JPH0718023B2 - Copper sulfate recovery method and apparatus - Google Patents
Copper sulfate recovery method and apparatusInfo
- Publication number
- JPH0718023B2 JPH0718023B2 JP10331691A JP10331691A JPH0718023B2 JP H0718023 B2 JPH0718023 B2 JP H0718023B2 JP 10331691 A JP10331691 A JP 10331691A JP 10331691 A JP10331691 A JP 10331691A JP H0718023 B2 JPH0718023 B2 JP H0718023B2
- Authority
- JP
- Japan
- Prior art keywords
- copper sulfate
- liquid
- crystallizer
- copper
- slurry
- 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 - Fee Related
Links
Landscapes
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、プリント配線基板など
の電気回路基板のエッチング処理において、エッチング
液中に溶解した銅を冷却晶析法によって硫酸銅5水塩の
結晶として析出させ、これを回収する方法及びその装置
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for etching an electric circuit board such as a printed wiring board by precipitating copper dissolved in an etching solution as crystals of copper sulfate pentahydrate by a cooling crystallization method. The present invention relates to a collecting method and an apparatus thereof.
【0002】[0002]
【従来の技術】プリント配線基板などの電気回路基板の
製造においては、特定量の銅又は銅合金を除くため、過
酸化水素と硫酸又は混酸等を主成分とするエッチング液
を使用し、その液温を45〜50℃程度に維持してエッ
チング処理が行われている。このエッチング液中には、
使用中に銅が溶け込んで蓄積されることから、その余剰
分を残留過酸化水素を分解することなく回収するには、
このエッチング液を晶析缶にて冷却して硫酸銅5水温
(以下単に硫酸銅と称す)の結晶として回収することが
行われていた。ところで、回収される硫酸銅結晶は、で
きるだけ液分の少ない状態であることが好ましく、晶析
缶から硫酸銅スラリを取り出し、固液分離機に移送して
液分の少ない硫酸銅結晶を回収し、分離された液分をエ
ッチング工程へ返送してエッチング液として再使用する
ことが好ましい。しかるに、硫酸銅回収後にエッチング
工程に返送される液分は、返送途中でも引続いて結晶が
析出し、返送配管の結晶による閉塞などによってポンプ
による強制返送が不可能になることがあるため、返送液
を一旦中間槽に受けて加温した後エッチング工程へ返送
することが、実開昭64−7266号公報などで知られ
ている。しかしながら、晶析缶から固液分離機に移送さ
れる硫酸銅スラリに対しては、結晶回収操作が後続する
関係上加温手段を適用することができず、晶析缶の硫酸
銅スラリ出口や移送配管中でも硫酸銅結晶の生長や析出
が生じ、これらの出口、移送配管ならびに弁類等が閉塞
し、硫酸銅スラリの移送が不可能になることも多かっ
た。2. Description of the Related Art In manufacturing an electric circuit board such as a printed wiring board, an etching solution containing hydrogen peroxide and sulfuric acid or a mixed acid as a main component is used to remove a specific amount of copper or copper alloy. The etching process is performed while maintaining the temperature at about 45 to 50 ° C. In this etching solution,
Since copper melts and accumulates during use, in order to recover the excess without decomposing residual hydrogen peroxide,
This etching solution was cooled in a crystallization can and collected as crystals having a water temperature of copper sulfate of 5 (hereinafter simply referred to as copper sulfate). By the way, the copper sulfate crystals to be recovered are preferably in a state with as little liquid content as possible, and the copper sulfate slurry is taken out from the crystallizer and transferred to a solid-liquid separator to recover the copper sulfate crystals with less liquid content. It is preferable that the separated liquid component be returned to the etching step and reused as an etching liquid. However, the liquid that is returned to the etching process after the copper sulfate is recovered will continue to precipitate crystals even during the return process, and it may not be possible to force-return by the pump due to blockage of crystals in the return pipe, etc. It is known, for example, from Japanese Utility Model Application Laid-Open No. 64-7266 that the solution is once received in an intermediate tank, heated and then returned to the etching step. However, a heating means cannot be applied to the copper sulfate slurry transferred from the crystallizer to the solid-liquid separator due to the subsequent crystal recovery operation, and the copper sulfate slurry outlet of the crystallizer or In many cases, copper sulfate crystals were grown and precipitated also in the transfer pipe, and the outlets, transfer pipes, valves, etc. of these were blocked, making it impossible to transfer the copper sulfate slurry.
【0003】[0003]
【発明が解決しようとする課題】本発明は、晶析缶の硫
酸銅スラリ出口や固液分離機への硫酸銅スラリの移送配
管中の硫酸銅結晶による閉塞を、硫酸銅回収系内の液を
利用して効果的に解消し、硫酸銅回収を円滑に行うこと
ができる方法及びその装置を提供することを目的とする
ものである。DISCLOSURE OF THE INVENTION The present invention is directed to a solution in a copper sulfate recovery system for clogging of a copper sulfate slurry outlet of a crystallizer or a copper sulfate slurry transfer pipe to a solid-liquid separator with copper sulfate crystals. It is an object of the present invention to provide a method and an apparatus for effectively recovering copper sulfate and smoothly recovering copper sulfate.
【0004】[0004]
【課題を解決するための手段】本発明は、銅を溶解した
エッチング液を晶析缶に導いて冷却することによって硫
酸銅5水塩の結晶を折出し、該晶析缶の下部出口から硫
酸銅5水塩スラリを取り出し固液分離機に移送して硫酸
銅5水塩の結晶を回収し、その分離液を中間槽にて加温
してエッチング工程に返送する硫酸銅回収方法におい
て、前記中間槽内の加温液により、前記晶析缶と固液分
離機との間の硫酸銅5水塩スラリ移送路の洗浄と前記晶
析缶の硫酸銅5水塩スラリ出口の逆洗を行うことを特徴
とする硫酸銅回収方法であり、また、エッチング液中に
溶解した銅を硫酸銅5水塩の結晶として冷却析出せしめ
る晶析缶の硫酸銅5水塩スラリ出口を移送配管により固
液分離機に連結し、該固液分離機の分離液流出部をエッ
チング槽に連なる加温用中間槽に連結し、さらに該加温
用中間槽内液を前記晶析缶と固液分離機間の移送配管中
に供給するように加温用中間槽と移送配管とを洗浄ポン
プを介して連結したことを特徴とする硫酸銅回収装置で
ある。According to the present invention, crystals of copper sulfate pentahydrate are broken out by introducing an etching solution in which copper is dissolved into a crystallization can and cooling it, and sulfuric acid is discharged from the lower outlet of the crystallization can. In the method for recovering copper sulfate, the copper pentahydrate salt slurry is taken out and transferred to a solid-liquid separator to recover copper sulfate pentahydrate crystals, and the separated liquid is heated in an intermediate tank and returned to the etching step. Washing of the copper sulfate pentahydrate slurry transfer passage between the crystallizer and the solid-liquid separator and backwashing of the copper sulfate pentahydrate slurry outlet of the crystallizer are performed by the warming liquid in the intermediate tank. And a copper sulphate pentahydrate slurry outlet of a crystallizer for cooling and precipitating copper dissolved in an etching solution as crystals of copper sulphate pentahydrate by a transfer pipe. It is connected to the separator, and the separated liquid outflow part of the solid-liquid separator is connected to the etching tank. The intermediate tank for heating is further connected to the intermediate tank for heating via a washing pump so that the liquid in the intermediate tank for heating is supplied into the transfer pipe between the crystallizer and the solid-liquid separator. It is a copper sulfate recovery device characterized by being connected together.
【0005】[0005]
【作用】エッチング工程で使用され、銅が高濃度に溶け
込んだエッチング液を晶析缶に導き、攪拌しながら温度
15℃程度に冷却すると、液中に溶解している銅が均一
粒径の硫酸銅結晶として析出し、晶析缶の底部に沈降す
る。沈降した硫酸銅結晶は、液と共に硫酸銅スラリとし
て晶析缶の出口から導出され、移送配管を経て固液分離
機に移送され、硫酸銅結晶が分離回収される(図2参
照)。一方、固液分離機で分離された分離液は、一旦中
間槽に至って温度30〜40℃に加温されて結晶の析出
をみることなく円滑にエッチング工程に返送されるが、
エッチング工程は温度45〜50℃程度で行われるとこ
ろから、中間槽でエッチング工程に適した温度にまで加
温することもできる。このような硫酸銅回収を行ってい
ると、晶析缶の硫酸銅スラリ出口や固液分離機への移送
配管中が硫酸銅結晶によって次第に閉塞されるから、移
送配管からの硫酸銅スラリの流出量低下等によって洗浄
時期を知り、硫酸銅スラリの移送を停止し、移送配管中
に中間槽内の加温されたエッチング液を供給して管内の
洗浄を行いながらエッチング液を中間槽に戻すように循
環させると、管内は短時間で効果的に洗浄される(図3
参照)。また、晶析缶の硫酸銅スラリ出口については、
中間槽内の加温されたエッチング液を間欠的に逆流させ
る逆洗により洗浄する(図4参照)。これら移送配管の
洗浄及び晶析缶出口の逆洗が終了した時は、再び前記の
硫酸銅回収操作を開始する。When the etching solution used in the etching process, in which copper is dissolved in a high concentration, is introduced into the crystallization can and cooled to about 15 ° C. with stirring, the copper dissolved in the solution is sulfuric acid having a uniform particle size. Precipitates as copper crystals and settles at the bottom of the crystallizer. The precipitated copper sulfate crystals are discharged together with the liquid as copper sulfate slurry from the outlet of the crystallizer, transferred to the solid-liquid separator through the transfer pipe, and the copper sulfate crystals are separated and recovered (see FIG. 2). On the other hand, the separated liquid separated by the solid-liquid separator once reaches the intermediate tank and is heated to a temperature of 30 to 40 ° C. and is smoothly returned to the etching step without observing the precipitation of crystals.
Since the etching process is performed at a temperature of about 45 to 50 ° C., it can be heated to a temperature suitable for the etching process in the intermediate tank. When such copper sulfate recovery is performed, the copper sulfate slurry outlet of the crystallizer and the transfer pipe to the solid-liquid separator are gradually blocked by the copper sulfate crystals, so the copper sulfate slurry flows out from the transfer pipe. Knowing the cleaning time by decreasing the amount, stop the transfer of copper sulfate slurry, and supply the heated etching solution in the intermediate tank into the transfer pipe to return the etching solution to the intermediate tank while cleaning the inside of the tube. When it is circulated, the inside of the pipe is effectively cleaned in a short time (Fig. 3).
reference). Regarding the copper sulfate slurry outlet of the crystallizer,
Cleaning is performed by backwashing in which the heated etching liquid in the intermediate tank is intermittently backflowed (see FIG. 4). When the cleaning of these transfer pipes and the backwashing of the crystallization can outlet are completed, the copper sulfate recovery operation is started again.
【0006】[0006]
【実施例】本発明の一実施例を図1を参照して説明すれ
ば、1は硫酸銅結晶を冷却晶析する晶析缶で、内部には
攪拌機等(図示せず)が設けられ、チラー2から送給さ
れる冷媒によって缶内液が冷却されるようになってい
る。晶析缶1の底部には硫酸銅スラリの出口3が設けら
れ、スラリ抽出弁4によって開閉される。スラリ抽出弁
4は、スラリ抽出ポンプ5及び逆洗弁6等を備えた移送
配管7により遠心分離機8に連結されている。遠心分離
機8の分離液流出部9は中間槽10に連結され、中間槽
10には図示しない電気ヒータなどの加熱器等が配備さ
れて槽内液を加温するようになっており、さらに中間槽
10は洗浄ポンプ11,洗浄弁12等を備えた洗浄配管
13を介して移送配管7に連結されている。また、中間
槽10はリターンポンプ14を介してエッチング槽15
に連なり、エッチング槽15からオーバーフローするエ
ッチング液を受けるオーバーフロー槽16は、ポンプ1
7を備えた配管18によって晶析缶1に連結されてい
る。EXAMPLE An example of the present invention will be described with reference to FIG. 1. Reference numeral 1 is a crystallization can for cooling and crystallizing copper sulfate crystals, and a stirrer or the like (not shown) is provided therein. The liquid in the can is cooled by the refrigerant sent from the chiller 2. An outlet 3 for copper sulfate slurry is provided at the bottom of the crystallization can 1 and is opened and closed by a slurry extraction valve 4. The slurry extraction valve 4 is connected to a centrifugal separator 8 by a transfer pipe 7 equipped with a slurry extraction pump 5, a backwash valve 6, and the like. The separated liquid outflow portion 9 of the centrifuge 8 is connected to the intermediate tank 10, and a heater such as an electric heater (not shown) is provided in the intermediate tank 10 to heat the liquid in the tank. The intermediate tank 10 is connected to the transfer pipe 7 via a cleaning pipe 13 including a cleaning pump 11, a cleaning valve 12 and the like. In addition, the intermediate tank 10 has an etching tank 15 via a return pump 14.
The overflow tank 16 connected to the pump 1 receives the etching solution overflowing from the etching tank 15
It is connected to the crystallization can 1 by a pipe 18 provided with 7.
【0007】しかして、本実施例においては、温度45
〜50℃の条件下にエッチング槽15で使用され、銅が
高濃度に溶け込んだエッチング液は、オーバーフローし
てオーバーフロー槽16に至り、ポンプ17によって配
管18を経て晶析缶1に導かれる。晶析缶1に導かれた
エッチング液は、チラー2から送給されるブラインなど
の冷媒によって温度15℃にまで冷却され、液中に溶解
している銅は硫酸銅結晶となり晶析缶1の底部に沈降す
る。晶析缶1の液位が高レベル(Hレベル)において、
スラリ抽出弁4を開き、遠心分離機8を起動し、スラリ
抽出ポンプ5を稼働して沈降した硫酸銅結晶を、液と共
に硫酸銅スラリとして出口3から移送配管7を経て遠心
分離機8に移送し、液分が分離されて硫酸銅結晶が回収
される。以上の結晶分離経路を図2に斜線部で示す。遠
心分離機8で分離された分離液は、分離液流出部9から
中間槽10に導かれ、温度30〜40℃に加温された後
リターンポンプ14でエッチング槽15へ円滑に返送さ
れ、エッチング液として再使用される。Therefore, in this embodiment, the temperature is 45
The etching solution used in the etching tank 15 under the condition of ˜50 ° C., in which copper is dissolved in a high concentration, overflows to the overflow tank 16 and is guided to the crystallization can 1 by the pump 17 through the pipe 18 and the pipe 18. The etching liquid introduced into the crystallization can 1 is cooled to a temperature of 15 ° C. by a coolant such as brine sent from the chiller 2, and the copper dissolved in the liquid becomes copper sulfate crystals to form a crystal in the crystallization can 1. Settle to the bottom. At the high level (H level) of the crystallizer 1,
The slurry extraction valve 4 is opened, the centrifuge 8 is started, the slurry extraction pump 5 is operated, and the precipitated copper sulfate crystals are transferred together with the liquid as copper sulfate slurry from the outlet 3 to the centrifugal separator 8 via the transfer pipe 7. Then, the liquid is separated and copper sulfate crystals are recovered. The above crystal separation path is shown by the shaded area in FIG. The separated liquid separated by the centrifuge 8 is guided from the separated liquid outflow portion 9 to the intermediate tank 10, heated to a temperature of 30 to 40 ° C., and then smoothly returned to the etching tank 15 by the return pump 14 for etching. It is reused as a liquid.
【0008】以上の硫酸銅回収操作を続けているうち
に、移送配管7からの硫酸銅スラリの流出量が低下す
る。硫酸銅スラリの移送経路中の機器類に異常がない場
合には、晶析缶1の出口3や移送配管7中に硫酸銅結晶
の蓄積が起こったと判断してそれらの洗浄を行う。即
ち、晶析缶1液位が低レベル(Lレベル)において、ス
ラリ抽出弁4を閉じ、スラリ抽出ポンプ5を停止する。
そして、洗浄弁12を開いて洗浄ポンプ11を稼働し、
中間槽10内の30〜40℃のエッチング液を洗浄配管
13から移送配管7中に供給し、移送配管7中の結晶を
溶解しながら遠心分離機8へ流出させ、再び中間槽10
へと循環させて一定時間移送配管7の洗浄を行う。以上
の移送管7の洗浄経路を図3に斜線部で示す。この移送
配管7の洗浄後、逆洗弁6を閉じスラリ抽出弁4を開閉
することによって、中間槽10内のエッチング液は出口
3を間欠的に逆流し、晶析缶1のスラリ出口3の逆洗が
行われる。以上のスラリ出口の洗浄経路を図4に斜線部
で示す。このような洗浄後は、洗浄ポンプ11を停止
し、逆洗弁6を開き、洗浄弁12を閉じて再び硫酸銅回
収を行う。上記の各工程のフローは図5に示すとおりで
ある。While the above copper sulfate recovery operation is continued, the amount of copper sulfate slurry flowing out from the transfer pipe 7 decreases. If there is no abnormality in the equipment in the copper sulfate slurry transfer route, it is determined that copper sulfate crystals have accumulated in the outlet 3 of the crystallizer 1 and the transfer pipe 7, and these are cleaned. That is, when the liquid level of the crystallization can 1 is low (L level), the slurry extraction valve 4 is closed and the slurry extraction pump 5 is stopped.
Then, the washing valve 12 is opened to operate the washing pump 11,
The etching liquid at 30 to 40 ° C. in the intermediate tank 10 is supplied from the cleaning pipe 13 into the transfer pipe 7, and the crystals in the transfer pipe 7 are dissolved and allowed to flow out to the centrifuge 8 again.
And the transfer pipe 7 is washed for a certain period of time. The above-mentioned cleaning path of the transfer pipe 7 is shown by the hatched portion in FIG. After cleaning the transfer pipe 7, the backwash valve 6 is closed and the slurry extraction valve 4 is opened / closed, whereby the etching solution in the intermediate tank 10 intermittently flows back through the outlet 3, and the slurry outlet 3 of the crystallization can 1 is discharged. Backwash is performed. The above-mentioned cleaning route of the slurry outlet is shown by the hatched portion in FIG. After such washing, the washing pump 11 is stopped, the backwash valve 6 is opened, the washing valve 12 is closed, and copper sulfate is recovered again. The flow of each of the above steps is as shown in FIG.
【0009】[0009]
【発明の効果】以上述べたように、本発明によれば、エ
ッチング液から硫酸銅を回収する際に、晶析缶から硫酸
銅スラリを固液分離機に移送して固液分離を行うことに
より、液分を最大限に除去した硫酸銅結晶を回収するこ
とができ、さらにその分離液を加温してエッチング工程
に返送することによって返送を円滑にすると共にエッチ
ング液として再使用しやすくし、さらにこの加温された
分離液の一部を利用して前記晶析缶の硫酸銅スラリの移
送経路の効果的洗浄を行い、硫酸銅回収を円滑に効率良
く行うことができるものである。As described above, according to the present invention, when copper sulfate is recovered from the etching solution, the copper sulfate slurry is transferred from the crystallizer to the solid-liquid separator for solid-liquid separation. The copper sulphate crystals can be collected with maximum removal of the liquid content, and by heating the separated liquid and returning it to the etching process, it can be smoothly returned and easily reused as an etching liquid. Further, a part of the heated separation liquid is utilized to effectively wash the transfer route of the copper sulfate slurry in the crystallizer, whereby the copper sulfate can be recovered smoothly and efficiently.
【図1】本発明の一実施例を示す系統説明図である。FIG. 1 is a system explanatory view showing an embodiment of the present invention.
【図2】本発明の結晶分離経路の説明図である。FIG. 2 is an explanatory diagram of a crystal separation route of the present invention.
【図3】本発明の移送管洗浄経路の説明図である。FIG. 3 is an explanatory diagram of a transfer pipe cleaning path of the present invention.
【図4】本発明のスラリ出口洗浄経路の説明図である。FIG. 4 is an explanatory diagram of a slurry outlet cleaning path of the present invention.
【図5】本発明の実施例における工程のフロー図であ
る。FIG. 5 is a flow chart of a process in an example of the present invention.
1 晶析缶 2 チラー 3 出口 4 スラリ抽出弁 5 スラリ抽出ポンプ 6 逆洗弁 7 移送配管 8 遠心分離機 9 分離液流出部 10 中間槽 11 洗浄ポンプ 12 洗浄弁 13 洗浄配管 14 リターンポンプ 15 エッチング槽 16 オーバーフロー槽 17 ポンプ 18 配管 1 Crystallizer 2 Chiller 3 Outlet 4 Slurry extraction valve 5 Slurry extraction pump 6 Backwash valve 7 Transfer pipe 8 Centrifuge 9 Separation liquid outflow part 10 Intermediate tank 11 Wash pump 12 Wash valve 13 Wash pipe 14 Return pump 15 Etching tank 16 Overflow tank 17 Pump 18 Piping
Claims (2)
いて冷却することによって硫酸銅5水塩の結晶を折出
し、該晶析缶の下部出口から硫酸銅5水塩スラリを取り
出し固液分離機に移送して硫酸銅5水塩の結晶を回収
し、その分離液を中間槽にて加温してエッチング工程に
返送する硫酸銅回収方法において、前記中間槽内の加温
液により、前記晶析缶と固液分離機との間の硫酸銅5水
塩スラリ移送路の洗浄と前記晶析缶の硫酸銅5水塩スラ
リ出口の逆洗を行うことを特徴とする硫酸銅回収方法。1. Crystals of copper sulfate pentahydrate are broken out by introducing an etching solution in which copper is dissolved into a crystallizer and cooling, and a copper sulfate pentahydrate slurry is taken out from the lower outlet of the crystallizer and solidified. In the copper sulfate recovery method in which crystals of copper sulfate pentahydrate are recovered by transferring to a liquid separator, and the separated liquid is heated in an intermediate tank and returned to the etching step, the heating solution in the intermediate tank is used. A copper sulfate pentahydrate slurry transfer passage between the crystallizer and the solid-liquid separator and a backwash of the copper sulfate pentahydrate slurry outlet of the crystallizer. Method.
水塩の結晶として冷却析出せしめる晶折缶の硫酸銅5水
塩スラリ出口を移送配管により固液分離機に連結し、該
固液分離機の分離液流出部をエッチング槽に連なる加温
用中間槽に連結し、さらに該加温用中間槽内液を前記晶
析缶と固液分離機間の移送配管中に供給するように加温
用中間槽と移送配管とを洗浄ポンプを介して連結したこ
とを特徴とする硫酸銅回収装置。2. Copper dissolved in an etching solution is replaced with copper sulfate 5
The copper sulfate 5 hydrate salt slurry outlet of a crystallizing can for cooling and precipitating as water salt crystals is connected to a solid-liquid separator by a transfer pipe, and the separated liquid outflow portion of the solid-liquid separator is connected to an etching tank for heating. The tank is connected to the tank, and the heating intermediate tank and the transfer pipe are connected via a washing pump so that the liquid in the heating intermediate tank is supplied into the transfer pipe between the crystallizer and the solid-liquid separator. A copper sulfate recovery device characterized in that
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10331691A JPH0718023B2 (en) | 1991-04-09 | 1991-04-09 | Copper sulfate recovery method and apparatus |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10331691A JPH0718023B2 (en) | 1991-04-09 | 1991-04-09 | Copper sulfate recovery method and apparatus |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0649665A JPH0649665A (en) | 1994-02-22 |
JPH0718023B2 true JPH0718023B2 (en) | 1995-03-01 |
Family
ID=14350799
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10331691A Expired - Fee Related JPH0718023B2 (en) | 1991-04-09 | 1991-04-09 | Copper sulfate recovery method and apparatus |
Country Status (1)
Country | Link |
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JP (1) | JPH0718023B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20040033146A (en) * | 2002-10-11 | 2004-04-21 | 김영준 | The recovery equipment and method of copper sulfate from spent soft etching solution for recycling etching solution |
US7175819B2 (en) * | 2005-03-04 | 2007-02-13 | Phibro-Tech, Inc. | Regeneration of cupric etchants and recovery of copper sulfate |
-
1991
- 1991-04-09 JP JP10331691A patent/JPH0718023B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH0649665A (en) | 1994-02-22 |
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