JPH0122830B2 - - Google Patents
Info
- Publication number
- JPH0122830B2 JPH0122830B2 JP4127384A JP4127384A JPH0122830B2 JP H0122830 B2 JPH0122830 B2 JP H0122830B2 JP 4127384 A JP4127384 A JP 4127384A JP 4127384 A JP4127384 A JP 4127384A JP H0122830 B2 JPH0122830 B2 JP H0122830B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- waste liquid
- added
- copper plating
- edta
- 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
- 239000010949 copper Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】
本発明は化学銅めつき廃液の処理方法に係り、
特に、EDTA及び銅を含む化学銅めつき廃液か
ら銅を高度に除去する方法に関する。[Detailed Description of the Invention] The present invention relates to a method for treating chemical copper plating waste liquid,
In particular, the present invention relates to a method for highly removing copper from chemical copper plating wastewater containing EDTA and copper.
化学銅めつき廃液中には多量のEDTA及び銅
が含まれており、このような廃液を処理するに
は、従来、電解法又はホルマリン還元法で銅を５
mg／〜10mg／まで除去した後、硫酸でPHを
1.8に調節してEDTAを500mg／程度まで除去す
る方法が採用されている。この廃水を更に放流規
準まで浄化処理するために、従来、消石灰を過剰
にしてPHを12以上に調節した後、これに高分子凝
集剤を添加し、固液分離を行つていた。しかし、
この方法では処理水中の銅濃度を３mg／までし
か低下できず、極めて処理効果が悪かつた。 Chemical copper plating waste liquid contains a large amount of EDTA and copper, and in order to treat such waste liquid, conventional methods have been to remove copper by electrolytic method or formalin reduction method.
mg/~10mg/, then adjust the pH with sulfuric acid.
A method has been adopted in which the amount of EDTA is adjusted to 1.8 and removed to about 500 mg/day. In order to further purify this wastewater to discharge standards, conventionally, excess slaked lime was added to adjust the pH to 12 or higher, and then a polymer flocculant was added to perform solid-liquid separation. but,
With this method, the copper concentration in the treated water could only be reduced to 3 mg/, and the treatment effect was extremely poor.
本発明の目的は、化学銅メツキ廃液から銅を高
い除去率で除去する処理方法を提供することにあ
る。この目的は本発明によれば、銅を硫化銅とし
て析出させ、遊離しているEDTAをアルミニウ
ム塩とすることによつて達成される。 An object of the present invention is to provide a treatment method for removing copper from chemical copper plating waste liquid at a high removal rate. This object is achieved according to the invention by precipitating the copper as copper sulphide and converting the free EDTA into an aluminum salt.
即ち、本発明による化学銅めつき廃液の処理方
法は、化学銅めつき廃液に硫化ナトリウム、ジメ
チルジチオカルバミン酸ナトリウム等の硫黄を含
む化合物を添加し、PHを約７に調節し、次いでポ
リ塩化アルミニウム、ベントナイト及び高分子凝
集剤を添加した後、固液分離することを特徴とす
る。 That is, the method for treating chemical copper plating waste liquid according to the present invention involves adding sulfur-containing compounds such as sodium sulfide and sodium dimethyldithiocarbamate to chemical copper plating waste liquid to adjust the pH to about 7, and then adding polyaluminum chloride to the chemical copper plating waste liquid. , is characterized by solid-liquid separation after adding bentonite and a polymer flocculant.
本発明方法において、EDTA及び銅を含む化
学銅めつき廃液に硫化ナトリウム、ジメチルジチ
オカルバミン酸等の硫黄含有化合物を添加する
と、これは廃液中に含まれていたEDTA−Cuと
反応して遊離のEDTA及び硫化銅を生成する。
次いで、アルカリ剤又は鉱酸を用いて廃液のPHを
約７すなわち実用上は５〜８に調節した後、ポリ
塩化アルミニウムを添加して遊離のEDTAを
EDTA−Alとする。ポリ塩化アルミニウムの添
加量は前記遊離したEDTAに対して当量以上で
あることが好ましく、通常、50〜500mg／で充
分である。 In the method of the present invention, when a sulfur-containing compound such as sodium sulfide or dimethyldithiocarbamic acid is added to a chemical copper plating waste solution containing EDTA and copper, this reacts with EDTA-Cu contained in the waste solution to release free EDTA. and produces copper sulfide.
Then, after adjusting the pH of the waste liquid to about 7, practically 5 to 8, using an alkaline agent or mineral acid, polyaluminum chloride is added to remove free EDTA.
Let it be EDTA-Al. The amount of polyaluminum chloride added is preferably at least equivalent to the liberated EDTA, and usually 50 to 500 mg/are sufficient.
他方、硫化銅のフロツクは微細で、軽いので、
その沈降性を増強するためにベントナイトを添加
する。ベントナイトの添加量は250〜1000mg／
であるのが好ましい。 On the other hand, copper sulfide flocs are fine and light, so
Bentonite is added to enhance its settling properties. The amount of bentonite added is 250 to 1000mg/
It is preferable that
生じた硫化銅とベントナイトのフロツクを更に
大きく成長させ、沈降性を良くするために、高分
子凝集剤を添加する。高分子凝集剤の添加量は、
通常、１〜５mg／で充分である。 A polymer flocculant is added to make the resulting copper sulfide and bentonite flocs grow larger and improve their settling properties. The amount of polymer flocculant added is
Usually, 1 to 5 mg/are sufficient.
本発明方法によれば、化学銅めつき廃液から銅
を極めて高い除去率で除去することができる。 According to the method of the present invention, copper can be removed from chemical copper plating waste liquid at an extremely high removal rate.
次に、実施例に基づいて本発明を詳述するが、
本発明はこれに限定されるものではない。 Next, the present invention will be explained in detail based on examples.
The present invention is not limited to this.
実施例
COD3600mg／、銅11mg／、EDTA480mg／
及びホルムアルデヒド20mg／を含むPH２の化
学銅メツキ廃液１を水酸化ナトリウムでPH７に
調節した後、ジメチルジチオカルバミン酸ナトリ
ウムを300mg／添加し、ジヤーテスターで
40rpmで10分間撹拌した。次いで、ポリ塩化アル
ミニウム50mg／及びベントナイト500mg／を
添加し、最終的にPHを７に調節した後、高分子凝
集剤としてハイモロツクSS−100を５mg／添加
し、固液分離を行つた。得られた処理水の銅濃度
を測定したところ、0.05mg／より低い濃度であ
つた。Example COD3600mg/, copper 11mg/, EDTA480mg/
After adjusting the pH of chemical copper plating waste 1 containing 20 mg of formaldehyde and 20 mg of formaldehyde to 7 with sodium hydroxide, 300 mg of sodium dimethyldithiocarbamate was added, and the mixture was heated with a jar tester.
Stirred at 40 rpm for 10 minutes. Next, 50 mg of polyaluminum chloride and 500 mg of bentonite were added, and the pH was finally adjusted to 7. After that, 5 mg of Himorok SS-100 was added as a polymer flocculant to perform solid-liquid separation. When the copper concentration of the obtained treated water was measured, it was found to be lower than 0.05 mg/.
従来法によれば、前記のように３mg／程度ま
でしか銅を除去できなかつたので、本発明方法に
よつて達成される銅の除去率は極めて高く、本発
明方法は従来法に比較して格別優れた処理法であ
る。 According to the conventional method, copper could only be removed to the extent of 3 mg/day as mentioned above, so the copper removal rate achieved by the method of the present invention is extremely high, and the method of the present invention is superior to the conventional method. This is an especially excellent treatment method.
なお、前記の実施例では硫黄を含む化合物とし
てジメチルジチオカルバミン酸ナトリウムを使用
したが、他の硫黄含有化合物、例えば硫化ナトリ
ウムを使用しても同様に良好な結果が得られる。 In the above examples, sodium dimethyldithiocarbamate was used as the sulfur-containing compound, but similarly good results can be obtained by using other sulfur-containing compounds, such as sodium sulfide.
Claims (1)
黄を含む化合物を添加し、PHを約７に調節し、次
いでポリ塩化アルミニウム、ベントナイト及び高
分子凝集剤を添加した後、固液分離することを特
徴とする化学銅めつき廃液の処理方法。1 Add a compound containing sulfur to the chemical copper plating waste liquid containing EDTA and copper, adjust the pH to about 7, then add polyaluminum chloride, bentonite and a polymer flocculant, and then perform solid-liquid separation. Characteristic method for treating chemical copper plating waste liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4127384A JPS60187394A (en) | 1984-03-06 | 1984-03-06 | Treatment of waste chemical copper plating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4127384A JPS60187394A (en) | 1984-03-06 | 1984-03-06 | Treatment of waste chemical copper plating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60187394A JPS60187394A (en) | 1985-09-24 |
| JPH0122830B2 true JPH0122830B2 (en) | 1989-04-27 |
Family
ID=12603830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4127384A Granted JPS60187394A (en) | 1984-03-06 | 1984-03-06 | Treatment of waste chemical copper plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60187394A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5190683A (en) * | 1990-06-19 | 1993-03-02 | Baker Hughes Incorporated | Water clarification composition containing a water clarifier component and a floc modifier component |
| JP6884986B2 (en) * | 2015-08-07 | 2021-06-09 | 東ソー株式会社 | How to purify zinc-containing aqueous solution |
| CN106915812A (en) * | 2015-12-28 | 2017-07-04 | 沈阳中科环境工程科技开发有限公司 | A kind of chemical nickle-plating wastewater inorganic agent and preparation method thereof |
-
1984
- 1984-03-06 JP JP4127384A patent/JPS60187394A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60187394A (en) | 1985-09-24 |
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