JP2002153889A - Method for treating copper chloride-containing waste etching solution, treating agent and method for recovering copper - Google Patents
Method for treating copper chloride-containing waste etching solution, treating agent and method for recovering copperInfo
- Publication number
- JP2002153889A JP2002153889A JP2000353449A JP2000353449A JP2002153889A JP 2002153889 A JP2002153889 A JP 2002153889A JP 2000353449 A JP2000353449 A JP 2000353449A JP 2000353449 A JP2000353449 A JP 2000353449A JP 2002153889 A JP2002153889 A JP 2002153889A
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- JP
- Japan
- Prior art keywords
- copper
- treating
- liquid
- hydrophilic polymer
- sludge
- 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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Classifications
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- 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
- Manufacture And Refinement Of Metals (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、塩化銅含有エッチ
ング廃液の処理方法、処理剤及び銅の回収方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating an etching waste solution containing copper chloride, a treating agent, and a method for recovering copper.
【0002】[0002]
【従来の技術】プリント配線板の回路は、銅箔がラミネ
ートされた銅張積層板や予め無電解銅めっきが施された
基板を、塩化第二銅を含むエッチング液を用いてエッチ
ングすることが広く行われている。このエッチング工程
では、塩化第二銅が金属銅と反応して塩化第一銅を生成
する。この際、銅の溶解に伴うエッチング能力の低下を
防ぐため、エッチング液の化学的再生と濃度調整が必要
で、添加薬剤による増量分がエッチング装置よりエッチ
ング廃液として排出される。このエッチング廃液は、一
般的にはエッチング液メーカーや産業廃棄物処理会社に
より収集され、種々の方式で処理されている。しかし、
廃液量の増加に伴い輸送にかかる費用が増大しているこ
とや、処理能力が限界に達していることによる処理コス
トの高騰が深刻な問題となっている。2. Description of the Related Art A circuit of a printed wiring board is formed by etching a copper-clad laminate having a copper foil laminated thereon or a substrate which has been previously subjected to electroless copper plating using an etching solution containing cupric chloride. Widely used. In this etching step, cupric chloride reacts with metallic copper to produce cuprous chloride. At this time, in order to prevent a decrease in etching ability due to dissolution of copper, chemical regeneration and concentration adjustment of the etching solution are necessary, and an increased amount due to the added chemical is discharged from the etching apparatus as an etching waste solution. This etching waste liquid is generally collected by an etchant manufacturer or an industrial waste treatment company, and is treated in various ways. But,
A serious problem is that the cost of transportation is increasing with the increase in the amount of waste liquid, and the processing cost is soaring because the processing capacity has reached its limit.
【0003】[0003]
【発明が解決しようとする課題】本発明は、塩化銅含有
エッチング廃液を効率よくかつ低められたスラッジ発生
量で処理するための方法及びそれに用いる塩化銅含有エ
ッチング廃液処理剤、ならびに、銅を含むスラッジから
銅を回収する方法を提供することをその課題とする。DISCLOSURE OF THE INVENTION The present invention relates to a method for efficiently and efficiently treating a copper chloride-containing etching waste liquid with a reduced amount of sludge, a copper chloride-containing etching waste liquid treating agent used therein, and copper. An object of the present invention is to provide a method for recovering copper from sludge.
【0004】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、塩化銅含有エッチン
グ廃液を処理する方法において、(i)リン酸イオン、
(ii)カルシウムイオン、(iii)鉄イオン及び(iv)
カルボキシル基含有親水性高分子物質及び/又はその加
水分解生成物の存在下で、該被処理液のpHを5〜14
の範囲に調整して、該溶存銅イオンを難溶性物質として
沈殿させることを特徴とする塩化銅含有エッチング廃液
の処理方法が提供される。また、本発明によれば、塩化
銅含有エッチング廃液を処理するための薬剤であって、
(i)リン酸化合物、(ii)カルシウム化合物、(ii
i)鉄化合物及び(iv)カルボキシル基含有親水性高分
子物質及び/又はその加水分解生成物とからなることを
特徴とする塩化銅含有エッチング廃液処理剤が提供され
る。さらに、本発明によれば、前記の方法で得られた沈
殿物を液中から分離して得られたスラッジに、アルカリ
溶液を加えて懸濁液を作り、この懸濁液に高分子凝集剤
を加えて液中の懸濁物を凝集させ、この凝集懸濁物を分
離させることを特徴とする銅を回収する方法が提供され
る。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, in the method for treating an etching waste liquid containing copper chloride, (i) phosphate ions,
(Ii) calcium ion, (iii) iron ion and (iv)
In the presence of a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof, the pH of the liquid to be treated is adjusted to 5 to 14
And a method for treating a copper chloride-containing etching waste liquid, wherein the dissolved copper ion is precipitated as a hardly soluble substance. Further, according to the present invention, there is provided an agent for treating a copper chloride-containing etching waste liquid,
(I) a phosphate compound, (ii) a calcium compound, (ii)
A copper chloride-containing etching waste liquid treating agent comprising i) an iron compound and (iv) a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof. Further, according to the present invention, an alkaline solution is added to a sludge obtained by separating the precipitate obtained by the above method from the liquid to form a suspension, and a polymer flocculant is added to the suspension. To agglomerate the suspension in the solution, and separating the aggregated suspension. A method for recovering copper is provided.
【0005】[0005]
【発明の実施の形態】本発明の塩化銅含有エッチング廃
液処理剤(以下、単に処理剤とも言う)の1つの態様
は、(i)リン酸化合物、(ii)カルシウム化合物、
(iii)鉄化合物及び(iv)カルボキシル基含有親水性
高分子物質及び/又はその加水分解生成物の混合物から
なるものである。本発明の処理剤は、通常、粉末状又は
水溶液状で用いられる。DETAILED DESCRIPTION OF THE INVENTION One embodiment of the copper chloride-containing etching waste liquid treating agent of the present invention (hereinafter, also simply referred to as a treating agent) comprises (i) a phosphate compound, (ii) a calcium compound,
It consists of a mixture of (iii) an iron compound and (iv) a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof. The treating agent of the present invention is usually used in the form of a powder or an aqueous solution.
【0006】リン酸化合物には、リン酸(H3PO4)の
他、水中で加水分解してリン酸を生成する化合物、例え
ば、リン酸ナトリウム、リン酸水素2ナトリウム、リン
酸2水素ナトリウム、リン酸カリウム、リン酸水素2カ
リウム、リン酸2水素カリウム、ヘキサンメタリン酸ナ
トリウム、トリポリリン酸ナトリウム等が挙げられる。
これらのリン酸化合物は、単独又は混合物の形態で用い
ることができる。[0006] Phosphoric acid compounds include, in addition to phosphoric acid (H 3 PO 4 ), compounds that hydrolyze in water to generate phosphoric acid, for example, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate , Potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium hexane metaphosphate, sodium tripolyphosphate and the like.
These phosphate compounds can be used alone or in the form of a mixture.
【0007】カルシウム化合物には、塩化カルシウム、
炭酸カルシウム、水酸化カルシウム等が挙げられる。本
発明において処理剤成分として用いるカルシウム化合物
は、単独又は混合物の形態で用いることができる。[0007] Calcium compounds include calcium chloride,
Examples include calcium carbonate and calcium hydroxide. The calcium compound used as the treating agent component in the present invention can be used alone or in the form of a mixture.
【0008】鉄化合物には、ポリ塩化鉄、ポリ硫酸鉄、
塩化第一鉄、塩化第二鉄、硫酸第一鉄及び硫酸第二鉄等
が挙げられる。これらの鉄化合物は、単独又は混合物の
形態で用いることができる。[0008] Iron compounds include polyiron chloride, polyiron sulfate,
Examples include ferrous chloride, ferric chloride, ferrous sulfate, and ferric sulfate. These iron compounds can be used alone or in the form of a mixture.
【0009】前記カルボキシル基含有親水性高分子物質
には、各種の水溶性高分子物質が包含される。このよう
な高分子物質としては、アルギン酸、ジエランガム、キ
サンタンガム、ペクチン、ペクチン酸、ペクチニン酸、
アニオン化でんぷん、アルギン酸プロピレングリコール
エステル、カルボキシメチルセルロース、デンプングリ
コール酸、繊維素グリコール酸等の多糖類及びそれらの
金属塩等が挙げられる。本発明では、特に、アルギン酸
ナトリウムやアルギン酸カルシウムの使用が好ましい
が、このものを用いる場合には、アルギン酸を構成して
いるマンヌマロン酸(M)とグルロン酸(G)の含有比
率(モル比)[M]/[G]が、0.1〜4.0、好ま
しくは0.1〜3の範囲にあるものの使用が好ましい。
グルロン酸の含有比率が多いもの程、フロック形成性に
すぐれている。The carboxyl group-containing hydrophilic polymer includes various water-soluble polymers. Such polymeric substances include alginic acid, dielan gum, xanthan gum, pectin, pectic acid, pectinic acid,
Examples include polysaccharides such as anionized starch, propylene glycol alginate, carboxymethyl cellulose, starch glycolic acid, and cellulose glycolic acid, and metal salts thereof. In the present invention, it is particularly preferable to use sodium alginate or calcium alginate. In the case of using these, the content ratio (molar ratio) of mannummalonic acid (M) and guluronic acid (G) constituting alginic acid [ M] / [G] in the range of 0.1 to 4.0, preferably 0.1 to 3, is preferably used.
The higher the content of guluronic acid, the better the floc-forming property.
【0010】本発明において用いる前記カルボキシル基
含有親水性高分子物質及び/又はその加水分解生成物
は、単独又は混合物の形態で用いることができる。混合
物としては、アルギン酸又はその塩を含有する混合物の
使用が好ましい。The carboxyl group-containing hydrophilic polymer substance and / or its hydrolysis product used in the present invention can be used alone or in the form of a mixture. As the mixture, it is preferable to use a mixture containing alginic acid or a salt thereof.
【0011】本発明において用いる前記アルギン酸及び
/又はその加水分解生成物は、単独又は混合物の形態で
用いることができる。この場合のアルギン酸又はその塩
を含有する好ましい混合物としては、(i)アルギン酸
又はその塩と、(ii)ジエランガム、キサンタンガム、
ペクチン、ペクチン酸、ペクチニン酸及びそれらの塩の
中から選ばれる少なくとも1種の親水性高分子物質との
混合物を挙げることができる。その混合比を示すと、例
えば、アルギン酸ナトリウムと他のアニオン基含有親水
性高分子物質との混合物を用いる場合、アルギン酸ナト
リウム(A)と他のアニオン基含有親水性高分子物質
(B)との重量比[A]/[B]は、1〜100、好ま
しくは2〜50である。The alginic acid and / or its hydrolysis product used in the present invention can be used alone or in the form of a mixture. In this case, preferred mixtures containing alginic acid or a salt thereof include (i) alginic acid or a salt thereof, (ii) dielan gum, xanthan gum,
Examples thereof include a mixture with at least one hydrophilic high-molecular substance selected from pectin, pectic acid, pectinic acid and salts thereof. When the mixture ratio is shown, for example, when a mixture of sodium alginate and another anion group-containing hydrophilic polymer is used, the mixture of sodium alginate (A) and another anion group-containing hydrophilic polymer (B) is used. The weight ratio [A] / [B] is 1 to 100, preferably 2 to 50.
【0012】本発明の処理剤を好ましく製造する場合、
先ず、カルボキシル含有親水性高分子物質、例えばアル
ギン酸を、アルカリ性物質を含む水中において加熱し、
加水分解させるとともに水中に溶解させる。例えば、ア
ルカリ性物質としての水酸化ナトリウムを含む水中にア
ルギン酸ナトリウムを存在させ、加熱し、そのアルギン
酸ナトリウムを溶解させる。このときの加熱温度は、沸
騰しない70℃以上から100℃未満が好ましく、より
好ましくは、75℃から90℃、さらに好ましくは80
℃から85℃である。加熱時間は、カルボキシル基含有
親水性物質が溶解すればよく、特に限定されないが、
0.5時間から2時間程度で十分である。次に、得られ
たカルボキシル基含有親水性高分子物質及び/又はその
加水分解生成物を含有するアルカリ性水溶液にリン酸化
合物、カルシウム化合物及び鉄化合物を混合する。When the treating agent of the present invention is preferably produced,
First, a carboxyl-containing hydrophilic polymer, for example, alginic acid, is heated in water containing an alkaline substance,
Hydrolyze and dissolve in water. For example, sodium alginate is present in water containing sodium hydroxide as an alkaline substance, and heated to dissolve the sodium alginate. The heating temperature at this time is preferably 70 ° C. or higher and less than 100 ° C., which does not boil, more preferably 75 ° C. to 90 ° C., and further preferably 80 ° C.
C to 85C. The heating time is not particularly limited as long as the carboxyl group-containing hydrophilic substance is dissolved,
About 0.5 to 2 hours is sufficient. Next, a phosphoric acid compound, a calcium compound, and an iron compound are mixed with the obtained alkaline aqueous solution containing a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof.
【0013】本発明の処理剤におけるカルボニル基含有
親水性高分子物質及び/又はその加水分解生成物とリン
酸化合物等の割合は、特に制約されないが、一般的に
は、カルボキシル基含有親水性高分子物質及び/又はそ
の加水分解生成物1重量部に対して、リン酸化合物は1
0〜10000重量部、好ましくは50〜5000重量
部、より好ましくは、100〜1000重量部の割合で
あり、カルシウム化合物は100〜200000重量
部、好ましくは500〜100000重量部、より好ま
しくは、1000〜50000重量部の割合であり、鉄
化合物は1〜10000重量部、好ましくは2〜500
0重量部、より好ましくは、5〜1000重量部の割合
である。The ratio of the carbonyl group-containing hydrophilic polymer substance and / or the hydrolysis product thereof to the phosphoric acid compound in the treating agent of the present invention is not particularly limited, but generally, the proportion of the carboxyl group-containing hydrophilic polymer is high. 1 part by weight of the molecular substance and / or its hydrolysis product
0 to 10000 parts by weight, preferably 50 to 5000 parts by weight, more preferably 100 to 1000 parts by weight, and the calcium compound is 100 to 200,000 parts by weight, preferably 500 to 100,000 parts by weight, more preferably 1000 to 1000 parts by weight. 50,000 parts by weight, and the iron compound is 1 to 10,000 parts by weight, preferably 2 to 500 parts by weight.
0 parts by weight, more preferably 5 to 1000 parts by weight.
【0014】本発明により塩化銅含有エッチング廃液を
処理するには、リン酸イオン、カルシウムイオン、鉄イ
オン及びカルボキシル基含有親水性高分子物質及び/又
はその加水分解生成物の存在下で、pHを5〜14、好
ましくは6〜12に調整すればよい。この場合、pH調
整剤としては、通常、アルカリ性物質が用いられるが、
このアルカリ性物質としては、特に制約はないが、スラ
ッジを減らすには水酸化ナトリウムの使用が好ましい。In order to treat the copper chloride-containing etching waste liquid according to the present invention, the pH is increased in the presence of a phosphate polymer, a calcium ion, an iron ion and a carboxyl group-containing hydrophilic polymer and / or a hydrolysis product thereof. It may be adjusted to 5 to 14, preferably 6 to 12. In this case, an alkaline substance is usually used as the pH adjuster,
The alkaline substance is not particularly limited, but it is preferable to use sodium hydroxide to reduce sludge.
【0015】リン酸化合物とカルシウム化合物との割合
は、リンとカルシウムとのモル比[P]/[Ca]で
0.001〜100、好ましくは0.01〜50であ
り、より好ましくは0.01〜10である。リン酸化合
物と鉄化合物との割合は、リンと鉄のモル比[P]/
[Fe]で1〜10000、好ましくは10〜500
0、より好ましくは50〜1000である。リン酸化合
物の割合は、被処理液中の銅イオン1モル当り、0.1
〜5000モル、好ましくは1〜1000モル、より好
ましくは1〜500モルである。The ratio between the phosphoric acid compound and the calcium compound is 0.001 to 100, preferably 0.01 to 50, and more preferably 0.1 to 50 in terms of the molar ratio [P] / [Ca] of phosphorus and calcium. 01 to 10. The ratio of the phosphoric acid compound to the iron compound is determined by the molar ratio of phosphorus to iron [P] /
[Fe] 1 to 10,000, preferably 10 to 500
0, more preferably 50 to 1,000. The ratio of the phosphoric acid compound is 0.1 mol / mol of copper ions in the liquid to be treated.
The amount is from 5,000 mol, preferably from 1 to 1,000 mol, more preferably from 1 to 500 mol.
【0016】本発明においては、前記被処理液中には、
カルボキシル基含有親水性高分子物質及び/又はその加
水分解生成物を存在させる。その割合は、リン酸化合物
1重量部当り、0.0001〜0.1重量部、好ましく
は0.0002〜0.01重量部、より好ましくは0.
0005〜0.01重量部である。In the present invention, the liquid to be treated contains:
A carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof is present. The ratio is 0.0001 to 0.1 part by weight, preferably 0.0002 to 0.01 part by weight, more preferably 0.1 to 0.1 part by weight per part by weight of the phosphoric acid compound.
0005 to 0.01 parts by weight.
【0017】本発明により塩化銅含有エッチング廃液を
処理する場合、その被処理液が酸性や中性の場合、処理
剤の添加後、沈殿が生じるようにpHを調整するのが好
ましい。そのpHは、一般的には、5〜14の範囲、好
ましくは6〜12の範囲である。When the etching waste liquid containing copper chloride is treated according to the present invention, if the liquid to be treated is acidic or neutral, it is preferable to adjust the pH so that precipitation occurs after the addition of the treating agent. The pH is generally in the range 5-14, preferably in the range 6-12.
【0018】本発明におけるpHの調整は、被処理液に
処理剤を添加後アルカリを加える方法、アルカリ水溶液
に対して、処理剤を添加した被処理液を添加する方法等
のいずれの方法によってもよい。In the present invention, the pH can be adjusted by any method such as a method of adding an alkali after adding a treating agent to a liquid to be treated, or a method of adding a treating liquid to which a treating agent is added to an aqueous alkali solution. Good.
【0019】本発明においては、凝集剤を併用するのが
好ましい。この場合の凝集剤は、フロックの凝集に用い
られているものであり、このようなものには、ポリアク
リルアミドのカチオン化変性物、ポリアクリル酸ジメチ
ルアミノエチルエステル、ポリメタクリル酸ジメチルア
ミノエチルエステル、ポリエチレンイミン、キトサン等
のカチオン性有機系凝集剤、ポリアクリルアミド等のノ
ニオン性有機系凝集剤、ポリアクリル酸、アクリルアミ
ドとアクリル酸との共重合体及びその塩等のアニオン性
有機系凝集剤が包含される。凝集剤の使用量は、水中に
おける濃度で、1〜200mg/L、好ましくは1〜1
00mg/Lである。In the present invention, a coagulant is preferably used in combination. The flocculant in this case is one used for flocculation of floc, such as a cationized modified product of polyacrylamide, poly (dimethylaminoethyl acrylate), poly (dimethylaminoethyl methacrylate), Includes cationic organic coagulants such as polyethyleneimine and chitosan; nonionic organic coagulants such as polyacrylamide; anionic organic coagulants such as polyacrylic acid, copolymers of acrylamide and acrylic acid, and salts thereof. Is done. The amount of the coagulant used is 1 to 200 mg / L, preferably 1 to 200 mg / L in water.
00 mg / L.
【0020】前記pH調整工程終了後の沈殿物のフロッ
クを含む被処理液は、固液分離処理される。この場合の
固液分離方法としては、慣用の方法、例えば、濾過分
離、遠心分離、沈降分離等が挙げられる。この固液分離
処理により液中の沈殿物は除去され、スラッジとなる。
このスラッジは銅を主体とするものであるが、不純物と
して塩素を含有しているので、これを除去する必要があ
る。本発明では、このスラッジ中の塩素を除去して銅を
回収する。スラッジ中に含まれる塩素を除去するために
は、そのスラッジに、アルカリ水溶液を加えて懸濁液を
作り、この懸濁液に高分子凝集剤を加えて液中の懸濁物
を凝集させ、この凝集懸濁液を分離させる。The liquid to be treated containing the floc of the precipitate after the completion of the pH adjustment step is subjected to a solid-liquid separation treatment. As the solid-liquid separation method in this case, a conventional method, for example, filtration separation, centrifugation, sedimentation and the like can be mentioned. By this solid-liquid separation treatment, precipitates in the liquid are removed and sludge is formed.
Although this sludge is mainly composed of copper, it contains chlorine as an impurity and must be removed. In the present invention, copper is recovered by removing chlorine in the sludge. In order to remove chlorine contained in the sludge, an alkaline aqueous solution is added to the sludge to form a suspension, and a polymer flocculant is added to the suspension to coagulate the suspension in the liquid. The aggregate suspension is separated.
【0021】スラッジに加えるアルカリ水溶液におい
て、そのアルカリとしては、水酸化ナトリウム、炭酸ナ
トリウム、炭酸水素ナトリウム、水酸化カリウム等が挙
げられる。水溶液中のアルカリ濃度は0.01〜10
%、好ましくは0.1〜5%である。スラッジに対して
アルカリ水溶液を加えて得られる懸濁液中のスラッジ懸
濁物の濃度は、0.1〜20%、好ましくは0.5〜1
0%である。In the aqueous alkali solution to be added to the sludge, examples of the alkali include sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide and the like. The alkali concentration in the aqueous solution is 0.01 to 10
%, Preferably 0.1 to 5%. The concentration of the sludge suspension in a suspension obtained by adding an aqueous alkali solution to the sludge is 0.1 to 20%, preferably 0.5 to 1%.
0%.
【0022】懸濁液に加える高分子凝集剤の具体例とし
ては、前記した各種のものが挙げられる。その添加量
は、0.1〜50ppm、好ましくは1〜10ppmで
ある。Specific examples of the polymer flocculant to be added to the suspension include those described above. The addition amount is 0.1 to 50 ppm, preferably 1 to 10 ppm.
【0023】懸濁液からの凝集懸濁物の分離は、濾過、
遠心、沈降等の慣用の固液分離法が採用される。The separation of the flocculated suspension from the suspension can be carried out by filtration,
Conventional solid-liquid separation methods such as centrifugation and sedimentation are employed.
【0024】前記のようにして銅を主体とする固形物
(スラッジ)が得られるが、この固形物中の銅含有率
は、乾燥物基準で、10%以上、好ましくは20%以
上、より好ましくは30%以上である。また、その固形
物中の塩素含有量は、乾燥物基準で、30%以下、好ま
しくは15%以下、より好ましくは5%以下である。こ
の固形物中に含まれる銅化合物は、通常、銅の水酸化物
の形態である。As described above, a solid (sludge) mainly composed of copper is obtained. The copper content in the solid is 10% or more, preferably 20% or more, more preferably 20% or more on a dry matter basis. Is 30% or more. Further, the chlorine content in the solid matter is 30% or less, preferably 15% or less, more preferably 5% or less on a dry matter basis. The copper compound contained in the solid is usually in the form of a copper hydroxide.
【0025】[0025]
【発明の効果】本発明の方法によれば、環境保全に大き
な問題となっていた塩化銅エッチング廃液を効率良く処
理し、廃液から再利用可能な銅を回収することができ
る。According to the method of the present invention, it is possible to efficiently treat copper chloride etching waste liquid, which has been a major problem in environmental protection, and recover reusable copper from the waste liquid.
【0026】[0026]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail by way of examples.
【0027】参考例1 500mlのビーカーで、1NのNaOH300mlに
2%のアルギン酸ナトリウムを添加した後、75℃〜8
5℃に加熱し30分以上1時間以内の時間攪拌する。攪
拌し終わった溶液を常温(25〜35℃)まで放冷した
後、10Lのビーカーで、前記常温のアルギン酸ナトリ
ウム溶液300mlと85%リン酸溶液5700mlを
混合した。次に、この液と塩化第二鉄水溶液(FeCl
3:37.5%(重量))を容量比4.9:0.1で混
合した。さらに、この混合液と35%塩化カルシウム水
溶液を容量比5:95で混合し処理剤[I]を得た。REFERENCE EXAMPLE 1 In a 500 ml beaker, 2% sodium alginate was added to 300 ml of 1N NaOH.
Heat to 5 ° C and stir for 30 minutes to 1 hour. After the stirred solution was allowed to cool to room temperature (25 to 35 ° C.), 300 ml of the room temperature sodium alginate solution and 5700 ml of 85% phosphoric acid solution were mixed in a 10 L beaker. Next, this solution and an aqueous solution of ferric chloride (FeCl
3 : 37.5% (weight)) at a volume ratio of 4.9: 0.1. Further, the mixed solution and a 35% aqueous solution of calcium chloride were mixed at a volume ratio of 5:95 to obtain a treating agent [I].
【0028】参考例2 参考例1において、塩化第二鉄水溶液の代わりに、ポリ
鉄塩水溶液(Fe3+11%以上含有)を使用して得られ
た混合液を処理剤[II]とする。REFERENCE EXAMPLE 2 A mixture obtained by using a polyiron salt aqueous solution (containing at least 11% of Fe 3+ ) in place of the ferric chloride aqueous solution in Reference Example 1 is referred to as a treating agent [II]. .
【0029】実施例1 pHが−0.98、銅イオン濃度118g/L、塩素濃
度250g/Lの銅エッチング廃液10mlに、処理剤
[I]3,000ppmを添加し3分間攪拌した。この
液を水酸化ナトリウム水溶液(1N)71mlに添加し
(添加量約9.2ml)、3分間撹拌してpH10の液
を得た。次に、高分子凝集剤ダイヤフロック(AP12
0C)を30ppm添加し2分間撹拌した。得られた沈
殿物を濾過した。処理液の銅イオンの濃度をICP装置
で測定すると、銅イオンの濃度は0.5mg/Lであっ
た。このときのスラッジ量は1.9g(絶乾)であっ
た。このスラッジを0.5Nの硝酸に溶解し銅と塩素の
濃度を、それぞれ、ICPとイオンクロマトグラフで測
定し、スラッジの銅と塩素の組成(乾燥物基準)をもと
めたところ、銅57%(重量)、塩素24%(重量)で
あった。次に、このスラッジ(含水率80%)を、20
0mlの水酸化ナトリウム水溶液(0.1N)に懸濁さ
せ(スラッジ濃度1%)、10分間撹拌し、ダイヤフロ
ックAP120Cを2.5ppm添加し、2分間撹拌し
た。濾過により固液分離し、乾燥後上述の方法で銅と塩
素の濃度を測定したところ、スラッジの銅と塩素の組成
は、銅62%(重量)、塩素1.2%(重量)であり、
高い銅回収率が得られた。また、スラッジからの銅の回
収に使用した水酸化ナトリウム水溶液の2分の1を再利
用して、次の廃液処理におけるスラッジの処理に使用し
たところ、同様の結果が得られた。Example 1 To 10 ml of a copper etching waste liquid having a pH of -0.98, a copper ion concentration of 118 g / L and a chlorine concentration of 250 g / L, 3,000 ppm of the treating agent [I] was added and stirred for 3 minutes. This liquid was added to 71 ml of an aqueous sodium hydroxide solution (1N) (addition amount: about 9.2 ml), and stirred for 3 minutes to obtain a liquid having a pH of 10. Next, a polymer flocculant Diafloc (AP12
0C) was added and stirred for 2 minutes. The resulting precipitate was filtered. When the concentration of copper ions in the treatment liquid was measured with an ICP apparatus, the concentration of copper ions was 0.5 mg / L. The amount of sludge at this time was 1.9 g (absolutely dry). The sludge was dissolved in 0.5N nitric acid, and the concentrations of copper and chlorine were measured by ICP and ion chromatography, respectively. The composition of copper and chlorine in the sludge (on a dry matter basis) was determined. Weight) and 24% (weight) chlorine. Next, this sludge (water content 80%) was
The suspension was suspended in 0 ml of an aqueous sodium hydroxide solution (0.1 N) (sludge concentration: 1%), stirred for 10 minutes, added with 2.5 ppm of Diafloc AP120C, and stirred for 2 minutes. The solid and liquid were separated by filtration, and after drying, the concentrations of copper and chlorine were measured by the method described above. The composition of copper and chlorine in the sludge was 62% by weight of copper and 1.2% by weight of chlorine.
High copper recovery was obtained. A similar result was obtained when one half of the aqueous sodium hydroxide solution used for the recovery of copper from the sludge was reused and used for sludge treatment in the next waste liquid treatment.
【0030】実施例2 実施例1の銅エッチング廃液10mlに、処理剤[I]
3,000ppmを添加し3分間攪拌した。この液に水
酸化ナトリウム水溶液(1N)71mlを添加し3分間
撹拌してpH10の液を得た。次に、高分子凝集剤ダイ
ヤフロック(AP120C)を5ppm添加(1ppm
ずつ添加)し2分間撹拌した。得られた沈殿物を濾過し
た。処理液の銅イオンの濃度をICP装置で測定する
と、銅イオンの濃度は0.4mg/Lであった。このと
きのスラッジ量は1.8g(絶乾)であった。このスラ
ッジを0.5Nの硝酸に溶解し銅と塩素の濃度を、それ
ぞれ、ICPとイオンクロマトグラフで測定し、スラッ
ジの銅と塩素の組成をもとめたところ、銅58%(重
量)、塩素23%(重量)であった。次に、このスラッ
ジを、200mlの水酸化ナトリウム水溶液(0.1
N)に懸濁させ(スラッジ濃度1%)、10分間撹拌
し、ダイヤフロックAP120Cを2.5ppm添加
し、2分間撹拌した。濾過により固液分離後上述の方法
で銅と塩素の濃度を測定したところ、スラッジの組成
は、銅60%(重量)、塩素1.5%(重量)であり、
高い銅回収率が得られた。Example 2 Treatment agent [I] was added to 10 ml of the copper etching waste liquid of Example 1.
3,000 ppm was added and stirred for 3 minutes. To this solution was added 71 ml of an aqueous sodium hydroxide solution (1N), and the mixture was stirred for 3 minutes to obtain a solution having a pH of 10. Next, 5 ppm of polymer flocculant Diafloc (AP120C) was added (1 ppm).
) And stirred for 2 minutes. The resulting precipitate was filtered. When the concentration of copper ions in the treatment liquid was measured with an ICP apparatus, the concentration of copper ions was 0.4 mg / L. The amount of sludge at this time was 1.8 g (absolutely dry). This sludge was dissolved in 0.5N nitric acid, and the concentrations of copper and chlorine were measured by ICP and ion chromatography, respectively. When the composition of copper and chlorine in the sludge was determined, 58% (weight) of copper and 23% of chlorine were detected. % (Weight). Next, this sludge was added to a 200 ml aqueous solution of sodium hydroxide (0.1 ml).
N) (1% sludge concentration) and stirred for 10 minutes, 2.5 ppm of Diafloc AP120C was added, and the mixture was stirred for 2 minutes. When the concentration of copper and chlorine was measured by the above-mentioned method after solid-liquid separation by filtration, the composition of the sludge was copper 60% (weight) and chlorine 1.5% (weight),
High copper recovery was obtained.
【0031】実施例3 実施例1の銅エッチング廃液10mlに、処理剤[II]
3,000ppmを添加し3分間攪拌した。この液に水
酸化ナトリウム水溶液(1N)70mlを添加し、3分
間撹拌してpH10の液を得た。次に、高分子凝集剤ダ
イヤフロック(AP120C)を5ppm添加(1pp
mずつ添加)し2分間撹拌した。得られた沈殿物を濾過
した。処理液の銅イオンの濃度をICP装置で測定する
と、銅イオンの濃度は0.6mg/Lであった。このと
きのスラッジ量は2.0g(絶乾)であった。このスラ
ッジを0.5Nの硝酸に溶解し銅と塩素の濃度を、それ
ぞれ、ICPとイオンクロマトグラフで測定し、スラッ
ジの銅と塩素の組成をもとめたところ、銅54%(重
量)、塩素26%(重量)であった。次に、このスラッ
ジを、100mlの水酸化ナトリウム水溶液(0.1
N)に懸濁させ(スラッジ濃度2%)、10分間撹拌
し、ダイヤフロックAP120Cを2.5ppm添加
し、2分間撹拌した。濾過により固液分離し、乾燥後上
述の方法で銅と塩素の濃度を測定したところ、スラッジ
の銅と塩素の組成は、銅59%(重量)、塩素2%(重
量)であり、高い銅回収率が得られた。Example 3 A treating agent [II] was added to 10 ml of the copper etching waste liquid of Example 1.
3,000 ppm was added and stirred for 3 minutes. To this solution was added 70 ml of an aqueous solution of sodium hydroxide (1N), and the mixture was stirred for 3 minutes to obtain a solution having a pH of 10. Next, 5 ppm of a polymer flocculant Diafloc (AP120C) was added (1 pp).
m) and stirred for 2 minutes. The resulting precipitate was filtered. When the concentration of copper ions in the treatment liquid was measured with an ICP apparatus, the concentration of copper ions was 0.6 mg / L. The amount of sludge at this time was 2.0 g (absolutely dry). This sludge was dissolved in 0.5N nitric acid, and the concentrations of copper and chlorine were measured by ICP and ion chromatography, respectively. When the composition of copper and chlorine in the sludge was determined, copper 54% (weight) and chlorine 26 % (Weight). Next, the sludge was added to a 100 ml aqueous solution of sodium hydroxide (0.1 ml).
N) (2% sludge concentration) and stirred for 10 minutes, 2.5 ppm of Diafloc AP120C was added, and the mixture was stirred for 2 minutes. The solids and liquids were separated by filtration, and after drying, the concentrations of copper and chlorine were measured by the method described above. The composition of copper and chlorine in the sludge was 59% copper (by weight) and 2% chlorine (by weight). A recovery was obtained.
【0032】実施例4 実施例1の銅エッチング廃液10mlに、処理剤[I]
3,000ppmを添加し3分間攪拌した。この液を水
酸化ナトリウム水溶液(0.5N)71mlにpHが1
0になるよう添加し(添加量約4.6ml)、3分間撹
拌した。次に、高分子凝集剤ダイヤフロック(AP12
0C)を30ppm添加し2分間撹拌した。得られた沈
殿物を濾過した。このときのスラッジ量は0.9g(絶
乾)であった。このスラッジを0.5Nの硝酸に溶解し
銅と塩素の濃度を、それぞれ、ICPとイオンクロマト
グラフで測定し、スラッジの銅と塩素の組成をもとめた
ところ、銅57%(重量)、塩素5%(重量)であっ
た。Example 4 A treatment agent [I] was added to 10 ml of the copper etching waste liquid of Example 1.
3,000 ppm was added and stirred for 3 minutes. This solution was added to 71 ml of an aqueous sodium hydroxide solution (0.5 N) at a pH of 1
0 (added amount: about 4.6 ml) and stirred for 3 minutes. Next, a polymer flocculant Diafloc (AP12
0C) was added and stirred for 2 minutes. The resulting precipitate was filtered. The amount of sludge at this time was 0.9 g (absolutely dry). This sludge was dissolved in 0.5N nitric acid, and the concentrations of copper and chlorine were measured by ICP and ion chromatography, respectively. When the composition of copper and chlorine in the sludge was determined, 57% (weight) of copper and 5% of chlorine were detected. % (Weight).
───────────────────────────────────────────────────── フロントページの続き (71)出願人 000005979 三菱商事株式会社 東京都千代田区丸の内2丁目6番3号 (74)上記3名の代理人 100074505 弁理士 池浦 敏明 (72)発明者 辰巳 憲司 茨城県つくば市小野川16番3 工業技術院 資源環境技術総合研究所内 (72)発明者 和田 愼二 茨城県つくば市小野川16番3 工業技術院 資源環境技術総合研究所内 (72)発明者 湯川 恭啓 茨城県つくば市千現2−1−6 三菱商事 プロジェクト開発部環境資源研究所内 Fターム(参考) 4D015 BA19 BA23 BB05 CA20 DB02 DB15 DB23 DB32 EA14 EA15 FA01 FA11 4D038 AA08 AB68 AB81 BB13 BB18 4D062 BA19 BA23 BB05 CA20 DB02 DB15 DB23 DB32 EA14 EA15 FA01 FA11 4K001 AA09 BA21 DB08 DB23 DB26 ──────────────────────────────────────────────────続 き Continued on the front page (71) Applicant 000005979 Mitsubishi Corporation 2-6-3 Marunouchi, Chiyoda-ku, Tokyo (74) The above three agents 100074505 Patent Attorney Toshiaki Ikeura (72) Inventor Kenji Tatsumi Ibaraki 16-3 Onogawa, Tsukuba, Japan Prefectural Institute of Technology, Resource and Environmental Technology Research Institute (72) Inventor Shinji Wada 16-3 Onogawa, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor, Yasuhiro Yukawa Ibaraki Prefecture 2-1-6 Sengen, Tsukuba Mitsubishi Corporation Project Development Department Environmental Resources Research Laboratory F-term (reference) 4D015 BA19 BA23 BB05 CA20 DB02 DB15 DB23 DB32 EA14 EA15 FA01 FA11 4D038 AA08 AB68 AB81 BB13 BB18 4D062 BA19 BA23 BB05 CA20 DB02 DB15 DB23 DB32 EA14 EA15 FA01 FA11 4K001 AA09 BA21 DB08 DB23 DB26
Claims (7)
法において、(i)リン酸イオン、(ii)カルシウムイ
オン、(iii)鉄イオン及び(iv)カルボキシル基含有
親水性高分子物質及び/又はその加水分解生成物の存在
下で、該被処理液のpHを5〜14の範囲に調整して、
該溶存銅イオンを難溶性物質として沈殿させることを特
徴とする塩化銅含有エッチング廃液の処理方法。1. A method for treating a copper chloride-containing etching waste liquid, comprising: (i) a phosphate ion, (ii) a calcium ion, (iii) an iron ion and (iv) a carboxyl group-containing hydrophilic polymer substance and / or In the presence of the hydrolysis product, the pH of the liquid to be treated is adjusted to a range of 5 to 14,
A method for treating a copper chloride-containing etching waste liquid, wherein the dissolved copper ions are precipitated as a hardly soluble substance.
が、(i)アルギン酸もしくはその塩又は(ii)アルギ
ン酸もしくはその塩と他のアニオン基含有親水性高分子
物質との混合物からなる請求項1の方法。2. The carboxyl group-containing hydrophilic polymer substance comprises (i) alginic acid or a salt thereof, or (ii) a mixture of alginic acid or a salt thereof and another hydrophilic polymer containing an anion group. the method of.
のいずれかの方法。3. The method according to claim 1, wherein a coagulant is added to said liquid.
Either way.
めの薬剤であって、(i)リン酸化合物、(ii)カルシ
ウム化合物、(iii)鉄化合物及び(iv)カルボキシル
基含有親水性高分子物質及び/又はその加水分解生成物
とからなることを特徴とする銅含有エッチング廃液処理
剤。4. An agent for treating an etching waste liquid containing copper chloride, comprising (i) a phosphate compound, (ii) a calcium compound, (iii) an iron compound, and (iv) a carboxyl group-containing hydrophilic polymer substance. And / or a hydrolysis product thereof.
が、(i)アルギン酸もしくはその塩又は(ii)アルギ
ン酸もしくはその塩と他のアニオン基含有親水性高分子
物質との混合物からなる請求項4の処理剤。5. The carboxyl group-containing hydrophilic polymer substance comprises (i) alginic acid or a salt thereof or (ii) a mixture of alginic acid or a salt thereof and another hydrophilic polymer containing an anion group. Treatment agent.
4〜5のいずれかの処理剤。6. The treating agent according to claim 4, wherein the phosphoric acid compound is phosphoric acid.
た沈殿物を液中から分離して得られたスラッジに、アル
カリ水溶液を加えて懸濁液を作り、この懸濁液に高分子
凝集剤を加えて液中の懸濁物を凝集させ、この凝集懸濁
物を分離させることを特徴とする銅を回収する方法。7. An aqueous alkali solution is added to sludge obtained by separating the precipitate obtained by the method according to claim 1 from the liquid to form a suspension. A method for recovering copper, comprising adding a polymer flocculant to flocculate a suspension in a liquid, and separating the flocculated suspension.
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CN117819760A (en) * | 2024-01-03 | 2024-04-05 | 中芯恒润环境科技(北京)有限公司 | Foil washing wastewater treatment method |
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