JPH11253928A - Treatment of waste liquid of hypophosphorous acid and phosphorus acid - Google Patents
Treatment of waste liquid of hypophosphorous acid and phosphorus acidInfo
- Publication number
- JPH11253928A JPH11253928A JP7305598A JP7305598A JPH11253928A JP H11253928 A JPH11253928 A JP H11253928A JP 7305598 A JP7305598 A JP 7305598A JP 7305598 A JP7305598 A JP 7305598A JP H11253928 A JPH11253928 A JP H11253928A
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- Prior art keywords
- copper
- waste liquid
- acid
- chloride
- phosphorous acid
- 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.)
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- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は例えば無電解ニッケ
ルメッキ液の還元剤として含まれる次亜リン酸とこの次
亜リン酸を含むメッキ液が老化して亜リン酸をも含んだ
廃液の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 the treatment of, for example, hypophosphorous acid contained as a reducing agent for an electroless nickel plating solution and a waste solution containing a phosphorous acid which ages due to aging of the plating solution containing this hypophosphorous acid. It is about the method.
【０００２】[0002]
【従来の技術】無電解めっき法は、電解CNめっき法と異
なり外部電流を使用せず、プラスチックスにもめっき可
能なため、その適用は大きく広がった。それに伴って、
無電解メッキ液の排出量も増加した。この廃液には、重
金属や有機物を多く含むだけでなく、次亜リン酸とこの
次亜リン酸が老化した亜リン酸とを多く含まれているた
め、一元的に処理するには非常に困難であることが分か
っている。現行の処理方法は重金属のみを対象としたも
のであり、次亜リン酸及び亜リン酸や有機物（COD換算
物）を対象にしたものは非常に少ない。2. Description of the Related Art Unlike the electrolytic CN plating method, the electroless plating method does not use an external current and can also be applied to plastics. Along with that,
The discharge of the electroless plating solution also increased. This waste liquid not only contains a lot of heavy metals and organic substances, but also contains a lot of hypophosphorous acid and this hypophosphorous acid, which is aged. I know that Current treatment methods are for heavy metals only, and very few are for hypophosphorous acid and phosphorous acid or organic substances (COD equivalent).
【０００３】従って、総合的な処理プロセスを確立する
際、次亜リン酸及び亜リン酸を含む廃液の酸化処理法の
開発・確立が重要課題となる。これまでの研究では、次
亜リン酸のＦｅ(III)イオンによる化学的酸化処理法が
報告されているが、取り扱う次亜リン酸や共存物質の濃
度は低く、無電解ニッケルメッキ廃液のように高濃度の
廃液への適用にはまだ至っていない。Therefore, when establishing a comprehensive treatment process, it is important to develop and establish a method for oxidizing waste liquid containing hypophosphorous acid and phosphorous acid. Previous studies have reported a chemical oxidation treatment of hypophosphorous acid with Fe (III) ions, but the concentration of hypophosphorous acid and coexisting substances to be handled is low, and it is difficult to use electroless nickel plating wastewater. It has not yet been applied to highly concentrated waste liquids.
【０００４】[0004]
【発明が解決しようとする課題】そこで、本発明者らは
鋭意努力の結果、次亜リン酸及び亜リン酸を酸化する酸
化剤をいくつか選び、検討した結果、２価の銅イオンを
利用することで次亜リン酸及び亜リン酸の酸化、そして
再度銅塩として固体回収が可能であることが示唆され、
本発明に至った。The inventors of the present invention have made intensive efforts to select hypophosphorous acid and some oxidizing agents for oxidizing phosphorous acid, and as a result, have studied the use of divalent copper ions. This suggests that it is possible to oxidize hypophosphorous acid and phosphorous acid, and to recover solid as a copper salt again,
The present invention has been reached.
【０００５】本発明は、無電解ニッケルメッキ廃液のよ
うに高濃度の次亜リン酸及び亜リン酸を含む廃液の処理
法を得ることを目的とする。更には、プリント基板のエ
ッチング工程などで排出される塩化銅(II)廃液から塩化
銅(Ｉ)を回収することのできる次亜リン酸及び亜リン酸
を含む廃液の処理法を得ることを目的とする。An object of the present invention is to provide a method for treating a waste liquid containing a high concentration of hypophosphorous acid and phosphorous acid such as an electroless nickel plating waste liquid. Another object of the present invention is to provide a method for treating hypophosphorous acid and a wastewater containing phosphorous acid capable of recovering copper (I) chloride from a copper (II) wastewater discharged in a printed circuit board etching step or the like. And
【０００６】[0006]
【課題を解決するための手段】本請求項１に記載された
発明に係る次亜リン酸及び亜リン酸廃液の処理法では、
次亜リン酸及び亜リン酸を含む廃液を２価の銅イオン存
在下で、予め定められた温度に加温する方法である。According to the method for treating hypophosphorous acid and the waste solution of phosphorous acid according to the first aspect of the present invention,
This is a method in which a waste liquid containing hypophosphorous acid and phosphorous acid is heated to a predetermined temperature in the presence of divalent copper ions.
【０００７】本請求項２に記載された発明に係る次亜リ
ン酸及び亜リン酸廃液の処理法では、請求項１に記載さ
れた予め定められた温度として、４０℃以上に加温する
方法である。[0007] In the method for treating hypophosphorous acid and phosphorous acid waste liquid according to the second aspect of the present invention, a method of heating to a predetermined temperature of 40 ° C or more according to the first aspect. It is.
【０００８】本請求項３に記載された発明に係る次亜リ
ン酸及び亜リン酸廃液の処理法では、請求項２に記載さ
れため定められた温度として、６０℃以上８０℃以下に
加温する方法である。[0008] In the method for treating hypophosphorous acid and a waste solution of phosphorous acid according to the third aspect of the present invention, the temperature is set to be not less than 60 ° C and not more than 80 ° C as set forth in the second aspect. How to
【０００９】本請求項４に記載された発明に係る次亜リ
ン酸及び亜リン酸廃液の処理法では、請求項１に記載さ
れた２価の銅イオンとして、塩化銅(II)廃液を用いる方
法である。In the method for treating a hypophosphorous acid and a phosphorous acid waste liquid according to the invention described in claim 4, copper (II) chloride waste liquid is used as the divalent copper ion described in claim 1. Is the way.
【００１０】[0010]
【発明の実施の形態】本発明においては、次亜リン酸及
び亜リン酸を含む廃液に２価の銅塩を添加した後、予め
定められた温度に加温することにより、次亜リン酸及び
亜リン酸を酸化することができる。詳しい反応は次の示
す通りであると考えられる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, hypophosphorous acid is added to a waste liquid containing hypophosphorous acid and phosphorous acid, and then heated to a predetermined temperature. And phosphorous acid can be oxidized. The detailed reaction is considered to be as follows.
【００１１】 Ｈ2ＰＯ2 -＋Ｈ2Ｏ→ＨＰＯ3 2-＋Ｈ+＋２Ｈ0 …（１） Ｃｕ2+＋２Ｈ0 →Ｃｕ↓＋２Ｈ+ …（２） ＣｕＣｌ2＋Ｈ0 →ＣｕＣｌ↓＋ＨＣｌ …（３） Ｃｕ2+＋ＨＰＯ3 2-＋Ｈ2Ｏ→Ｃｕ↓＋ＨＰＯ4 2-＋２Ｈ+ …（４） ２ＣｕＣｌ2＋ＨＰＯ3 2-＋Ｈ2Ｏ→２ＣｕＣｌ↓＋ＨＰＯ4 2-＋ＨＣｌ …（５）H 2 PO 2 − + H 2 O → HPO 3 2− + H + + 2H 0 (1) Cu 2+ + 2H 0 → Cu ↓ + 2H + (2) CuCl 2 + H 0 → CuCl ↓ + HCl (3) Cu 2+ + HPO 3 2+ H 2 O → Cu ↓ + HPO 4 2+ 2H + ... (4) 2CuCl 2 + HPO 3 2+ H 2 O → 2CuCl ↓ + HPO 4 2+ HCl ... (5)
【００１２】即ち、（１）式に示す通り、次亜リン酸は
亜リン酸に至る過程で２つの水素原子（Ｈ0）を放出す
る。この水素原子は（２）式に示す通り、２価の銅イオ
ンを金属銅として析出させる。また、特別に塩化銅(II)
を用いた場合には、塩化銅(II)中の２価の銅イオンが金
属銅として析出する前に、（３）式に示す通り、塩化銅
(II)を塩化銅(Ｉ)にして析出させる。また、亜リン酸は
同じく還元性が高いため、（４）式に示す通り、メタリ
ン酸に至る過程で銅イオンを析出させたり、（５）式に
示す通り、塩化銅(II)を塩化銅(Ｉ)にして析出させる。That is, as shown in the formula (1), hypophosphorous acid releases two hydrogen atoms (H 0 ) in the process of reaching phosphorous acid. This hydrogen atom precipitates divalent copper ions as metallic copper as shown in equation (2). Also specially copper (II) chloride
Is used, before the divalent copper ions in copper (II) chloride precipitate as metallic copper, as shown in equation (3),
(II) is converted to copper (I) chloride and precipitated. Also, since phosphorous acid has a high reducibility, copper ions are precipitated in the process of metaphosphoric acid as shown in equation (4), and copper (II) chloride is converted to copper chloride as shown in equation (5). (I) and precipitated.
【００１３】銅塩の中でも塩化銅(II)についてはその形
態に関係なく塩化銅(Ｉ)として回収でき、添加する銅塩
が固体状態でも溶液状態でも、反応は同じように進行
し、30分程度でほぼ反応が終了する。Among copper salts, copper (II) chloride can be recovered as copper (I) chloride irrespective of its form, and the reaction proceeds in the same manner regardless of whether the added copper salt is in a solid state or a solution state, and the reaction proceeds for 30 minutes. The reaction is almost completed when the reaction is completed.
【００１４】本発明においては、前述の金属銅及び塩化
銅(Ｉ)の析出反応を起こさせるには、好ましくは４０℃
以上に加温する必要があることが判った。また、６０℃
以上の加温で析出量がほぼ平衡状態となるため、より好
ましくは、６０℃以上に加温する必要があることが判っ
た。尚、８０℃を越えて加温することは、加温に対する
析出量もさほど変わりがなく、エネルギー面、熱に対す
る加熱槽の対処等を考慮して、８０℃以下の加温で充分
である。In the present invention, in order to cause the above-described precipitation reaction of metallic copper and copper (I) chloride, the reaction is preferably carried out at 40 ° C.
It turned out that it was necessary to heat above. Also, 60 ° C
It has been found that it is necessary to heat to 60 ° C. or more, more preferably, because the amount of precipitation becomes almost equilibrium by the above heating. Heating above 80 ° C. does not significantly change the amount of deposition with respect to heating, and heating at 80 ° C. or less is sufficient in consideration of the energy surface and how the heating tank handles heat.
【００１５】本発明で用いる２価の銅イオンとしては、
前述の反応式に示す通り、硫酸銅(II)、酢酸銅(II)とい
った銅塩を添加すると金属銅として回収でき、塩化銅(I
I)を添加した場合、白色沈殿物［塩化銅(Ｉ)〕として回
収できる。得られる金属銅は微粉状で、濾過性に乏しい
が、得られる白色沈殿物［塩化銅(Ｉ)］は沈降性及び脱
水性がよく、含水率も15％程度と低く、固液分離を行い
やすいため、２価の銅イオンとしては塩化銅(II)を用い
ることが好ましい。The divalent copper ions used in the present invention include:
As shown in the above reaction formula, when copper salts such as copper (II) sulfate and copper (II) acetate are added, it can be recovered as metallic copper, and copper chloride (I
When I) is added, it can be recovered as a white precipitate [copper (I) chloride]. The resulting metallic copper is in the form of fine powder and poor in filterability, but the resulting white precipitate [copper (I) chloride] has good sedimentation and dehydration properties, has a low water content of about 15%, and undergoes solid-liquid separation. It is preferable to use copper (II) chloride as the divalent copper ion.
【００１６】本発明で用いる塩化銅(II)としては、塩化
銅(II)廃液を利用してもよい。この塩化銅(II)廃液は、
電子部品の需要増加とともに、その排出量が大きく増大
しているプリント基板のエッチング工程などで排出され
るものである。この塩化銅廃液には多量の２価の銅イオ
ンが含まれており、銅の濃度は十万mg／リットル以上と
非常に高い。そのため廃液中の銅の回収・リサイクル化
が大きく注目される。また、他の銅含有廃液でもその銅
化合物の種類によっては金属銅としてリサイクルが可能
である。As the copper (II) chloride used in the present invention, a copper (II) chloride waste liquid may be used. This copper (II) chloride waste liquid,
With the increase in demand for electronic components, these are emitted in a process of etching a printed circuit board, the amount of which is greatly increasing. This copper chloride waste liquid contains a large amount of divalent copper ions, and the concentration of copper is as high as 100,000 mg / liter or more. Therefore, attention is paid to the collection and recycling of copper in waste liquid. Further, other copper-containing waste liquid can be recycled as metallic copper depending on the type of the copper compound.
【００１７】従って、本発明は、次亜リン酸及び亜リン
酸廃液を利用して塩化銅(II)廃液から銅を回収する方法
という側面を有する。本発明は次亜リン酸及び亜リン酸
廃液の一次処理法としても有効であるだけでなく、銅の
リサイクルとしても有効であるという両面性をもつもの
である。Accordingly, the present invention has an aspect of a method for recovering copper from a copper (II) chloride waste liquid by using hypophosphorous acid and a phosphorous acid waste liquid. INDUSTRIAL APPLICABILITY The present invention is effective not only as a primary treatment method for hypophosphorous acid and phosphorous acid waste liquid, but also for recycling copper.
【００１８】[0018]
【実施例】１．試料 実験に使用した次亜リン酸及び亜リン酸含有廃液は３種
類でその組成を以下の表１に示す。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Samples The hypophosphorous acid and phosphorous acid-containing waste liquid used in the experiment were of three types, and their compositions are shown in Table 1 below.
【００１９】[0019]
【表１】 [Table 1]
【００２０】塩化銅溶液は薬品から調整したものと、実
廃液との２種類を使用した。各々の銅イオン濃度、及び
比重を表２に示す。Two types of copper chloride solutions were used, one prepared from chemicals and the other, a real waste liquid. Table 2 shows the respective copper ion concentrations and specific gravities.
【００２１】[0021]
【表２】 [Table 2]
【００２２】２．基本操作 実験液（無電解ニッケルメッキ廃液）を適量取り、液温
調節した後、塩化銅廃液および酸を添加し、反応を観測
するとともに、目的に応じて析出した銅、ＣＯＤ，Ｐ量
などを測定した。2. Basic operation Take an appropriate amount of experimental solution (electroless nickel plating waste solution), adjust the temperature of the solution, add copper chloride waste solution and acid, observe the reaction, and determine the amount of copper, COD, P, etc. deposited according to the purpose. It was measured.
【００２３】３．実験例１（反応温度の影響） 添加する塩化銅と次亜リン酸（Ｐ2）の比（Cu/Ｐ2）を
一定にし、反応させる液温の影響について検討した。図
１は廃液Ａと廃液Ｚとを用いた場合の所定の温度での銅
の回収率及び回収量を示す線図である。図２は廃液Ｂと
調整液とを用いた場合の所定の温度での銅の回収率及び
回収量を示す線図である。図３は廃液Ｃと調整液とを用
いた場合（Cu／Ｐ2＝1.0）の所定の温度での銅の回収率
及び回収量を示す線図である。図４は廃液Ｃと調整液と
を用いた場合（Cu／Ｐ2＝2.0）の所定の温度での銅の回
収率及び回収量を示す線図である。3. Experimental Example 1 (Effect of Reaction Temperature) The ratio of the added copper chloride and hypophosphorous acid (P 2 ) (Cu / P 2 ) was kept constant, and the effect of the liquid temperature for the reaction was examined. FIG. 1 is a diagram showing the recovery rate and the recovery amount of copper at a predetermined temperature when waste liquid A and waste liquid Z are used. FIG. 2 is a diagram showing the recovery rate and the recovery amount of copper at a predetermined temperature when the waste liquid B and the adjustment liquid are used. FIG. 3 is a diagram showing the recovery rate and the recovery amount of copper at a predetermined temperature when the waste liquid C and the adjustment liquid are used (Cu / P 2 = 1.0). FIG. 4 is a diagram showing the recovery rate and the recovery amount of copper at a predetermined temperature when the waste liquid C and the adjustment liquid are used (Cu / P 2 = 2.0).
【００２４】図１〜図４に示す通り、反応する温度の上
昇に応じて析出する塩化銅(Ｉ)の量が増えることが判っ
た。図１においては図２〜図４とは相違した傾向が見ら
れた。しかし、廃液Ｂや廃液Ｃと廃液Ｚとを反応させて
も図２〜図４と同じ傾向であったことから、この傾向の
相違は廃液Ｚによるものではなく、廃液Ａに含まれてい
る他の成分によるものと考えられた。また、図２〜図４
に示す通り塩化銅(Ｉ)の沈殿物生成は６０℃でほぼ平衡
となることが判った。As shown in FIGS. 1 to 4, it was found that the amount of precipitated copper (I) chloride increased as the reaction temperature increased. In FIG. 1, a tendency different from FIGS. 2 to 4 was observed. However, even when the waste liquid B or the waste liquid C was reacted with the waste liquid Z, the tendency was the same as in FIGS. 2 to 4. Therefore, the difference in the tendency was not due to the waste liquid Z but included in the waste liquid A. It was thought to be due to the components of 2 to 4
It was found that the formation of a precipitate of copper (I) chloride was almost equilibrated at 60 ° C. as shown in FIG.
【００２５】４．実験２（銅とリン（Ｐ2）との比（Cu
／Ｐ2）による影響） 反応温度を一定に保ち（80℃）、塩化銅の添加量を変化
させ、銅の回収に及ぼす銅／リン比（Cu／Ｐ2）の影響
について検討した。図５は廃液Ａと廃液Ｚとを用いて銅
とリンとの比を相違させた場合の銅の回収率及び回収量
を示す線図である。図６は廃液Ｂと調整液とを用いて銅
とリンとの比を相違させた場合の銅の回収率及び回収量
を示す線図である。図７は廃液Ｃと調整液とを用いて銅
とリンとの比を相違させた場合の銅の回収率及び回収量
を示す線図である。4. Experiment 2 (copper to phosphorus (P 2 ) ratio (Cu
/ P 2 ) The reaction temperature was kept constant (80 ° C.), the amount of copper chloride added was varied, and the effect of the copper / phosphorus ratio (Cu / P 2 ) on copper recovery was examined. FIG. 5 is a diagram showing the recovery rate and the recovery amount of copper when the ratio of copper to phosphorus is changed using the waste liquid A and the waste liquid Z. FIG. 6 is a diagram showing the recovery rate and the recovery amount of copper when the ratio of copper to phosphorus is changed using the waste liquid B and the adjustment liquid. FIG. 7 is a diagram showing the recovery rate and the recovery amount of copper when the ratio of copper to phosphorus is changed using the waste liquid C and the adjustment liquid.
【００２６】図５〜図７に示す通り、塩化銅の添加量を
増やすことにより、回収される銅の量が増えていること
が判った。また、回収率としては塩化銅の添加量の変化
に殆ど変わりがなく、６０〜８０％となった。As shown in FIGS. 5 to 7, it was found that the amount of copper recovered was increased by increasing the amount of copper chloride added. In addition, the recovery rate was 60 to 80%, with almost no change in the amount of copper chloride added.
【００２７】[0027]
【発明の効果】本発明は以上説明したとおり、無電解ニ
ッケルメッキ廃液のように高濃度の次亜リン酸及び亜リ
ン酸を含む廃液の処理法を得ることができ、更には、プ
リント基板のエッチング工程などで排出される塩化銅(I
I)廃液から塩化銅(Ｉ)を回収することのできる次亜リン
酸及び亜リン酸を含む廃液の処理法を得ることができる
という効果がある。As described above, according to the present invention, it is possible to obtain a method for treating a waste solution containing a high concentration of hypophosphorous acid and phosphorous acid, such as an electroless nickel plating waste solution. Copper chloride (I
I) There is an effect that it is possible to obtain a method for treating a waste liquid containing hypophosphorous acid and phosphorous acid that can recover copper (I) chloride from the waste liquid.
【図１】廃液Ａと廃液Ｚとを用いた場合の所定の温度で
の銅の回収率及び回収量を示す線図である。FIG. 1 is a diagram showing a recovery rate and a recovery amount of copper at a predetermined temperature when a waste liquid A and a waste liquid Z are used.
【図２】廃液Ｂと調整液とを用いた場合の所定の温度で
の銅の回収率及び回収量を示す線図である。FIG. 2 is a diagram showing a recovery rate and a recovery amount of copper at a predetermined temperature when a waste liquid B and an adjustment liquid are used.
【図３】廃液Ｃと調整液とを用いた場合（Cu／Ｐ2＝1.
0）の所定の温度での銅の回収率及び回収量を示す線図
である。FIG. 3 shows a case in which a waste liquid C and a conditioning liquid are used (Cu / P 2 = 1.
FIG. 2 is a diagram showing the recovery rate and the recovery amount of copper at a predetermined temperature of 0).
【図４】廃液Ｃと調整液とを用いた場合（Cu／Ｐ2＝2.
0）の所定の温度での銅の回収率及び回収量を示す線図
である。FIG. 4 shows a case in which a waste liquid C and a conditioning liquid are used (Cu / P 2 = 2.
FIG. 2 is a diagram showing the recovery rate and the recovery amount of copper at a predetermined temperature of 0).
【図５】廃液Ａと廃液Ｚとを用いて銅とリンとの比を相
違させた場合の銅の回収率及び回収量を示す線図であ
る。FIG. 5 is a diagram showing the recovery rate and the recovery amount of copper when the ratio of copper to phosphorus is changed by using the waste liquid A and the waste liquid Z.
【図６】廃液Ｂと調整液とを用いて銅とリンとの比を相
違させた場合の銅の回収率及び回収量を示す線図であ
る。FIG. 6 is a graph showing the recovery rate and the recovery amount of copper when the ratio of copper to phosphorus is changed by using the waste liquid B and the adjustment liquid.
【図７】廃液Ｃと調整液とを用いて銅とリンとの比を相
違させた場合の銅の回収率及び回収量を示す線図であ
る。FIG. 7 is a diagram showing a copper recovery rate and a copper recovery amount when the ratio of copper to phosphorus is changed using the waste liquid C and the adjustment liquid.
Claims (4)
価の銅イオン存在下で、予め定められた温度に加温する
ことを特徴とする次亜リン酸及び亜リン酸廃液の処理
法。1. A waste liquid containing hypophosphorous acid and phosphorous acid
A method for treating hypophosphorous acid and a waste solution of phosphorous acid, comprising heating to a predetermined temperature in the presence of multivalent copper ions.
以上に加温することを特徴とする請求項１に記載された
次亜リン酸及び亜リン酸廃液の処理法。2. The predetermined temperature is 40 ° C.
The method for treating hypophosphorous acid and phosphorous acid waste liquid according to claim 1, wherein the heating is performed as described above.
以上８０℃以下に加温することを特徴とする請求項２に
記載された次亜リン酸及び亜リン酸廃液の処理法。3. The method according to claim 1, wherein the predetermined temperature is 60 ° C.
The method for treating hypophosphorous acid and a phosphorous acid waste solution according to claim 2, wherein the solution is heated to at least 80 ° C.
を用いることを特徴とする請求項１に記載された次亜リ
ン酸及び亜リン酸廃液の処理法。4. The method according to claim 1, wherein said divalent copper ion is copper (II) chloride.
A method for treating hypophosphorous acid and a waste solution of phosphorous acid according to claim 1, characterized by using:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07305598A JP3448730B2 (en) | 1998-03-09 | 1998-03-09 | Method for treating hypophosphorous acid and waste liquid of phosphorous acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07305598A JP3448730B2 (en) | 1998-03-09 | 1998-03-09 | Method for treating hypophosphorous acid and waste liquid of phosphorous acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11253928A true JPH11253928A (en) | 1999-09-21 |
| JP3448730B2 JP3448730B2 (en) | 2003-09-22 |
Family
ID=13507304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07305598A Expired - Fee Related JP3448730B2 (en) | 1998-03-09 | 1998-03-09 | Method for treating hypophosphorous acid and waste liquid of phosphorous acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3448730B2 (en) |
-
1998
- 1998-03-09 JP JP07305598A patent/JP3448730B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3448730B2 (en) | 2003-09-22 |
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