JP2002248480A - Method for treating copper-containing waste acid - Google Patents
Method for treating copper-containing waste acidInfo
- Publication number
- JP2002248480A JP2002248480A JP2001049686A JP2001049686A JP2002248480A JP 2002248480 A JP2002248480 A JP 2002248480A JP 2001049686 A JP2001049686 A JP 2001049686A JP 2001049686 A JP2001049686 A JP 2001049686A JP 2002248480 A JP2002248480 A JP 2002248480A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- hydrochloric acid
- containing waste
- copper sulfate
- sulfuric 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Removal Of Specific Substances (AREA)
- ing And Chemical Polishing (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プリント基板の製
造工程等において塩化第２銅溶液を用いた銅エッチング
法（以下、塩銅法と記す）による銅エッチング工程など
から排出される含銅廃酸の処理方法に関する。The present invention relates to a copper-containing waste discharged from a copper etching process by a copper etching method using a cupric chloride solution (hereinafter, referred to as a copper salt method) in a manufacturing process of a printed circuit board or the like. The present invention relates to a method for treating an acid.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】塩銅法
による銅エッチング工程より排出される含銅廃塩酸は、
銅及び塩酸を含有しており、これらを回収して再利用す
ることが望まれていた。そこで、本発明者らは、特開平
７−７０７８４号公報及び特願２０００−２３９３４８
号において、含銅廃塩酸の処理方法を提案した。即ち、
特開平７−７０７８４号公報では、電解法により、塩銅
法による銅エッチング工程から排出される含銅廃塩酸中
の余剰銅を陰極で採取し、陽極から発生する塩素を吹き
込んで銅エッチング液として再生するものである。しか
しながら、電解液中に多量の塩素イオンを含むので、発
生塩素ガスの拡散、各部の腐食、銅の電析効率の低下、
及び銅の析出形態が針状又は樹枝状である等の問題点が
あり、それらを解決するため、電解槽は発生塩素ガスの
回収装置、隔膜、及び析出銅の掻き取り機等を備えた複
雑なものとなり、電極を始めとする各部の材質には耐塩
素腐食性を有する高価なものを用いなければならないと
いう欠点があった。また、銅の回収形態が銅粉であるた
め、塩素の混入によりその品位は下がり、それを改善す
るためには更なる工程を必要とした。2. Description of the Related Art Waste copper-containing hydrochloric acid discharged from a copper etching process by a salt copper method is:
It contains copper and hydrochloric acid, and it has been desired to recover and reuse these. Then, the present inventors disclosed in Japanese Patent Application Laid-Open No. 7-70784 and Japanese Patent Application No. 2000-239348.
No. 2 proposed a treatment method for copper-containing waste hydrochloric acid. That is,
In JP-A-7-70784, the excess copper in the copper-containing waste hydrochloric acid discharged from the copper etching step by the salt copper method is collected by a cathode by an electrolytic method, and chlorine generated from the anode is blown into a copper etching solution. It is something to play. However, since the electrolyte contains a large amount of chlorine ions, diffusion of generated chlorine gas, corrosion of various parts, reduction of copper electrodeposition efficiency,
In order to solve these problems, the electrolytic cell must be equipped with a chlorine gas recovery device, a diaphragm, and a scraper for the deposited copper. There is a disadvantage that expensive materials having resistance to chlorine corrosion must be used for the material of each part including the electrodes. In addition, since copper is recovered in the form of copper powder, its quality is reduced by the incorporation of chlorine, and further steps are required to improve the quality.
【０００３】特願２０００−２３９３４８号は、これら
の欠点を改善するために提案したもので、含銅廃塩酸に
硫酸を添加し、減圧下で加熱して塩酸と硫酸銅溶液に複
分解し、得られた硫酸銅溶液を電解して板状の金属銅を
回収する方法である。しかしながら、電解液中に多量の
遊離硫酸が存在してｐＨが低いため、得られる銅の表面
が褐色となり、品位が低下し易い場合があった。[0003] Japanese Patent Application No. 2000-239348 is proposed to improve these drawbacks. Sulfuric acid is added to copper-containing waste hydrochloric acid, and the mixture is heated under reduced pressure to give a double decomposition into hydrochloric acid and a copper sulfate solution. This is a method of recovering plate-like metallic copper by electrolyzing the obtained copper sulfate solution. However, since a large amount of free sulfuric acid is present in the electrolyte and the pH is low, the surface of the obtained copper becomes brown, and the quality may be easily deteriorated.
【０００４】本発明は、上記の問題点を改善するために
なされたもので、含銅廃塩酸から再利用可能な塩酸及び
板状で品位の高い銅を、簡易な装置で効率的に、かつ副
生廃棄物を出さずに回収する処理方法を提供することを
目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is intended to efficiently recycle hydrochloric acid and plate-like high-quality copper from waste copper-containing waste hydrochloric acid with a simple apparatus. An object of the present invention is to provide a processing method for collecting by-product waste without producing it.
【０００５】[0005]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記目的を達成するために鋭意検討を行なっ
た結果、本発明に到達したもので、本発明は、塩化第２
銅及び塩酸を含有する含銅廃塩酸に硫酸を添加し、減圧
下で加熱して、この廃液中に含まれる塩化第２銅を硫酸
銅と塩酸に分解する第１工程と、第１工程で発生する塩
化水素ガスを回収する第２工程と、第１工程で得られる
硫酸銅を含む溶液を冷却して硫酸銅の結晶を晶析する第
３工程と、この硫酸銅結晶を分離回収する第４工程と、
得られた硫酸銅結晶を再溶解し、電解法により陰極で金
属銅を回収する第５工程と、第４工程で得られた母液及
び第５工程の銅回収後の残液を第１工程へ戻す第６工程
とを含むことを特徴とする含銅廃酸の処理方法及び、第
１工程で添加する硫酸の代わりに含銅廃硫酸を利用する
含銅廃酸の処理方法を提供する。Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention.
Sulfuric acid is added to copper-containing waste hydrochloric acid containing copper and hydrochloric acid and heated under reduced pressure to decompose cupric chloride contained in the waste liquid into copper sulfate and hydrochloric acid; A second step of recovering the generated hydrogen chloride gas, a third step of cooling the solution containing copper sulfate obtained in the first step to crystallize copper sulfate crystals, and a third step of separating and recovering the copper sulfate crystals. 4 steps,
The fifth step of re-dissolving the obtained copper sulfate crystal and recovering metallic copper at the cathode by an electrolytic method, and the mother liquor obtained in the fourth step and the remaining liquid after copper recovery in the fifth step are transferred to the first step. A method for treating copper-containing waste acid, comprising: returning a sixth step; and a method for treating copper-containing waste acid by using copper-containing waste sulfuric acid instead of sulfuric acid added in the first step.
【０００６】本発明によれば、含銅廃塩酸に硫酸を添加
して塩化銅を硫酸銅と塩酸に複分解し、塩酸は塩化水素
ガスとして取り出し、冷却して回収する一方、硫酸銅は
結晶を晶析して分離した後、再溶解し、電解して板状の
金属銅として回収することができ、しかも硫酸銅結晶分
離後の母液及び電解後の残液はこれを第１工程において
塩化銅を複分解する硫酸溶液として使用することができ
る。一方、回収塩酸は１７〜２６％の濃度でプリント基
板の銅エッチングには十分使用できる。従って、含銅廃
塩酸を有価物質に再生回収してリサイクルすることがで
きるものである。According to the present invention, sulfuric acid is added to copper-containing waste hydrochloric acid to double-decompose copper chloride into copper sulfate and hydrochloric acid. Hydrochloric acid is taken out as hydrogen chloride gas, cooled and recovered, while copper sulfate removes crystals. After crystallization and separation, it can be redissolved, electrolyzed and recovered as plate-like metallic copper, and the mother liquor after the copper sulfate crystal separation and the remaining liquid after the electrolysis are mixed with copper chloride in the first step. Can be used as a sulfuric acid solution for metathesis. On the other hand, the concentration of recovered hydrochloric acid at a concentration of 17 to 26% can be sufficiently used for etching copper on a printed circuit board. Therefore, the copper-containing waste hydrochloric acid can be recycled and recovered as a valuable substance.
【０００７】本発明での硫酸銅溶液の電解は、塩化銅溶
液の電解と異なり、塩素発生の問題がないので隔膜の必
要がなく、構造が簡便な電解装置が使用できるし、得ら
れる電析される金属銅も板状又は皮膜状であるので、回
収し易いばかりでなく、塩素の混入がなく、高品位の９
９．９０％以上のものである。それ故、本発明の方法
は、工業的有利に含銅廃塩酸の処理を行うことができる
ものである。The electrolysis of the copper sulfate solution according to the present invention is different from the electrolysis of the copper chloride solution, because there is no problem of chlorine generation, there is no need for a diaphragm, and an electrolysis apparatus having a simple structure can be used. Since the metal copper to be formed is also in the form of a plate or a film, it is not only easy to recover, but also free of chlorine contamination and high quality 9
9.90% or more. Therefore, the method of the present invention is capable of industrially advantageously treating copper-containing waste hydrochloric acid.
【０００８】以下、本発明につき更に詳しく説明する。
本発明の含銅廃酸の処理方法において、この含銅廃酸
は、例えばプリント配線基板の製造工程において銅張積
層板等を塩化第２銅を用いた銅エッチング液でエッチン
グする際に排出される塩化銅及び塩酸を含有する含銅廃
塩酸や硫酸と過酸化水素水でレジストを剥離する際に排
出される含銅廃硫酸などを用いることができる。Hereinafter, the present invention will be described in more detail.
In the method for treating copper-containing waste acid of the present invention, the copper-containing waste acid is discharged when, for example, a copper-clad laminate or the like is etched with a copper etching solution using cupric chloride in a printed wiring board manufacturing process. Copper-containing waste hydrochloric acid containing copper chloride and hydrochloric acid, and copper-containing waste sulfuric acid discharged when the resist is stripped off with sulfuric acid and aqueous hydrogen peroxide.
【０００９】本発明においては、図１に示したように、
第１工程としてこのような含銅廃塩酸溶液に硫酸を添加
し、塩化銅を硫酸銅と塩酸とに複分解する。この場合、
硫酸は、添加後の濃度が５０〜７０重量％になるように
減圧蒸留することが好ましいので、添加する硫酸の濃度
は自由であるが、３０〜９８重量％の濃度が好ましい。
更に好ましくは５０〜７５重量％濃度である。また、硫
酸の代わりに含銅廃硫酸を使用することもできる。硫酸
又は含銅廃硫酸の添加量は、塩化銅が硫酸銅と塩酸とに
複分解する反応時の硫酸濃度が４０〜７０重量％、特に
５０〜７０重量％濃度になるようにすることがよく、特
に得られる硫酸銅が１〜３水和物であることが好まし
い。この硫酸添加による反応は減圧下３００Ｔｏｒｒ以
下、好ましくは５０〜２００Ｔｏｒｒで６０〜１２０℃
で行うことが好ましく、この条件であると上記分解反応
が効率よく行われると共に、塩化水素ガスを揮発除去
し、第２工程でこれを冷却することによってコンデンサ
ーで回収できる。In the present invention, as shown in FIG.
As a first step, sulfuric acid is added to such a copper-containing waste hydrochloric acid solution, and copper chloride is metathesized into copper sulfate and hydrochloric acid. in this case,
The sulfuric acid is preferably distilled under reduced pressure so that the concentration after the addition becomes 50 to 70% by weight. Therefore, the concentration of the sulfuric acid to be added is free, but a concentration of 30 to 98% by weight is preferable.
More preferably, the concentration is 50 to 75% by weight. Further, copper-containing waste sulfuric acid can be used instead of sulfuric acid. The addition amount of sulfuric acid or copper-containing waste sulfuric acid is preferably adjusted so that the sulfuric acid concentration at the time of double decomposition of copper chloride into copper sulfate and hydrochloric acid is 40 to 70% by weight, particularly 50 to 70% by weight. In particular, it is preferable that the obtained copper sulfate is 1-3 hydrate. The reaction by the addition of sulfuric acid is performed at a reduced pressure of 300 Torr or less, preferably 50 to 200 Torr and 60 to 120 ° C.
Under these conditions, the above decomposition reaction can be carried out efficiently, and the hydrogen chloride gas can be volatilized and removed, and then cooled in the second step to be recovered by a condenser.
【００１０】ここで、連続運転を想定し、塩素イオンの
殆どが混合後速やかに塩化水素ガスとして蒸発する条件
を一例として図２に示す。図２において、曲線より上側
が塩化水素ガスとして蒸発する条件（温度，圧力）であ
る。Here, assuming continuous operation, FIG. 2 shows an example of a condition in which most of the chlorine ions evaporate as hydrogen chloride gas immediately after mixing. In FIG. 2, the upper side of the curve is the conditions (temperature and pressure) for evaporating as hydrogen chloride gas.
【００１１】反応容器としては、上記反応条件に対応
し、かつ耐食性を持つもの、例えば、内側をＦＲＰ、又
はテフロン（登録商標）でコーティングしたステンレス
容器等が使用できる。硫酸は、第４工程で回収される母
液及び第５工程で回収される電解後の残液を再利用して
用いることができる。理論上は、系外への硫酸の流出は
なく、補充する必要がないため、経済的に有利であり、
環境面から考えても好ましい。最初に用いる硫酸として
は、上述したように銅エッチング工程において、硫酸と
過酸化水素水を用いてレジストを剥離する際に排出され
るものを始めとする含銅廃硫酸も使用できる。As the reaction vessel, those having the corrosion resistance corresponding to the above reaction conditions, for example, a stainless steel vessel coated on the inside with FRP or Teflon (registered trademark) can be used. Sulfuric acid can be used by reusing the mother liquor recovered in the fourth step and the residual liquid after electrolysis recovered in the fifth step. Theoretically, there is no outflow of sulfuric acid out of the system and there is no need to replenish it, which is economically advantageous,
It is also preferable from an environmental point of view. As the sulfuric acid to be used first, copper-containing waste sulfuric acid such as that discharged when the resist is peeled off using sulfuric acid and hydrogen peroxide in the copper etching step as described above can also be used.
【００１２】なお、第２工程で回収される塩酸は、第１
工程反応前の硫酸濃度を反応後の濃度に合わせれば、含
銅廃塩酸中の塩素イオン濃度と同程度の濃度で得られ
る。塩銅法による銅エッチング工程から出る含銅廃塩酸
の場合、塩素イオン濃度は２０重量％前後であるので、
調整してエッチング液の原料として有効的に再利用でき
る。The hydrochloric acid recovered in the second step is
If the concentration of sulfuric acid before the reaction in the process is adjusted to the concentration after the reaction, it can be obtained at the same concentration as the chloride ion concentration in the copper-containing waste hydrochloric acid. In the case of copper-containing waste hydrochloric acid from the copper etching process by the salt copper method, the chloride ion concentration is around 20% by weight.
It can be adjusted and effectively reused as a raw material of the etching solution.
【００１３】次に、第３工程は、第１工程の反応溶液
（硫酸銅を含む溶液）を冷却して硫酸銅の結晶を晶析す
る工程であり、第４工程はこの硫酸銅結晶を分離回収す
る工程である。Next, the third step is a step of cooling the reaction solution (solution containing copper sulfate) of the first step to crystallize copper sulfate crystals, and the fourth step is to separate the copper sulfate crystals. This is the step of collecting.
【００１４】この場合、冷却速度は、５〜２０℃／ｈｒ
であることが好ましい。この時、冷却は撹拌しながら行
うのが好ましい。静置して行うと、冷却効率が悪い上、
結晶成長により設備の閉塞や固液分離の効率悪化を招く
おそれがある。冷却温度は、低い程より多くの結晶が晶
析するが、下げ過ぎると母液を第１工程に戻すために加
熱する際、より多くの熱量を必要とする。回収される硫
酸銅結晶は、図２に示した条件で行った場合、従来あま
り知られていない２水和物が主体となる。In this case, the cooling rate is 5 to 20 ° C./hr.
It is preferred that At this time, cooling is preferably performed while stirring. If done standing, the cooling efficiency is poor and
Crystal growth may lead to blockage of equipment and deterioration of the efficiency of solid-liquid separation. The lower the cooling temperature, the more crystals are crystallized, but if the cooling temperature is too low, more heat is required when heating the mother liquor to return to the first step. When the copper sulfate crystals to be recovered are subjected to the conditions shown in FIG. 2, mainly dihydrate, which is not well known, is mainly used.
【００１５】第５工程は、第４工程で回収した硫酸銅の
結晶を硫酸水溶液に再溶解し、電解法により陰極に銅を
回収する工程である。電解の際、電解液中の硫酸濃度が
濃くなると陰極で水素が発生し、また、得られる銅は塩
基性金属となってその価値が低下する。表１に常温にお
ける硫酸濃度と得られる銅表面の色の関係を示す。な
お、電解時の温度を上げれば、更に濃い濃度下において
も高純度の銅が回収できる。The fifth step is a step in which the copper sulfate crystals recovered in the fourth step are redissolved in an aqueous sulfuric acid solution, and copper is recovered at the cathode by an electrolytic method. At the time of electrolysis, if the concentration of sulfuric acid in the electrolytic solution increases, hydrogen is generated at the cathode, and the obtained copper becomes a basic metal and its value decreases. Table 1 shows the relationship between the sulfuric acid concentration at room temperature and the color of the obtained copper surface. If the temperature at the time of electrolysis is increased, high-purity copper can be recovered even under a higher concentration.
【００１６】[0016]
【表１】 [Table 1]
【００１７】本発明の第５工程の硫酸銅溶液の電解は公
知の方法で行うことができる。この場合、陽極として
は、カーボン、チタン、鉛、ステンレス、白金、チタン
膜を表面にコーティングした白金などの不溶性の陽極が
使用できる。また、陰極としては、ステンレス、銅板の
表面にニカワ等を塗布したものなど、銅皮膜が容易に剥
離し得るものが用いられる。電解に際し、陰極の電流密
度は０．１〜２０Ａ／ｄｍ2の範囲とし得る。また、電
解時の温度は特別に定めないが、５０〜６０℃位で処理
するのが好ましい。The electrolysis of the copper sulfate solution in the fifth step of the present invention can be performed by a known method. In this case, an insoluble anode such as carbon, titanium, lead, stainless steel, platinum, and platinum coated on the surface of titanium film can be used as the anode. Further, as the cathode, those which can easily peel off the copper film, such as stainless steel and copper plate coated with glue or the like, are used. Upon electrolysis, the current density of the cathode may range from 0.1~20A / dm 2. Further, the temperature at the time of electrolysis is not particularly defined, but it is preferable to perform the treatment at about 50 to 60 ° C.
【００１８】第６工程は、上記第４工程で硫酸銅結晶を
晶析、回収した後の母液、第５工程で硫酸銅溶液を電解
し、銅を電析した後の電解液を第１工程の硫酸として使
用するものである。従って、本発明の方法は、副生廃棄
物を出さず、工業的に有利に含銅廃塩酸を有価物質に再
生、回収できるものである。In the sixth step, the mother liquor after crystallizing and recovering the copper sulfate crystals in the fourth step, and in the fifth step, the copper sulfate solution is electrolyzed and the electrolytic solution after the copper is electrodeposited is used in the first step. It is used as sulfuric acid. Therefore, the method of the present invention is capable of industrially advantageously recovering and recovering copper-containing waste hydrochloric acid into a valuable substance without producing by-product waste.
【００１９】[0019]
【発明の効果】本発明によれば、塩銅法による銅エッチ
ング工程より排出される含銅廃塩酸から使用可能な塩酸
と板状の高品位銅を効率よく得るクロズドシステムでリ
サイクル性に優れた含銅廃塩酸の処理方法を提供するこ
とができる。According to the present invention, excellent recyclability is achieved with a closed system that efficiently obtains usable hydrochloric acid and plate-like high-grade copper from the copper-containing waste hydrochloric acid discharged from the copper etching process by the salt copper method. And a method for treating copper-containing waste hydrochloric acid.
【００２０】[0020]
【実施例】以下、実施例を示し、本発明を具体的に説明
するが、本発明は下記の実施例に制限されるものではな
い。The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.
【００２１】［実施例１］Ｃｕ：１１０ｇ／Ｌ、Ｃｌ：
２３０ｇ／Ｌの含銅廃塩酸８４０ｍＬを、６５重量％硫
酸４Ｌに２００Ｔｏｒｒ、９５℃の条件下で添加したと
ころ、Ｃｌ：２００ｇ／Ｌの塩酸８６５ｍＬ、Ｃｕ：３
１０ｇ／ｋｇ、ＳＯ4：４８０ｇ／ｋｇ、Ｃｌ：１２ｇ
／ｋｇの硫酸銅結晶２５６ｇ、及びＣｕ：３ｇ／Ｌ、Ｓ
Ｏ4：９８０ｇ／Ｌ、Ｃｌ：４ｇ／Ｌの母液３８９０ｍ
Ｌが回収できた。Example 1 Cu: 110 g / L, Cl:
When 840 mL of 230 g / L copper-containing waste hydrochloric acid was added to 4 L of 65% by weight sulfuric acid at 200 Torr and 95 ° C., 865 mL of Cl: 200 g / L hydrochloric acid, Cu: 3
10 g / kg, SO 4 : 480 g / kg, Cl: 12 g
G / kg of copper sulfate crystals and Cu: 3 g / L, S
3890 m of mother liquor of O 4 : 980 g / L, Cl: 4 g / L
L could be recovered.
【００２２】得られた硫酸銅結晶２５０ｇを２４０ｍＬ
の水に順次溶解し、電流密度２０Ａ／ｄｍ2の条件で電
解を行ったところ、７３．５ｇの銅が回収でき、品位は
９９．９８％であった。残液の各成分濃度はＣｕ：１５
ｇ／Ｌ、ＳＯ4：５００ｇ／Ｌ、Ｃｌ：１２ｇ／Ｌであ
った。250 g of the obtained copper sulfate crystal is 240 mL
Was sequentially dissolved in water and electrolysis was performed under the conditions of a current density of 20 A / dm 2. As a result, 73.5 g of copper could be recovered, and the grade was 99.98%. The concentration of each component in the residual liquid is Cu: 15
g / L, SO 4 : 500 g / L, Cl: 12 g / L.
【００２３】硫酸の代わりに、得られた母液、及び電解
後の残液の混合液を用いて行っても同様な結果が得られ
た。Similar results were obtained by using a mixture of the obtained mother liquor and the remaining liquid after electrolysis instead of sulfuric acid.
【００２４】［実施例２］塩銅法による銅エッチング工
程より排出された含銅廃塩酸（塩化第１銅５ｇ／Ｌ、塩
化第二銅１４０ｇ／Ｌ、塩酸（塩化水素）２００ｇ／Ｌ
含有）１，０００ｇに、９８重量％濃度の硫酸溶液１，
０００ｇを添加し、１００Ｔｏｒｒ、６０℃において３
０分反応させた。これにより上記廃塩酸溶液中の塩酸は
殆ど塩化水素ガスとして除去された。[Example 2] Copper-containing waste hydrochloric acid (5 g / L of cuprous chloride, 140 g / L of cupric chloride, 200 g / L of hydrochloric acid (hydrogen chloride)) discharged from the copper etching process by the salt copper method
Containing) 98% by weight sulfuric acid solution 1,
At 100 Torr and 60 ° C.
The reaction was performed for 0 minutes. Thereby, the hydrochloric acid in the waste hydrochloric acid solution was almost removed as hydrogen chloride gas.
【００２５】次に、得られた硫酸銅溶液を撹拌下に１０
℃／ｈｒの冷却速度で２０℃まで冷却し、硫酸銅結晶
（２水塩）１６２．９ｇを回収した。これを硫酸溶解
し、硫酸銅（２水塩）１６２．９ｇ／Ｌと硫酸３００ｇ
／Ｌの溶液を得た。この硫酸銅溶液を、陽極として鉛、
陰極として銅板を用い、電流密度２０Ａ／ｄｍ2、５０
℃の条件で１２時間電解を行った。その結果、上記硫酸
銅溶液中の銅分は殆ど電析処理された。得られた銅の品
位は９９．９８％であった。Next, the obtained copper sulfate solution was stirred for 10 minutes.
The mixture was cooled to 20 ° C at a cooling rate of ° C / hr, and 162.9 g of copper sulfate crystals (dihydrate) were recovered. This was dissolved in sulfuric acid, and copper sulfate (dihydrate) 162.9 g / L and sulfuric acid 300 g
/ L solution was obtained. This copper sulfate solution is used as an anode for lead,
A copper plate was used as the cathode, and the current density was 20 A / dm 2 , 50
Electrolysis was performed at 12 ° C. for 12 hours. As a result, the copper content in the copper sulfate solution was almost electrodeposited. The grade of the obtained copper was 99.98%.
【００２６】なお、上記硫酸銅結晶を回収した後の母液
及び銅電析後の電解液は、いずれも含銅廃塩酸溶液の複
分解用硫酸溶液として良好なものだった。The mother liquor after recovering the copper sulfate crystals and the electrolytic solution after copper electrodeposition were both favorable sulfuric acid solutions for double decomposition of copper-containing waste hydrochloric acid solution.
【図１】本発明法の一例を説明するフローシートであ
る。FIG. 1 is a flow sheet illustrating an example of the method of the present invention.
【図２】第１工程で塩化水素ガスが蒸発する条件の一例
を示すグラフである。FIG. 2 is a graph showing an example of conditions under which hydrogen chloride gas evaporates in a first step.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２５Ｃ 7/06 ３０１ Ｃ２５Ｃ 7/06 ３０１Ａ (72)発明者 内藤 大 埼玉県上尾市瓦葺1485−７ Ｆターム(参考） 4D038 AB68 BA04 4K058 AA18 AA22 BA21 BB04 CA04 CA17 CA22 EB13 ED04 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C25C 7/06 301 C25C 7/06 301A (72) Inventor Dai Dai Naito 1485-7 F-term roof tile roof, Ageo City, Saitama Prefecture (Reference) 4D038 AB68 BA04 4K058 AA18 AA22 BA21 BB04 CA04 CA17 CA22 EB13 ED04
Claims (3)
酸に硫酸を添加し、減圧下で加熱して、この廃液中に含
まれる塩化第２銅を硫酸銅と塩酸に分解する第１工程
と、第１工程で発生する塩化水素ガスを回収する第２工
程と、第１工程で得られる硫酸銅を含む溶液を冷却して
硫酸銅の結晶を晶析する第３工程と、この硫酸銅結晶を
分離回収する第４工程と、得られた硫酸銅結晶を再溶解
し、電解法により陰極で金属銅を回収する第５工程と、
第４工程で得られた母液及び第５工程の銅回収後の残液
を第１工程へ戻す第６工程とを含むことを特徴とする含
銅廃酸の処理方法。1. A sulfuric acid is added to copper-containing waste hydrochloric acid containing cupric chloride and hydrochloric acid, and heated under reduced pressure to decompose cupric chloride contained in the waste liquid into copper sulfate and hydrochloric acid. One step, a second step of recovering hydrogen chloride gas generated in the first step, and a third step of cooling the solution containing copper sulfate obtained in the first step to crystallize copper sulfate crystals, A fourth step of separating and recovering the copper sulfate crystal, a fifth step of re-dissolving the obtained copper sulfate crystal, and recovering metallic copper at the cathode by an electrolytic method,
And a sixth step of returning the mother liquor obtained in the fourth step and the residual liquid after the copper recovery in the fifth step to the first step, a sixth step.
使用するようにした請求項１記載の処理方法。2. The treatment method according to claim 1, wherein copper-containing waste sulfuric acid is used in place of sulfuric acid in the first step.
下、温度を１２０℃以下で行う請求項１又は２記載の処
理方法。3. The processing method according to claim 1, wherein the pressure reduction in the first step is performed at 300 Torr or less and the temperature is 120 ° C. or less.
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|---|---|---|---|
| JP2001049686A JP3736618B2 (en) | 2001-02-26 | 2001-02-26 | Treatment method of waste acid containing copper |
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| JP3736618B2 JP3736618B2 (en) | 2006-01-18 |
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