JP2000167569A - Method and equipment for treating copper-containing acidic waste water - Google Patents
Method and equipment for treating copper-containing acidic waste waterInfo
- Publication number
- JP2000167569A JP2000167569A JP10347513A JP34751398A JP2000167569A JP 2000167569 A JP2000167569 A JP 2000167569A JP 10347513 A JP10347513 A JP 10347513A JP 34751398 A JP34751398 A JP 34751398A JP 2000167569 A JP2000167569 A JP 2000167569A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- containing acidic
- acidic wastewater
- reaction
- wastewater
- 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.)
- Pending
Links
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅めっき排水、銅
の電解製錬工程で発生する排水など、銅イオンを含む銅
含有酸性排水の処理方法および処理設備に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and a facility for treating copper-containing acidic wastewater containing copper ions, such as copper plating wastewater and wastewater generated in an electrolytic smelting process of copper.
【０００２】[0002]
【従来の技術】従来、銅めっき排水、銅の電解製錬工程
で発生する排水などの銅イオンを含む銅含有酸性排水
（以下銅含有酸性排水とも記す）は、石灰で中和し石膏
を生成し、石膏と共に水酸化銅を共沈させることによっ
て処理していた。しかし、上記した方法の場合、廃棄す
るスラッジの量が多く、また、排水に含まれる銅などの
有価金属を簡易かつ経済性に優れた方法で回収すること
は不可能であり、廃棄するスラッジは有害廃棄物とな
り、その処理費用は年々増加している。2. Description of the Related Art Conventionally, copper-containing acidic wastewater (hereinafter also referred to as copper-containing acidic wastewater) containing copper ions, such as copper plating wastewater and wastewater generated in the electrolytic smelting process of copper, is neutralized with lime to produce gypsum. And by co-precipitating copper hydroxide with gypsum. However, in the case of the above-mentioned method, the amount of sludge to be discarded is large, and it is impossible to recover valuable metals such as copper contained in the wastewater by a simple and economical method. It becomes hazardous waste, and its disposal cost is increasing year by year.
【０００３】さらに、銅含有酸性排水に砒素などが含ま
れる場合、上記した石灰処理後に多量の塩化第二鉄を加
え、鉄との共沈によって砒素などを除去する必要があ
り、さらに廃棄物が増加すると共に、その処理費用は益
々増加する。Further, when arsenic or the like is contained in the copper-containing acidic wastewater, it is necessary to add a large amount of ferric chloride after the above-mentioned lime treatment and remove arsenic and the like by coprecipitation with iron. As it increases, its processing costs increase.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、前記した従
来技術の問題点を解決し、硫酸銅含有酸性排水などの銅
含有酸性排水中の銅を効果的に除去すると共に、有害な
廃棄物を生じることの無い銅含有酸性排水の処理方法お
よび処理設備を提供することを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, effectively removes copper in copper-containing acidic wastewater such as copper sulfate-containing acidic wastewater, and removes harmful waste. It is an object of the present invention to provide a method and a facility for treating a copper-containing acidic wastewater which does not produce any wastewater.
【０００５】[0005]
【課題を解決するための手段】第１の発明は、銅含有酸
性排水にアルカリ化合物を添加しpH≧９、液温≧70℃の
条件下で反応せしめ、得られた反応液を固液分離するこ
とを特徴とする銅含有酸性排水の処理方法である。前記
した第１の発明は、Cuに加えて、さらにAs、Cr、Se、Z
n、PbおよびＰから選ばれる１種または２種以上を含有
する銅含有酸性排水の処理方法として好適に用いられ
る。According to a first aspect of the present invention, an alkaline compound is added to a copper-containing acidic wastewater and reacted under conditions of pH ≧ 9 and liquid temperature ≧ 70 ° C., and the obtained reaction solution is subjected to solid-liquid separation. It is a method of treating copper-containing acidic wastewater. The first invention described above further includes, in addition to Cu, As, Cr, Se, Z
It is suitably used as a method for treating copper-containing acidic wastewater containing one or more selected from n, Pb and P.
【０００６】また、前記した第１の発明においては、前
記銅含有酸性排水を、予め加温した後、アルカリ化合物
を添加し、得られた液を反応槽に送給し、pH≧９、液温
≧70℃の条件下で反応せしめ、得られた反応液を固液分
離することが好ましい。また、前記した第１の発明にお
いては、反応槽内の液温を液温≧70℃に保持するよう
に、加温しながら、銅含有酸性排水およびアルカリ化合
物を反応槽に供給し、pH≧９、液温≧70℃の条件下で反
応せしめ、得られた反応液を固液分離することがより好
ましい。[0006] In the first aspect of the present invention, the copper-containing acidic wastewater is preliminarily heated, an alkali compound is added, and the resulting liquid is fed to a reaction tank, and the pH of the liquid is adjusted to pH ≧ 9. The reaction is preferably performed under the condition of a temperature ≧ 70 ° C., and the obtained reaction liquid is preferably subjected to solid-liquid separation. In the first aspect, the copper-containing acidic wastewater and the alkali compound are supplied to the reaction tank while heating so that the liquid temperature in the reaction tank is maintained at a liquid temperature ≧ 70 ° C. 9. It is more preferable that the reaction is performed under the condition of a liquid temperature of ≧ 70 ° C., and the obtained reaction liquid is subjected to solid-liquid separation.
【０００７】また、前記した第１の発明においては、前
記銅含有酸性排水に、液温＜70℃の条件下でアルカリ化
合物を添加した後、反応槽に送給し、pH≧９、液温≧70
℃の条件下で反応せしめ、得られた反応液を固液分離す
ることがさらに好ましい。また、前記した第１の発明
は、硫酸銅含有酸性排水である銅含有酸性排水の処理方
法として好適に用いられる。In the first invention, an alkali compound is added to the copper-containing acidic wastewater under the condition of a liquid temperature of <70 ° C., and then fed to a reaction tank, where pH ≧ 9 and a liquid temperature of ≧ 70
It is further preferable that the reaction is carried out under the condition of ° C, and the obtained reaction liquid is subjected to solid-liquid separation. Further, the first invention described above is suitably used as a method for treating copper-containing acidic wastewater that is copper-sulfate-containing acidic wastewater.
【０００８】さらに、前記した第１の発明においては、
前記したアルカリ化合物が苛性ソーダであることが好ま
しい。第２の発明は、予めアルカリ化合物を添加した銅
含有酸性排水を反応せしめるための反応槽１と、該反応
槽１内の反応液の加温手段２と、前記反応槽１で反応後
の反応液を固液分離するための固液分離装置３と、前記
反応槽１へ銅含有酸性排水を供給するための酸性排水供
給配管系統４と、前記反応槽１と前記固液分離装置３と
の間に設けられた反応液送給配管系統５と、前記酸性排
水供給配管系統４に設けられたアルカリ化合物添加手段
７を有することを特徴とする銅含有酸性排水の処理設備
である。Further, in the first aspect,
Preferably, the alkali compound is caustic soda. The second invention comprises a reaction tank 1 for reacting a copper-containing acidic wastewater to which an alkali compound has been added in advance, a heating means 2 for a reaction solution in the reaction tank 1, and a reaction after the reaction in the reaction tank 1. A solid-liquid separation device 3 for separating the liquid into a solid-liquid, an acidic wastewater supply piping system 4 for supplying the copper-containing acidic wastewater to the reaction tank 1, and a solid-liquid separation device 3 for the reaction tank 1. This is a copper-containing acidic wastewater treatment facility comprising: a reaction liquid supply piping system 5 provided therebetween; and an alkali compound addition means 7 provided in the acidic wastewater supply piping system 4.
【０００９】また、前記した第２の発明のより好適な態
様の処理設備は、予めアルカリ化合物を添加した銅含有
酸性排水を反応せしめるための反応槽１と、該反応槽１
内の反応液の加温手段２と、前記反応槽１で反応後の反
応液を固液分離するための固液分離装置３と、前記反応
槽１へ銅含有酸性排水を供給するための酸性排水供給配
管系統４と、前記反応槽１と前記固液分離装置３との間
に設けられた反応液送給配管系統５と、該反応液送給配
管系統５および前記酸性排水供給配管系統４の両者と接
続され、該反応液送給配管系統５の反応液と前記酸性排
水供給配管系統４の酸性排水とを間接的に熱交換し、反
応液の熱回収を行うと共に前記酸性排水を予め予備加温
するための間接熱交換器６と、前記酸性排水供給配管系
統４に設けられたアルカリ化合物添加手段７を有するこ
とを特徴とする銅含有酸性排水の処理設備である。Further, the processing equipment according to a more preferred embodiment of the second aspect of the present invention comprises: a reaction tank 1 for reacting a copper-containing acidic wastewater to which an alkali compound has been added in advance;
Means for heating the reaction solution in the reactor, a solid-liquid separator 3 for solid-liquid separation of the reaction solution after the reaction in the reaction tank 1, and an acid for supplying the copper-containing acidic wastewater to the reaction tank 1. A drainage supply piping system 4, a reaction solution supply piping system 5 provided between the reaction tank 1 and the solid-liquid separation device 3, a reaction solution supply piping system 5, and the acidic wastewater supply piping system 4. The indirect heat exchange between the reaction liquid of the reaction liquid supply piping system 5 and the acidic waste water of the acidic waste water supply piping system 4 is performed, and heat recovery of the reaction liquid is performed and the acid waste water is previously discharged. A treatment equipment for copper-containing acidic wastewater, comprising an indirect heat exchanger 6 for preheating and an alkali compound adding means 7 provided in the acidic wastewater supply piping system 4.
【００１０】前記した第２の発明のより好適な態様の処
理設備においては、前記アルカリ化合物添加手段７が、
前記酸性排水供給配管系統４と前記熱交換器６との接続
箇所の上流側で、酸性排水が予備加温前である酸性排水
供給配管系統4aに設けられることが好ましい。また、前
記した第２の発明は、Cuに加えて、さらにAs、Cr、Se、
Zn、PbおよびＰから選ばれる１種または２種以上を含有
する銅含有酸性排水の処理設備として好適に用いられ
る。In the processing equipment according to a more preferred embodiment of the second invention, the alkali compound adding means 7 comprises:
It is preferable that the acidic wastewater is provided in the acidic wastewater supply piping system 4a before the preheating, on the upstream side of the connection point between the acidic wastewater supply piping system 4 and the heat exchanger 6. Further, the second invention described above further includes, in addition to Cu, As, Cr, Se,
It is suitably used as a treatment facility for copper-containing acidic wastewater containing one or more selected from Zn, Pb and P.
【００１１】また、前記した第２の発明は、前記銅含有
酸性排水が、硫酸銅含有酸性排水である銅含有酸性排水
の処理設備として好適に用いられる。さらに、前記した
第２の発明においては、前記アルカリ化合物が苛性ソー
ダであることが好ましい。Further, the above-mentioned second invention is suitably used as a treatment facility for the copper-containing acidic wastewater, wherein the copper-containing acidic wastewater is a copper sulfate-containing acidic wastewater. Further, in the second invention, the alkali compound is preferably caustic soda.
【００１２】[0012]
【発明の実施の形態】以下、本発明をさらに詳細に説明
する。本発明者らは、前記した課題を解決するために鋭
意検討した結果、下記知見(1) 〜(8) を見出し、本発明
に至った。 (1)：硫酸銅含有酸性排水などの銅含有酸性排水にアル
カリ化合物を添加しpH≧９、液温≧70℃の条件下で反応
せしめることによって、排水中の銅イオンを迅速に酸化
銅とすることができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found the following findings (1) to (8), and have accomplished the present invention. (1): An alkaline compound is added to a copper-containing acidic wastewater such as a copper sulfate-containing acidic wastewater and reacted under conditions of pH ≧ 9 and liquid temperature ≧ 70 ° C., so that copper ions in the wastewater can be quickly converted to copper oxide. can do.
【００１３】(2)：上記 (1)で生成した酸化銅を含有す
るスラリーは、濾過性に優れ、容易に脱水処理ができ
る。 (3)：上記 (1)および (2)によって、銅含有酸性排水中
の銅イオンを、除去率に優れると共に工業的に簡易な方
法で除去することができる。 (4)：酸化銅を含有するスラリーの脱水処理で得られた
銅スラッジは、銅を高濃度で含有しており、容易に有価
金属である銅を回収できる。(2): The slurry containing copper oxide produced in the above (1) has excellent filterability and can be easily dehydrated. (3): By the above (1) and (2), copper ions in the copper-containing acidic wastewater can be removed by an industrially simple method while having an excellent removal rate. (4): The copper sludge obtained by the dehydration treatment of the slurry containing copper oxide contains copper at a high concentration, so that copper, which is a valuable metal, can be easily recovered.
【００１４】(5)：銅イオンと共に砒素を含有する銅含
有酸性排水を本発明の方法、設備で処理することによっ
て、砒素は酸化銅と共沈し、排水基準値未満とすること
ができる。また、この場合、塩化鉄などの他の薬剤を用
いる必要が無く、処理方法、処理設備も簡易であり、経
済性に優れた方法、設備で砒素を含有する銅含有酸性排
水を処理することができる。(5) Arsenic can be coprecipitated with copper oxide by treating the copper-containing acidic wastewater containing arsenic together with copper ions with the method and equipment according to the present invention, and the arsenic can be reduced below the wastewater standard value. Further, in this case, there is no need to use other chemicals such as iron chloride, the treatment method and treatment equipment are simple, and it is possible to treat the copper-containing acidic wastewater containing arsenic with an economical method and equipment. it can.
【００１５】(6)：銅含有酸性排水へのアルカリ化合物
の添加、排水の加温の順序は制限されないが、銅含有酸
性排水へアルカリ化合物を添加した後、液温≧70℃に加
温し、pH≧９の条件下で反応せしめることによって排水
中の砒素の除去率がさらに向上する。 (7)：さらに、本発明の方法、装置によれば、銅イオ
ン、砒素以外に、銅含有酸性排水中のクロム(Cr)、セレ
ン(Se)、亜鉛(Zn)、鉛(Pb)、燐(P) も高除去率で除去す
ることができる。(6): The order of adding the alkali compound to the copper-containing acidic wastewater and heating the wastewater is not limited, but after adding the alkali compound to the copper-containing acidic wastewater, the solution is heated to a temperature of ≧ 70 ° C. By performing the reaction under the condition of pH ≧ 9, the removal rate of arsenic in the wastewater is further improved. (7): Further, according to the method and the apparatus of the present invention, in addition to copper ions and arsenic, chromium (Cr), selenium (Se), zinc (Zn), lead (Pb), phosphorus (P) can also be removed at a high removal rate.
【００１６】(8)：添加するアルカリ化合物として苛性
ソーダを用いることによって、従来硫酸銅含有酸性排水
の処理時に大量に発生していた石膏スラッジなどの廃棄
物が全く発生しない。本発明の銅含有酸性排水の処理方
法、処理設備は、銅の電解製錬工程で発生する排水、銅
めっき排水、エッチング廃液など、硫酸銅含有酸性排
水、ピロリン酸化合物−銅含有酸性排水、塩化銅含有酸
性排水などの処理方法、処理設備として好適に用いられ
る。(8) By using caustic soda as an alkali compound to be added, waste such as gypsum sludge which has conventionally been generated in large amounts during the treatment of copper sulfate-containing acidic wastewater is not generated at all. The treatment method and treatment equipment for the copper-containing acidic wastewater of the present invention include a copper sulfate-containing acidic wastewater, a pyrophosphate compound-copper-containing acidic wastewater, a wastewater generated in a copper electrolytic smelting process, a copper plating wastewater, an etching wastewater, and the like. It is suitably used as a treatment method and treatment equipment for copper-containing acidic wastewater.
【００１７】本発明によれば、上記した銅含有酸性排水
中の銅含有量を排水基準値である１mg-Cu/l 未満となる
ように処理できる。また、本発明の銅含有酸性排水の処
理方法、処理設備は、Cuに加えて、さらにAs、Cr、Se、
Zn、PbおよびＰから選ばれる１種または２種以上を含有
する銅含有酸性排水中のこれらの成分を排水基準値未満
（As＜0.1mg/l 、Cr＜２mg/l、Se＜0.1mg/l 、Zn＜５mg
/l、Pb＜0.1mg/l 、Ｐ＜８mg/l）とすることが可能であ
る。According to the present invention, it is possible to treat the above-mentioned copper-containing acidic wastewater so that the copper content is less than the wastewater standard value of 1 mg-Cu / l. In addition, the method for treating copper-containing acidic wastewater of the present invention, the treatment equipment, in addition to Cu, further As, Cr, Se,
These components in the copper-containing acidic wastewater containing one or more selected from Zn, Pb and P are less than the wastewater standard values (As <0.1 mg / l, Cr <2 mg / l, Se <0.1 mg / l). l, Zn <5mg
/ l, Pb <0.1 mg / l, P <8 mg / l).
【００１８】次に、図１に、本発明の銅含有酸性排水の
処理方法および処理設備の一例を、工程図によって示
す。図１において、１は銅含有酸性排水を反応せしめる
ための反応槽、２は反応槽１内の反応液の加温手段、３
は反応槽１で反応後の反応液を固液分離するための固液
分離装置、４は反応槽１へ銅含有酸性排水を供給するた
めの酸性排水供給配管系統、4aは酸性排水供給配管系統
４と熱交換器６との接続箇所の上流側で、酸性排水が予
備加温前である酸性排水供給配管系統、4bは酸性排水が
予備加温後である酸性排水供給配管系統、５は反応槽１
と固液分離装置３との間に設けられた反応液送給配管系
統、６は反応液送給配管系統５および酸性排水供給配管
系統４の両者と接続された熱交換器（：間接熱交換
器）、７は酸性排水供給配管系統４(4a)に設けられたア
ルカリ化合物添加手段を示す。Next, FIG. 1 is a flow chart showing an example of the method and equipment for treating copper-containing acidic waste water of the present invention. In FIG. 1, reference numeral 1 denotes a reaction tank for reacting copper-containing acidic wastewater, 2 denotes a heating means for the reaction solution in the reaction tank 1,
Is a solid-liquid separator for solid-liquid separation of the reaction solution after the reaction in the reaction tank 1, 4 is an acidic wastewater supply piping system for supplying the copper-containing acidic wastewater to the reaction tank 1, and 4a is an acidic wastewater supply piping system On the upstream side of the connection point between the heat exchanger 4 and the heat exchanger 6, an acidic wastewater supply piping system in which the acidic wastewater has not been preheated, 4b an acidic wastewater supply piping system in which the acid wastewater has been preheated, and 5 a reaction Tank 1
A reaction liquid supply piping system provided between the reaction liquid supply system and the solid-liquid separation device 3, and a heat exchanger (6: indirect heat exchange) connected to both the reaction liquid supply piping system 5 and the acidic wastewater supply piping system 4. And 7 indicate alkali compound adding means provided in the acidic drainage supply piping system 4 (4a).
【００１９】なお、図１に示されるように、熱交換器６
は、反応液加熱における省エネルギーのために配設する
もので、反応液送給配管系統５の反応液と酸性排水供給
配管系統４の酸性排水とを間接的に熱交換し、反応液の
熱回収を行うと共に酸性排水を予め予備加温する熱交換
器である。図１に示す本発明の銅含有酸性排水の処理方
法および処理設備においては、処理対象である銅含有酸
性排水（以下酸性排水とも記す）の熱交換器による予備
加温の前に、酸性排水に苛性ソーダなどのアルカリ化合
物を添加する。As shown in FIG. 1, the heat exchanger 6
Is provided for energy saving in heating the reaction liquid, and indirectly exchanges heat between the reaction liquid in the reaction liquid supply piping system 5 and the acidic wastewater in the acidic wastewater supply piping system 4 to recover heat of the reaction liquid. And a heat exchanger for preheating the acidic wastewater in advance. In the method and equipment for treating copper-containing acidic wastewater of the present invention shown in FIG. 1, the copper-containing acidic wastewater (hereinafter also referred to as “acidic wastewater”) to be treated is subjected to acid wastewater before preliminary heating by a heat exchanger. Add an alkaline compound such as caustic soda.
【００２０】これは、後記の実施例で例示されるよう
に、酸性排水が低温の状態でアルカリ化合物を添加する
ことによって、砒素を含有する酸性排水においてCuの除
去率のみならず、Asの除去率が向上するためである。予
めアルカリ化合物を添加した銅含有酸性排水は、熱交換
器６において、加温された反応後の反応液との間接熱交
換によって予備加温され反応槽１に供給される。This is because, as exemplified in the examples described below, not only the removal rate of Cu but also the removal of As in the acid wastewater containing arsenic can be obtained by adding an alkali compound while the acid wastewater is at a low temperature. This is because the rate is improved. The copper-containing acidic wastewater to which an alkali compound has been added in advance is preheated in the heat exchanger 6 by indirect heat exchange with the heated reaction solution after the reaction, and is supplied to the reaction tank 1.
【００２１】反応槽１に供給された酸性排水は、酸性排
水（反応液）中への蒸気吹き込み装置などの反応液の加
温手段２によって、液温を70℃以上、より好ましくは液
温を80℃以上、沸点温度未満に保持する。また、前記し
たアルカリ化合物の添加によって、反応液のpHを９以上
に保持する。The acidic wastewater supplied to the reaction tank 1 is heated to a temperature of 70 ° C. or higher, more preferably, by a reaction liquid heating means 2 such as a steam blowing device into the acidic wastewater (reaction liquid). Keep at 80 ° C or higher and lower than the boiling point temperature. Further, the pH of the reaction solution is maintained at 9 or more by the addition of the above-mentioned alkali compound.
【００２２】反応液のpHが９未満、液温が70℃未満の場
合は、酸化銅の生成反応が進まず、銅イオンの一部もし
くは全てが水酸化銅の状態となり、濾過性に優れた酸化
銅を迅速に得ることができない。なお、本発明において
用いられる反応液の加温手段２としては、上記した蒸気
吹き込み装置に限定されず、反応槽１の槽壁もしくは反
応槽１槽内に設けた加熱装置、酸性排水供給配管系統４
に設けた加熱装置などを用いることが可能であり、その
方式、装置は限定されるものではない。When the pH of the reaction solution is less than 9 and the solution temperature is less than 70 ° C., the formation reaction of copper oxide does not proceed, and some or all of the copper ions are in a state of copper hydroxide, and the filterability is excellent. Copper oxide cannot be obtained quickly. The heating means 2 for the reaction liquid used in the present invention is not limited to the above-described steam blowing device, but may be a heating device provided in the tank wall of the reaction tank 1 or the inside of the reaction tank 1, and an acidic drainage supply piping system. 4
It is possible to use a heating device or the like provided in the above, and the method and device are not limited.
【００２３】また、本発明において用いられるアルカリ
化合物としては、苛性ソーダ、炭酸ソーダ、水酸化マグ
ネシウムおよび石灰から選ばれる１種または２種以上が
好ましく例示されるが、酸性排水をpHが９以上となるよ
うに調整可能で、酸性排水中の酸と反応して多量のスラ
ッジを生成することのないアルカリ化合物であれば、そ
の成分は特に限定されるものではない。The alkali compound used in the present invention is preferably one or more selected from the group consisting of caustic soda, sodium carbonate, magnesium hydroxide and lime. The component is not particularly limited as long as it is an alkali compound which can be adjusted as described above and does not react with the acid in the acidic wastewater to generate a large amount of sludge.
【００２４】ただし、アンモニア水は、水酸化銅と反応
し、銅アンモニアイオンを生じ、銅が水に溶解するため
不適である。また、前記した従来技術に示すように、硫
酸銅含有酸性排水にアルカリ化合物として石灰を添加す
る場合、石膏が生成し、廃棄するスラッジが多くなる。
このため、本発明においては、アルカリ化合物として、
より好ましくは苛性ソーダ、炭酸ソーダおよび水酸化マ
グネシウムから選ばれる１種または２種以上を用いるこ
とが好ましく、さらに好ましくは苛性ソーダおよび／ま
たは炭酸ソーダを用いることが好ましい。However, ammonia water is not suitable because it reacts with copper hydroxide to produce copper ammonia ions, and copper dissolves in water. Further, as shown in the above-mentioned prior art, when lime is added as an alkaline compound to copper sulfate-containing acidic wastewater, gypsum is generated and waste sludge is increased.
Therefore, in the present invention, as the alkali compound,
More preferably, one or more selected from caustic soda, sodium carbonate, and magnesium hydroxide are used, and more preferably, caustic soda and / or sodium carbonate are used.
【００２５】上記したアルカリ化合物は、水溶液とした
後、酸性排水もしくは反応槽１内の反応液に添加する
か、固体状、液体状、ガス状のアルカリ化合物を、その
ままの状態で酸性排水もしくは反応槽１内の反応液に添
加することができる。反応槽１における反応で生成した
酸化銅を含有する反応液は、固液分離装置３に送給さ
れ、固液分離によって得られた処理水は処理水槽に貯液
する。The above-mentioned alkali compound is converted into an aqueous solution and then added to an acidic wastewater or a reaction solution in the reaction tank 1, or a solid, liquid or gaseous alkali compound is directly added to an acidic wastewater or a reaction solution. It can be added to the reaction solution in the tank 1. The reaction liquid containing copper oxide generated by the reaction in the reaction tank 1 is sent to the solid-liquid separation device 3, and the treated water obtained by the solid-liquid separation is stored in the treatment water tank.
【００２６】貯液された処理水は、pH測定、成分分析を
行い、排水基準を満足しない場合は、pH調整などの処理
を行った後、放流する。一方、上記した固液分離によっ
て得られた残渣である酸化銅含有スラリーは、スラリー
タンクを経由して脱水機に送給される。本発明において
得られる酸化銅含有スラリーは、濾過性に優れ、容易に
脱水処理ができる。The stored treated water is subjected to pH measurement and component analysis, and if not satisfying the drainage standard, is subjected to treatment such as pH adjustment and then discharged. On the other hand, the copper oxide-containing slurry, which is a residue obtained by the above-described solid-liquid separation, is sent to a dehydrator via a slurry tank. The copper oxide-containing slurry obtained in the present invention has excellent filterability and can be easily dewatered.
【００２７】脱水によって得られた酸化銅ケーキは、銅
の含有量が多く、有価金属回収設備において容易に銅を
有価金属として回収することができる。また、脱水機か
らの処理液は、再度、固液分離装置３に送液され、処理
される。本発明において用いられる上記した固液分離装
置の方式としては、シックナ、遠心分離機などの重力沈
降法、比重分離法が好適に用いられるが、その方式は特
に制限されるものではない。The copper oxide cake obtained by dehydration has a high copper content, and copper can be easily recovered as a valuable metal in a valuable metal recovery facility. Further, the processing liquid from the dehydrator is sent to the solid-liquid separation device 3 again to be processed. As a method of the above-mentioned solid-liquid separator used in the present invention, a gravity sedimentation method such as a thickener and a centrifugal separator, and a specific gravity separation method are preferably used, but the method is not particularly limited.
【００２８】また、上記した脱水機としては、ベルトフ
ィルタ、フィルタプレス、遠心脱水機、真空脱水機など
が例示されるが、その方式は特に制限されるものではな
い。表１に、前記した図１に示す本発明の処理方法およ
び処理設備を用いて銅メッキ工程で発生する排水を処理
した場合の物質収支、処理設備内の各箇所における排
水、反応液、処理水などの分析結果を示す。Examples of the dehydrator include a belt filter, a filter press, a centrifugal dehydrator, and a vacuum dehydrator, but the type of the dehydrator is not particularly limited. Table 1 shows the material balance when the wastewater generated in the copper plating process was treated using the treatment method and treatment equipment of the present invention shown in FIG. 1 described above, the wastewater at each point in the treatment equipment, the reaction solution, and the treated water. This shows the analysis results.
【００２９】表１に示されるとおり、本発明の処理方法
および処理設備によれば、石膏スラッジなどの多量の廃
棄物の生成を伴うことなく、酸性排水中のCuイオンを高
除去率で除去できるばかりでなく、酸性排水中のAsを排
水基準値0.1mg/l 以下とすることが可能となった。As shown in Table 1, according to the treatment method and treatment equipment of the present invention, Cu ions in acidic wastewater can be removed at a high removal rate without generating a large amount of waste such as gypsum sludge. Not only that, it became possible to reduce As in the acidic wastewater to a wastewater standard value of 0.1 mg / l or less.
【００３０】[0030]
【表１】 [Table 1]
【００３１】次に、本発明の銅含有酸性排水の処理方
法、処理設備におけるアルカリ化合物の添加、酸性排水
の加温に関する好適な操作条件、装置配列について述べ
る。本発明者らは、本発明の銅含有酸性排水の処理方
法、処理設備において、アルカリ化合物の添加、酸性排
水の加温における操作手順によって、Cuイオンなどの金
属イオンの除去率、Ｐの除去率が左右されることを見出
した。Next, the method for treating the copper-containing acidic wastewater of the present invention, the addition of an alkali compound in the treatment equipment, and the suitable operating conditions and the arrangement of the equipment for heating the acidic wastewater will be described. The present inventors, in the treatment method and treatment equipment for the copper-containing acidic wastewater of the present invention, the removal rate of metal ions such as Cu ions, P removal rate by the operation procedure in addition of an alkali compound and heating of the acidic wastewater. Was determined to be affected.
【００３２】図１〜図３に示すように、本発明において
は、アルカリ化合物の添加、酸性排水の加温における操
作手順として下記の方法を用いることができる。 (1) ：銅含有酸性排水に例えば常温近傍の低温条件下で
苛性ソーダなどのアルカリ化合物を添加した後、反応槽
に送給し、pH≧９、液温≧70℃の条件下で反応を行う
（図１）〔以下処理方法(1) と記す〕。As shown in FIGS. 1 to 3, in the present invention, the following method can be used as an operation procedure for adding an alkali compound and heating an acidic wastewater. (1): An alkaline compound such as caustic soda is added to a copper-containing acidic wastewater under a low temperature condition, for example, near normal temperature, and then fed to a reaction tank, where the reaction is carried out under conditions of pH ≧ 9 and liquid temperature ≧ 70 ° C. (FIG. 1) [Hereinafter referred to as processing method (1)].
【００３３】(2) ：反応槽内の液温を液温≧70℃に保持
するように、蒸気にて加温しながら、銅含有酸性排水お
よびアルカリ化合物を反応槽に供給し、pH≧９、液温≧
70℃の条件下で反応を行う（図２）〔以下処理方法(2)
と記す〕。 (3) ：銅含有酸性排水を、予め、例えば液温が70℃とな
るように加温した後、アルカリ化合物を添加し、得られ
た液を反応槽に送給し、pH≧９、液温≧70℃の条件下で
反応を行う（図３）〔以下処理方法(3) と記す〕。(2): A copper-containing acidic wastewater and an alkali compound are supplied to the reaction tank while heating with steam so that the liquid temperature in the reaction tank is maintained at a liquid temperature ≧ 70 ° C., and the pH is ≧ 9. , Liquid temperature ≧
Perform the reaction at 70 ° C (Fig. 2) [Processing method (2)
It is written.] (3): The copper-containing acidic wastewater is heated in advance so that the temperature of the solution becomes, for example, 70 ° C., and then an alkali compound is added. The reaction is carried out at a temperature of ≧ 70 ° C. (FIG. 3) [hereinafter referred to as treatment method (3)].
【００３４】本発明によれば、上記した処理方法(1) 〜
処理方法(3) のいずれの方法によっても、酸性排水中の
Cuイオンを高除去率で除去することが可能であるが、後
記の実施例で示されるように、Cuイオン、Asなどの金属
のイオン、Ｐの除去率の面から、上記した処理方法(1)
、処理方法(2) が好ましく、さらには、処理方法(1)が
最適の処理方法である。According to the present invention, the above-mentioned processing methods (1) to (1)
In any of the treatment methods (3), acid wastewater
Although it is possible to remove Cu ions at a high removal rate, as shown in Examples described later, Cu ions, ions of metals such as As, and P removal rates are used in view of the above-described treatment method (1). )
The processing method (2) is preferable, and the processing method (1) is the most suitable processing method.
【００３５】最適の処理方法である処理方法(1) におい
ては、銅含有酸性排水に、70℃未満、より好ましくは50
℃以下の液温の条件下で、アルカリ化合物を添加した
後、反応槽に送給し、pH≧９、液温≧70℃の条件下で反
応を行う。また、本発明の銅含有酸性排水の処理設備に
おける最も好適な装置配列は、図１に示すように、酸性
排水供給配管系統４に、アルカリ化合物添加手段を設け
た装置配列であり、さらに好ましい装置配列は、熱交換
器６による酸性排水の予備加温前である酸性排水供給配
管系統4aに、アルカリ化合物添加手段７を設けた装置配
列である。In the treatment method (1), which is the most suitable treatment method, the copper-containing acidic wastewater is treated at a temperature of less than 70 ° C.,
After the addition of the alkali compound under the condition of the liquid temperature of not more than ° C, the mixture is fed to the reaction tank, and the reaction is performed under the condition of pH ≧ 9 and the liquid temperature ≧ 70 ° C. In addition, as shown in FIG. 1, the most preferable arrangement of the apparatus for treating copper-containing acidic wastewater of the present invention is an arrangement of an acidic wastewater supply piping system 4 provided with an alkali compound adding means. The arrangement is an arrangement in which an alkali compound addition means 7 is provided in an acidic drainage supply pipe system 4a before preheating the acidic wastewater by the heat exchanger 6.
【００３６】[0036]
【実施例】以下、本発明を実施例に基づいてさらに具体
的に説明する。前記した図１〜図３に示す本発明の銅含
有酸性排水の処理方法、処理設備を用いて、銅めっき排
水（：ピロリン酸化合物−銅含有酸性排水）および銅の
電解製錬工程で発生する排水（：硫酸銅含有酸性排水）
の処理を行った。EXAMPLES The present invention will be described below more specifically based on examples. The copper plating wastewater (: pyrophosphate compound-copper-containing acidic wastewater) and copper electrolytic smelting process are generated using the copper-containing acidic wastewater treatment method and treatment equipment of the present invention shown in FIGS. 1 to 3 described above. Wastewater (: Copper sulfate containing acidic wastewater)
Was performed.
【００３７】本処理実験の処理条件、処理前後の排水の
性状を表２に示す。なお、表中の処理方法(1) 〜処理方
法(3) は、前記したように、下記処理方法を示す。ま
た、排水中のCu含有量は、排水中のCu2+イオン、Cu+ イ
オンおよびピロリン酸銅である銅の合計量（金属銅換
算）である。Table 2 shows the treatment conditions of this treatment experiment and the properties of the wastewater before and after the treatment. The processing methods (1) to (3) in the table indicate the following processing methods as described above. The Cu content in the wastewater is the total amount (in terms of metallic copper) of Cu2 + ions, Cu + ions, and copper that is copper pyrophosphate in the wastewater.
【００３８】処理方法(1) ：〔図１〕 表２に示す原排水液温の銅含有酸性排水に苛性ソーダ水
溶液を添加した後、反応槽に送給し、表２に示す反応槽
液温、反応槽液pHの条件下で反応を行った。 処理方法(2) ：〔図２〕 反応槽内の液温を表２に示す液温に保持するように、蒸
気にて加温しながら、銅含有酸性排水および苛性ソーダ
水溶液を、反応槽に供給し、表２に示す反応槽液温、反
応槽液pHの条件下で反応を行った。Treatment method (1): [FIG. 1] An aqueous caustic soda solution was added to the copper-containing acidic wastewater at the raw wastewater temperature shown in Table 2 and then fed to the reaction tank. The reaction was performed under the condition of the pH of the reaction tank liquid. Treatment method (2): [Fig. 2] Copper-containing acidic wastewater and caustic soda aqueous solution were supplied to the reaction tank while heating with steam so as to maintain the liquid temperature in the reaction tank at the liquid temperature shown in Table 2. Then, the reaction was carried out under the conditions of the reaction tank liquid temperature and the reaction tank liquid pH shown in Table 2.
【００３９】処理方法(3) ：〔図３〕 銅含有酸性排水供給配管系統4bの配管内に蒸気を吹き込
み、酸性排水を液温が70℃以上となるように加温した
後、苛性ソーダ水溶液を添加し、得られた液を反応槽に
送給し、表２に示す反応槽液温、反応槽液pHの条件下で
反応を行った。表２に示されるように、本発明の処理方
法、処理設備によれば下記の優れた効果が得られる。Treatment method (3): [FIG. 3] Steam is blown into the copper-containing acidic drainage supply piping system 4b to heat the acidic wastewater so that the liquid temperature becomes 70 ° C. or higher. The obtained solution was fed to the reaction tank, and the reaction was performed under the conditions of the reaction tank liquid temperature and the reaction tank liquid pH shown in Table 2. As shown in Table 2, according to the treatment method and treatment equipment of the present invention, the following excellent effects can be obtained.
【００４０】(1)：銅含有酸性排水中の銅を、除去率に
優れると共に工業的に簡易な方法で除去することができ
る。(2)：酸化銅を含有するスラリーの脱水処理で得ら
れた銅スラッジは、銅を高濃 度で含有しており、容易に有価金属である銅を回収でき
る。 (3)：本発明によれば、酸性排水中の銅ばかりでなく、
酸性排水中の砒素、クロム、セレン、亜鉛、鉛、燐も高
除去率で除去することができる。(1): The copper in the acidic wastewater containing copper can be removed by an industrially simple method while having an excellent removal rate. (2): The copper sludge obtained by the dehydration treatment of the slurry containing copper oxide contains copper at a high concentration, so that copper, which is a valuable metal, can be easily recovered. (3): According to the present invention, not only copper in acidic wastewater,
Arsenic, chromium, selenium, zinc, lead, and phosphorus in acidic wastewater can also be removed at a high removal rate.
【００４１】なお、上記した砒素、クロム、セレン、亜
鉛、鉛、燐の除去は、これらの元素と酸化銅との共沈、
後工程における固液分離に伴うものと推定される。 (4)：本発明の処理方法、処理設備におけるアルカリ化
合物の添加、酸性排水の加温に関する好適な操作条件、
装置配列によれば、上記した銅、砒素の除去率をさらに
高くすることが可能となった。The removal of arsenic, chromium, selenium, zinc, lead and phosphorus is performed by co-precipitation of these elements with copper oxide,
It is presumed that this is due to solid-liquid separation in the subsequent process. (4): the treatment method of the present invention, the addition of an alkali compound in the treatment equipment, suitable operating conditions for heating the acidic wastewater,
According to the device arrangement, it has become possible to further increase the removal rate of copper and arsenic described above.
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【発明の効果】本発明によれば、銅含有酸性排水中の銅
を、除去率に優れると共に工業的に簡易な方法で除去す
ることができ、さらには、銅ばかりでなく、銅含有酸性
排水中の砒素、クロム、セレン、亜鉛、鉛、燐も高除去
率で除去することができる。According to the present invention, the copper in the copper-containing acidic wastewater can be removed by an industrially simple method while being excellent in the removal rate. Further, not only copper but also the copper-containing acidic wastewater can be removed. Arsenic, chromium, selenium, zinc, lead, and phosphorus therein can be removed at a high removal rate.
【図１】本発明の銅含有酸性排水の処理方法および処理
設備の一例を示す工程図である。FIG. 1 is a process chart showing an example of a method and a facility for treating copper-containing acidic wastewater of the present invention.
【図２】本発明の銅含有酸性排水の処理方法および処理
設備の一例を示す工程図である。FIG. 2 is a process chart showing an example of a method and a facility for treating copper-containing acidic wastewater of the present invention.
【図３】本発明の銅含有酸性排水の処理方法および処理
設備の一例を示す工程図である。FIG. 3 is a process chart showing an example of a method and equipment for treating copper-containing acidic wastewater of the present invention.
１ 反応槽 ２ 反応槽内の反応液の加温手段 ３ 固液分離装置 ４、4a、4b 酸性排水供給配管系統 ５ 反応液送給配管系統 ６ 熱交換器（：間接熱交換器） ７ アルカリ化合物添加手段 DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Heating means of reaction liquid in reaction tank 3 Solid-liquid separation device 4, 4a, 4b Acid drainage supply piping system 5 Reaction liquid supply piping system 6 Heat exchanger (: indirect heat exchanger) 7 Alkaline compound Addition means
Claims (11)
し、pH≧９、液温≧70℃の条件下で反応せしめ、得られ
た反応液を固液分離することを特徴とする銅含有酸性排
水の処理方法。1. A copper-containing acidic wastewater comprising adding an alkali compound to a copper-containing acidic wastewater, reacting the mixture under conditions of pH ≧ 9 and liquid temperature ≧ 70 ° C., and subjecting the obtained reaction solution to solid-liquid separation. Wastewater treatment method.
PbおよびＰから選ばれる１種または２種以上を含有する
ことを特徴とする請求項１記載の銅含有酸性排水の処理
方法。2. The method according to claim 1, wherein said copper-containing acidic waste water is As, Cr, Se, Zn,
The method for treating copper-containing acidic wastewater according to claim 1, wherein the method comprises one or more selected from Pb and P.
後、アルカリ化合物を添加し、得られた液を反応槽に送
給し、pH≧９、液温≧70℃の条件下で反応せしめ、得ら
れた反応液を固液分離することを特徴とする請求項１ま
たは２記載の銅含有酸性排水の処理方法。3. The copper-containing acidic wastewater is pre-heated, an alkali compound is added, and the obtained liquid is fed to a reaction tank, where the reaction is carried out under conditions of pH ≧ 9 and liquid temperature ≧ 70 ° C. The method for treating copper-containing acidic wastewater according to claim 1 or 2, wherein the obtained reaction solution is subjected to solid-liquid separation.
ように、加温しながら、銅含有酸性排水およびアルカリ
化合物を反応槽に供給し、pH≧９、液温≧70℃の条件下
で反応せしめ、得られた反応液を固液分離することを特
徴とする請求項１または２記載の銅含有酸性排水の処理
方法。4. A copper-containing acidic wastewater and an alkali compound are supplied to the reaction tank while heating so that the liquid temperature in the reaction tank is maintained at a liquid temperature ≧ 70 ° C., and the pH is ≧ 9 and the liquid temperature is ≧ 70. The method for treating copper-containing acidic wastewater according to claim 1 or 2, wherein the reaction is carried out at a temperature of ° C, and the obtained reaction solution is subjected to solid-liquid separation.
件下でアルカリ化合物を添加した後、反応槽に送給し、
pH≧９、液温≧70℃の条件下で反応せしめ、得られた反
応液を固液分離することを特徴とする請求項１または２
記載の銅含有酸性排水の処理方法。5. An alkali compound is added to the copper-containing acidic wastewater under the condition of a liquid temperature of <70 ° C., and then the mixture is fed to a reaction tank.
The reaction is carried out under conditions of pH ≧ 9 and liquid temperature ≧ 70 ° C., and the obtained reaction solution is subjected to solid-liquid separation.
The method for treating copper-containing acidic wastewater according to the above.
排水であることを特徴とする請求項１〜５いずれかに記
載の銅含有酸性排水の処理方法。6. The method for treating copper-containing acidic wastewater according to claim 1, wherein the copper-containing acidic wastewater is copper sulfate-containing acidic wastewater.
ことを特徴とする請求項１〜６いずれかに記載の銅含有
酸性排水の処理方法。7. The method according to claim 1, wherein the alkaline compound is caustic soda.
性排水を反応せしめるための反応槽(1) と、該反応槽
(1) 内の反応液の加温手段(2) と、前記反応槽(1) で反
応後の反応液を固液分離するための固液分離装置(3)
と、前記反応槽(1) へ銅含有酸性排水を供給するための
酸性排水供給配管系統(4) と、前記反応槽(1) と前記固
液分離装置(3) との間に設けられた反応液送給配管系統
(5) と、前記酸性排水供給配管系統(4) に設けられたア
ルカリ化合物添加手段(7) を有することを特徴とする銅
含有酸性排水の処理設備。8. A reaction tank (1) for reacting a copper-containing acidic wastewater to which an alkali compound has been added in advance, and said reaction tank
(1) means for heating the reaction solution in (2), and solid-liquid separation device (3) for solid-liquid separation of the reaction solution after the reaction in the reaction tank (1)
And an acidic wastewater supply piping system (4) for supplying copper-containing acidic wastewater to the reaction tank (1), and provided between the reaction tank (1) and the solid-liquid separation device (3). Reaction liquid supply piping system
(5) A facility for treating copper-containing acidic wastewater, comprising: an alkaline compound addition means (7) provided in the acidic wastewater supply piping system (4).
PbおよびＰから選ばれる１種または２種以上を含有する
ことを特徴とする請求項８記載の銅含有酸性排水の処理
設備。9. The method according to claim 9, wherein the copper-containing acidic waste water is As, Cr, Se, Zn,
The treatment equipment for copper-containing acidic wastewater according to claim 8, comprising one or more selected from Pb and P.
性排水であることを特徴とする請求項８または９記載の
銅含有酸性排水の処理設備。10. The treatment equipment for copper-containing acidic wastewater according to claim 8, wherein the copper-containing acidic wastewater is copper sulfate-containing acidic wastewater.
ることを特徴とする請求項８〜10いずれかに記載の銅含
有酸性排水の処理設備。11. The facility for treating copper-containing acidic wastewater according to claim 8, wherein the alkali compound is caustic soda.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10347513A JP2000167569A (en) | 1998-12-07 | 1998-12-07 | Method and equipment for treating copper-containing acidic waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10347513A JP2000167569A (en) | 1998-12-07 | 1998-12-07 | Method and equipment for treating copper-containing acidic waste water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000167569A true JP2000167569A (en) | 2000-06-20 |
Family
ID=18390739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10347513A Pending JP2000167569A (en) | 1998-12-07 | 1998-12-07 | Method and equipment for treating copper-containing acidic waste water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000167569A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002126758A (en) * | 2000-10-30 | 2002-05-08 | Taiheiyo Cement Corp | Method for treating water |
| JP2005538205A (en) * | 2002-09-04 | 2005-12-15 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Method and apparatus for bonding two plate-shaped objects |
| JP2006334492A (en) * | 2005-06-01 | 2006-12-14 | Dowa Holdings Co Ltd | Method for treating selenium-containing water |
| JP2007260660A (en) * | 2006-03-02 | 2007-10-11 | Mitsui Mining & Smelting Co Ltd | Arsenic removing method and apparatus for arsenic-containing substance, and reaction vessel therefor |
| US8986541B2 (en) | 2011-06-08 | 2015-03-24 | Kabushiki Kaisha Toshiba | Copper recovery apparatus |
-
1998
- 1998-12-07 JP JP10347513A patent/JP2000167569A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002126758A (en) * | 2000-10-30 | 2002-05-08 | Taiheiyo Cement Corp | Method for treating water |
| JP4629851B2 (en) * | 2000-10-30 | 2011-02-09 | 太平洋セメント株式会社 | Wastewater treatment method |
| JP2005538205A (en) * | 2002-09-04 | 2005-12-15 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Method and apparatus for bonding two plate-shaped objects |
| KR101016979B1 (en) | 2002-09-04 | 2011-02-28 | 코닌클리즈케 필립스 일렉트로닉스 엔.브이. | A method and a device for bonding two plate-shaped objects |
| JP2006334492A (en) * | 2005-06-01 | 2006-12-14 | Dowa Holdings Co Ltd | Method for treating selenium-containing water |
| JP2007260660A (en) * | 2006-03-02 | 2007-10-11 | Mitsui Mining & Smelting Co Ltd | Arsenic removing method and apparatus for arsenic-containing substance, and reaction vessel therefor |
| JP4597107B2 (en) * | 2006-03-02 | 2010-12-15 | 三井金属鉱業株式会社 | Arsenic removing method and arsenic removing apparatus from arsenic containing body |
| US8986541B2 (en) | 2011-06-08 | 2015-03-24 | Kabushiki Kaisha Toshiba | Copper recovery apparatus |
| US9701553B2 (en) | 2011-06-08 | 2017-07-11 | Kabushiki Kaisha Toshiba | Copper recovery apparatus |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4947640B2 (en) | Waste acid solution treatment method | |
| JP4216626B2 (en) | Method for recovering nickel sulfate from nickel-containing waste liquid sludge | |
| CN109319823B (en) | Method for treating copper-containing etching waste liquid | |
| JP5431998B2 (en) | Method and apparatus for recovering copper from acidic waste liquid containing copper | |
| JP6288217B1 (en) | Method and apparatus for treating wastewater containing sulfuric acid, fluorine and heavy metal ions | |
| JP3625270B2 (en) | Waste disposal method | |
| KR19980023972A (en) | Semen Method of Copper Electrolyte | |
| WO2015159810A1 (en) | Method for treating copper-containing acidic liquid waste | |
| JP2005015272A (en) | Recovery method of nickel salt from nickel-containing waste solution sludge | |
| JP5118572B2 (en) | Sewage treatment method | |
| JP2011129336A (en) | Recovery method of manganese from battery | |
| JP3151182B2 (en) | Copper electrolyte cleaning method | |
| JP2000167569A (en) | Method and equipment for treating copper-containing acidic waste water | |
| JP5808132B2 (en) | Treatment and recovery method for copper-containing acidic waste liquid and equipment therefor | |
| JP3945216B2 (en) | Waste acid gypsum manufacturing method | |
| CN108163880B (en) | Method for preparing gypsum powder by using zinc smelting waste acid | |
| JP3549560B2 (en) | Method for recovering valuable metals and calcium fluoride from waste solution of pickling process | |
| JP4239801B2 (en) | Method for producing waste acid gypsum | |
| CN113735363A (en) | Treatment method of chrome tanning waste liquid | |
| KR100349154B1 (en) | Composition for eliminating fluorine from wastewater and method for eliminating fluorine from wastewater using the same | |
| JP3810963B2 (en) | Method for separating and concentrating Ga | |
| JP2017136539A (en) | Method for treating blast furnace drain water | |
| JP3186094B2 (en) | Treatment method for wastewater containing heavy metals | |
| JP3593726B2 (en) | Method for treating wastewater containing sulfuric acid and copper | |
| CN109437316A (en) | A kind of preparation method of nanometer level superfine iron zinc composite oxide material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A625 | Written request for application examination (by other person) |
Free format text: JAPANESE INTERMEDIATE CODE: A625 Effective date: 20040909 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080311 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080418 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20080930 |