waste liquid until the pH is 4 or less, then add heavy metals such as divalent iron, trivalent iron, copper, nickel, zinc, trivalent chromium, etc. and calcium. A treatment process in which free calcium ions, heavy metal ions, and heavy metal chelates are produced and coexisted by adding sludge, and then an alkali is added until the pH becomes 9 or higher, and then a flocculant is added to produce heavy metal floc. 1. A method for treating heavy metal chelate waste liquid, comprising a treatment step of separating.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14425084A JPS6125692A (en) | 1984-07-13 | 1984-07-13 | Treatment of waste liquid containing heavy metal chelate |
| EP85108492A EP0168752B2 (en) | 1984-07-13 | 1985-07-09 | Method of treating liquid wastes containing heavy metal chelate compounds |
| DE8585108492T DE3582964D1 (en) | 1984-07-13 | 1985-07-09 | METHOD FOR THE TREATMENT OF WASTE CONTAINING LIQUID, CHELATE OF HEAVY METALS. |
| KR1019850004878A KR890002277B1 (en) | 1984-07-13 | 1985-07-09 | Method for treating waste liquid containing heavy metal chelate compound |
| US07/064,562 US4802993A (en) | 1984-07-13 | 1987-06-22 | Method of treating liquid wastes containing heavy metal chelate compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14425084A JPS6125692A (en) | 1984-07-13 | 1984-07-13 | Treatment of waste liquid containing heavy metal chelate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6125692A JPS6125692A (en) | 1986-02-04 |
| JPH0460717B2 true JPH0460717B2 (en) | 1992-09-28 |
Family
ID=15357727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14425084A Granted JPS6125692A (en) | 1984-07-13 | 1984-07-13 | Treatment of waste liquid containing heavy metal chelate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6125692A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4374636B2 (en) * | 1999-01-11 | 2009-12-02 | 栗田工業株式会社 | Treatment method of waste liquid containing heavy metal complex |
| CN105084509B (en) * | 2015-07-10 | 2017-06-16 | 广东粤绿环境工程中心 | A kind of purification process technique of industrial wastes |
| CN105152289B (en) * | 2015-07-10 | 2017-06-06 | 郑宇欣 | A kind of purifying agent of alkaline waste water |
| CN112645482A (en) * | 2020-11-06 | 2021-04-13 | 江苏泉之源环境技术有限公司 | Treatment method of carboxyl complex heavy metal wastewater |
-
1984
- 1984-07-13 JP JP14425084A patent/JPS6125692A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6125692A (en) | 1986-02-04 |
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