JPH01310793A - Treatment of waste plating solution - Google Patents
Treatment of waste plating solutionInfo
- Publication number
- JPH01310793A JPH01310793A JP14016588A JP14016588A JPH01310793A JP H01310793 A JPH01310793 A JP H01310793A JP 14016588 A JP14016588 A JP 14016588A JP 14016588 A JP14016588 A JP 14016588A JP H01310793 A JPH01310793 A JP H01310793A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- plating solution
- reaction
- hydrogen peroxide
- pref
- 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
- 239000002699 waste material Substances 0.000 title claims abstract description 31
- 238000007747 plating Methods 0.000 title claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 16
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 16
- -1 tungstate ions Chemical class 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- PNEHEYIOYAJHPI-UHFFFAOYSA-N lithium tungsten Chemical compound [Li].[W] PNEHEYIOYAJHPI-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、亜リン酸及び／又は次亜リン酸を含むめっき
廃液を処理し、処理の容易なリン酸を生成させるめっき
廃液の処理方法に関するものである。[Detailed Description of the Invention] [Technical Field] The present invention relates to a method for treating plating waste liquid containing phosphorous acid and/or hypophosphorous acid to generate easily treatable phosphoric acid. be.
従来、次亜リン酸を還元剤とする化学めっき法を用いる
無電解めっき液は知られており、カメラ工業や電子部品
工業等において広く利用されている。Conventionally, electroless plating solutions using a chemical plating method using hypophosphorous acid as a reducing agent have been known, and are widely used in the camera industry, electronic parts industry, and the like.
この無電解めっき法においては、めっき廃液として、亜
リン酸や次亜リン酸を多量含むめっき廃液が生しる。こ
のようなめっき廃液を廃棄するには、リン濃度を−・定
基準値以−トにする必要あり、亜リン酸や次亜リン酸を
除去する技術が望まれているが、亜リン酸や次亜リン酸
は非常に処理困難な物質であるため、現在のところ、未
だ工業的に有利な方法は開発されていない。In this electroless plating method, a plating waste liquid containing a large amount of phosphorous acid and hypophosphorous acid is produced as a plating waste liquid. In order to dispose of such plating waste liquid, it is necessary to bring the phosphorus concentration below a certain standard value, and a technology to remove phosphorous acid and hypophosphorous acid is desired. Since hypophosphorous acid is a substance that is extremely difficult to process, no industrially advantageous method has been developed yet.
本発明は、めっき廃液からそれに含まれる亜リン酸や次
亜リン酸を除去するための有利な方法を提供することを
目的とする。An object of the present invention is to provide an advantageous method for removing phosphorous acid and hypophosphorous acid contained in a plating waste solution.
ｃ問題点を解決するための′ｆ′−法〕本発明者らは、
前記［１的を達成すべく種々研究を重ねた結果、めっき
廃液中に含まわる処理困難な亜リン酸や次亜リン酸は、
これをいったん処理の容易なリン酸に酸化することによ
り、容易に除去し得ることに着目し、本発明を完成する
に至った。'f'-method for solving problem c] The present inventors
As a result of various studies aimed at achieving the above-mentioned goal 1, we found that phosphorous acid and hypophosphorous acid, which are difficult to treat, contained in plating waste liquid,
The present invention was completed based on the fact that this can be easily removed by oxidizing it to phosphoric acid, which is easy to treat.
即ち、本発明によれば、亜リン酸及び／又は次亜リン酸
を含むめっき廃ＮＵを、タングステン酸イオン及び／又
はモリブデン酸イオンの存在下、過酸化水素水と反応さ
せ、リン酸を生成させることを特徴とするめっき廃液の
処理方法が提供される。That is, according to the present invention, plating waste NU containing phosphorous acid and/or hypophosphorous acid is reacted with a hydrogen peroxide solution in the presence of tungstate ions and/or molybdate ions to generate phosphoric acid. A method for treating plating waste liquid is provided.
本発明の方法な好まし〈実施するには、めっき廃液に対
し、過酸化水素水を添加反応させる。この場合、めっき
廃液中には、触媒として、タングステン酸イオン及び／
又はモリブデン酸イオンを存在させる。この触媒斌は多
い程好ましいが、−般には、廃液１ａに対し、０．００
１〜０．１モル、好ましくは０．００５〜０．０５モル
の範囲である。反応時のめっき廃液のｐｏは特に制約さ
れず、アルカリ性条件でもよいが、反応速度の点から、
中性〜酸性条件に調節するのがよい。々ｆましいｐＨ条
件は、２〜５の範囲である。反応温度は、室温〜１００
°Ｃ１好ましくは４０〜９０℃である。高い温度の方が
反応速度が速くなる。Preferably, the method of the present invention is carried out by adding hydrogen peroxide solution to the plating waste solution. In this case, the plating waste liquid contains tungstate ions and/or catalysts.
or the presence of molybdate ions. The number of catalyst particles is preferably as large as possible; however, in general, 0.00
It ranges from 1 to 0.1 mol, preferably from 0.005 to 0.05 mol. The PO of the plating waste solution during the reaction is not particularly restricted, and alkaline conditions may be used, but from the viewpoint of reaction rate,
It is best to adjust the conditions to neutral to acidic conditions. Preferred pH conditions range from 2 to 5. The reaction temperature is room temperature to 100
°C1 is preferably 40 to 90 °C. The higher the temperature, the faster the reaction rate.
反応を行う場合、めっき廃液と過酸化水素水とを一時に
混合して実施することも可能であるが、めっき廃液に対
し、過酸化水素水を多段階にわたって、好ましくは滴下
して行うのが好士しい。過酸化水素水の滴下速度は、；
３５％過醜化水素水として廃液ＩＱ、及び１分間当り、
０．０５−３０ｃｃ、好ましく（ＪＯ１１〜＋−Ｏｃｃ
の割合である５、
〔発明の効果〕
本発明によれば、めっき廃液中に含まれる１■シリン酸
や次１１Ｉｉリン酸は、リン酸に酸化される。このＩＪ
ン酸は、廃液中から、通常の方法、例えば、リン酸カル
シウムやマクネシウム等の不溶性塩とし−Ｃ回収するこ
とかできるし、また、リン酸ナトリウムとして回収する
ことができる。When performing the reaction, it is possible to carry out the reaction by mixing the plating waste solution and the hydrogen peroxide solution at once, but it is preferable to carry out the reaction by dropping the hydrogen peroxide solution into the plating waste solution over multiple stages, preferably dropwise. It's nice. The dropping rate of hydrogen peroxide solution is;
Waste liquid IQ as 35% hydrogenated water and per minute,
0.05-30cc, preferably (JO11~+-Occ
The ratio is 5. [Effects of the Invention] According to the present invention, 1I syric acid and 11Ii phosphoric acid contained in the plating waste solution are oxidized to phosphoric acid. This IJ
The phosphoric acid can be recovered from the waste liquid using a conventional method, for example, as an insoluble salt such as calcium phosphate or magnesium phosphate, or it can be recovered as sodium phosphate.
本発明により処理された廃液は、これをめっき液原料と
して再び使用することもｉｉＪ能である。The waste liquid treated according to the present invention can also be used again as a raw material for plating solution.
次に本発明を実施例によりさらに説明する。 Next, the present invention will be further explained by examples.
実施例１
次亜リン酸すＩ−リウム：３０ＦＸ／Ｑと亜リン酸す１
−ＩノウＡ１５０バ／Ｑを含む水溶液からなるモデル廃
液（ｐｌ＋７）ＩＱに触媒を加え、：（５％過酸化水素
水１００ｔｎＱを３０分間Ｃ滴下シ１．て６０分間撹拌
後、表−１に示した時間反応祭行い、次亜リン酸及び亜
リン酸のリン酸への酸化状況をイオンクロマトグラフィ
ーで測定した。Example 1 Hypophosphite I-lium: 30FX/Q and phosphorous acid I
A catalyst was added to the model waste solution (pl+7) IQ consisting of an aqueous solution containing 150% of hydrogen peroxide, and after stirring for 60 minutes, 1. The reaction was carried out for the indicated time, and the oxidation status of hypophosphorous acid and phosphorous acid to phosphoric acid was measured by ion chromatography.
その結果を次表に示す。The results are shown in the table below.
表−１
実施例２
実施例１に示したモデル廃液ＩＱに苅し、タングステン
酸す１〜リウム１ｇを添加し、３錦過酸化水素水１２０
ｍ１を下記バッチ方式と滴下方式で加えてリン酸生成率
を測定した。その結果を表−２に示す。Table 1 Example 2 The model waste liquid IQ shown in Example 1 was poured, 1 to 1 g of lithium tungsten acid was added, and 120 g of 3-brocade hydrogen peroxide solution was added.
ml was added using the batch method and dropwise method described below, and the phosphoric acid production rate was measured. The results are shown in Table-2.
（１）バッチ方式
モデル廃液ＩＱに対し、過酸化水素水１２０ｍ１を添加
し、撹拌して反応を行った。(1) Batch method model 120 ml of hydrogen peroxide solution was added to the waste liquid IQ, and the mixture was stirred and reacted.
（２）滴下方式
モデル廃液ＩＱに対し、過酸化水素水１．２０ ＋ｄを
０．６− Ｊ −−−
時間で滴下して加え、撹拌して反応を行った。(2) Drop-dropping method 1.20 + d of hydrogen peroxide solution was added dropwise to the model waste liquid IQ over 0.6-J --- hours, and the reaction was carried out by stirring.
表−２
実施例３
実施例１に示したモデル廃液ＩＱに対し、水酸化すｊ・
リウム２０ｇを加え、タングステン酸す１−リウムを種
々の址加え、！］０℃に加熱しながら３５％過酸化水素
水２００証を６０分間で滴下し、その後４時間反応を行
った。得られた反応結果を表−３に示す。Table 2 Example 3 For the model waste liquid IQ shown in Example 1, hydroxide
Add 20g of lithium, add various amounts of 1-lium tungstate, and! ] While heating to 0°C, 35% hydrogen peroxide solution (200%) was added dropwise over 60 minutes, and the reaction was then carried out for 4 hours. The reaction results obtained are shown in Table-3.
表−３
実施例４
実施例１で示したモデル廃液ＩＱにタングステン酸す［
−リウム２５ｇを加え、ｐＨを水酸化すＩ−リウム又は
硫酸で所定の値に調整後、９０℃に加熱しなから３５％
過酸化水素水１００証を３０分間で滴下し、その後１．
５時間反応を行った。得られた反応結果を次表に示す。Table 3 Example 4 Tungstic acid was added to the model waste liquid IQ shown in Example 1.
- Add 25g of Lithium, adjust the pH to the specified value with I-Liium hydroxide or sulfuric acid, and then heat to 90°C to 35%
Drop 100% hydrogen peroxide solution over 30 minutes, then 1.
The reaction was carried out for 5 hours. The reaction results obtained are shown in the following table.
表−４
前δ１シ実験において得らオした処理液において、ｐＨ
２では次亜リン酸及び亜リン酸は認められず、Ｐ１１７
ては次亜リン酸Ｏ０錦及び亜リン酸０．錦が確認され、
ｐＨ２，７では次亜リン酸１．４％、弔ｉリン酸２４．
２２；が確認された。この結果より、酸性条件上での反
応の力がリン酸の４Ｆ成が速いことが判明した。Table 4 In the treatment solution obtained in the previous δ1 experiment, the pH
Hypophosphorous acid and phosphorous acid were not observed in P117.
Hypophosphorous acid O0 brocade and phosphorous acid 0. Nishiki was confirmed,
At pH 2.7, hypophosphorous acid is 1.4% and phosphorous acid is 24%.
22; was confirmed. From this result, it was found that the reaction force under acidic conditions was such that the formation of 4F from phosphoric acid was rapid.
Claims (1)
を、タングステン酸イオン及び／又はモリブデン酸イオ
ンの存在下、過酸化水素水と反応させ、リン酸を生成さ
せることを特徴とするめっき廃液の処理方法。(1) A plating waste solution containing phosphorous acid and/or hypophosphorous acid is reacted with a hydrogen peroxide solution in the presence of tungstate ions and/or molybdate ions to generate phosphoric acid. Processing method for plating waste liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14016588A JPH01310793A (en) | 1988-06-07 | 1988-06-07 | Treatment of waste plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14016588A JPH01310793A (en) | 1988-06-07 | 1988-06-07 | Treatment of waste plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01310793A true JPH01310793A (en) | 1989-12-14 |
| JPH0336597B2 JPH0336597B2 (en) | 1991-05-31 |
Family
ID=15262391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14016588A Granted JPH01310793A (en) | 1988-06-07 | 1988-06-07 | Treatment of waste plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01310793A (en) |
-
1988
- 1988-06-07 JP JP14016588A patent/JPH01310793A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0336597B2 (en) | 1991-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |