JPH03130400A - Method for recovering valuable metallic matter from waste plating solution - Google Patents
Method for recovering valuable metallic matter from waste plating solutionInfo
- Publication number
- JPH03130400A JPH03130400A JP12187989A JP12187989A JPH03130400A JP H03130400 A JPH03130400 A JP H03130400A JP 12187989 A JP12187989 A JP 12187989A JP 12187989 A JP12187989 A JP 12187989A JP H03130400 A JPH03130400 A JP H03130400A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- soln
- plating solution
- content
- waste liquid
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 77
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims description 38
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 230000008929 regeneration Effects 0.000 claims abstract description 23
- 238000011069 regeneration method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002739 metals Chemical class 0.000 claims abstract description 21
- 239000013522 chelant Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 230000001172 regenerating effect Effects 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 20
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 238000001914 filtration Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、鋼板のメッキ処理等において排出されるメッ
キ廃液からＮｉ、Ｚｎ等の金属有価物を回収し、メッキ
液の一部として再利用する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention recovers valuable metals such as Ni and Zn from the plating waste liquid discharged during the plating process of steel plates, etc., and reuses them as part of the plating liquid. Regarding how to.
［従来の技術］
一般に、メッキ廃液中には、不純物以外にＮｉ、Ｚｎ等
の有価金属が多量に含有されている。そこでこれら有価
金属を含む洗浄廃液をそのまま廃棄せずに、メッキ液と
して再利用しようとする技術が、例えば特開昭６２−２
３５４９９号公報に開示されている。[Prior Art] Generally, plating waste liquid contains a large amount of valuable metals such as Ni and Zn in addition to impurities. Therefore, a technique for reusing cleaning waste liquid containing valuable metals as a plating solution without directly disposing of it is proposed, for example, in Japanese Patent Laid-Open No. 62-11
It is disclosed in Japanese Patent No. 35499.
この公報技術においては、同一メッキラインで２種類以
上のメッキ液を切り換えて電気メッキを行うもので、切
り換え時まで使用していたメッキ液をメッキ槽から抜取
り、そのメッキ槽を洗浄した後、洗浄廃液に過酸化水素
を添加して鉄イオンを３価の鉄イオンにした後、水酸化
ナトリウムを添加し水酸化第２鉄として沈澱させ、この
沈澱を除去して脱鉄処理をなし、次いでキレート樹脂に
通して鉄以外の２価の陽イオンを吸着させ、その後キレ
ート樹脂を硫酸により洗浄して有価陽イオンとして回収
し、続いて脱硫酸化処理し、その後濃縮処理してメッキ
液として再利用を図るものである。In this technique, electroplating is performed by switching between two or more types of plating solutions on the same plating line. Hydrogen peroxide is added to the waste liquid to convert iron ions into trivalent iron ions, sodium hydroxide is added to precipitate ferric hydroxide, this precipitate is removed to perform iron removal treatment, and then chelation is performed. The resin is passed through a resin to adsorb divalent cations other than iron, and then the chelate resin is washed with sulfuric acid to recover valuable cations, followed by desulfation treatment, and then concentration treatment and reuse as a plating solution. This is what we aim to do.
［発明が解決しようとする課題］
しかしながら、上記公報技術では、■後記実施例に示す
ように、有価金属の回収率が低いため、有価金属の回収
益よりも設備費およびランニングコストの方が高くつい
てしまう。また、■回収過程の各工程で再度、廃液が発
生するため、特に濾過材およびキレート樹脂の再生工程
で高濃度の廃液が生じ、これらを処理するための水処理
設備が必要となり、この点でも設備費および運転費が上
昇する。さらに、■回収工程が複雑なため、運転条件が
かなり厳しいものとなる。このため、装置を熟知した作
業者が常時運転および点検を続ける必要があり、煩にた
えない。[Problems to be solved by the invention] However, in the above-mentioned published technology, as shown in ■Examples below, the recovery rate of valuable metals is low, so the equipment costs and running costs are higher than the recovery of valuable metals. It sticks to me. In addition, as waste liquid is generated again in each step of the recovery process, particularly in the regeneration process of filter media and chelate resin, highly concentrated waste liquid is generated, and water treatment equipment is required to treat this. Equipment and operating costs will increase. Furthermore, (1) the recovery process is complicated, so the operating conditions are quite severe. Therefore, it is necessary for a worker who is familiar with the device to constantly operate and inspect the device, which is a hassle.
そこで本発明の主たる目的は、回収効率がきわめて高く
、かつたとえば前述の設備を有効に活用でき、高い回収
効率を示すことに鑑みれば、設備費およびランニングコ
ストがきわめて低い、有価金属を効率的に回収し再利用
する方法を提供することにある。Therefore, the main purpose of the present invention is to efficiently recover valuable metals, which has extremely high recovery efficiency, can effectively utilize the above-mentioned equipment, and exhibits high recovery efficiency, and which has extremely low equipment costs and running costs. The idea is to provide a way to collect and reuse them.
［課題を解決するための手段］
上記課題は、メッキ液中の不純物を、濾材およびキレー
ト樹脂のうち少なくとも一方の不純物除去材に前記メッ
キ廃液を通すことで除去した後、メッキ槽へ戻し再利用
を図るとともに、前記不純物除去材の能力低下時水を通
してその再生を図る方法において、
再利用のための運転期間と前記不純物除去材の再生運転
期間とを交互に定め、再生運転期間中において、前記不
純物除去材に純水を通水し、その再生期間の金属有価物
含有量が多い段階において前記不純物除去材を通って排
出される高濃度の金属有価物を含有する廃液を系外に排
出せずにメッキ液の一部として使用するとともに、前記
再生期間の金属有価物含有量が少ない段階において排出
される廃液を系外に排出することで解決できる。[Means for solving the problem] The above problem is to remove impurities in the plating solution by passing the plating waste solution through at least one impurity removal material of a filter medium and a chelate resin, and then return it to the plating tank for reuse. In this method, when the capacity of the impurity removing material decreases, the impurity removing material is regenerated by passing water through it. Pure water is passed through the impurity removing material, and the waste liquid containing a high concentration of metal valuables that is discharged through the impurity removing material during the regeneration period when the metal valuables content is high is discharged to the outside of the system. This can be solved by using the plating solution as part of the plating solution and discharging the waste solution from the system during the regeneration period when the content of valuable metals is low.
［作 用］
本発明者らは、不純物除去材の再生過程で、不純物除去
材を通った再生廃液の成分について着目したところ、そ
の再生過程の前半と後半とで排出される再生廃液の成分
濃度として、前半ではＮｉ、Ｚｎを多量に含有し、不純
物含量は極めて少ないのに対し、後半では逆に、不純物
含量が増大し、Ｎｉ、Ｚｎが激減するという傾向がある
ことが判った。[Function] The present inventors focused on the components of the recycled waste liquid that passed through the impurity removing material during the regeneration process of the impurity removing material, and found that the component concentration of the recycled waste liquid discharged in the first and second half of the regeneration process. It was found that the first half contains a large amount of Ni and Zn and the impurity content is extremely low, whereas in the second half, the impurity content increases and Ni and Zn drastically decrease.
そこで、本発明では、再生過程の前半と後半とで、さら
に詳細には再生工程の各段階で金属有価物含有量が異な
ることに鑑みて、その含有量の多少に応じて、再生廃液
の処理方法を異ならせ、金属有価物含有量が多い再生廃
液をメッキ液として循環再利用する一方、金属有価物含
有量が少ない再生廃液は逆に不純物が多いので系外へ廃
棄するようにしである。かくして、従来系外に廃棄され
ていた金属有価物まで回収できるから、後記実施例に示
されているように、回収効率が著しく高まる。Therefore, in the present invention, in view of the fact that the content of valuable metals differs between the first half and the second half of the regeneration process, and more specifically at each stage of the regeneration process, the recycled waste liquid is treated according to the content. The method is different: recycled waste liquid with a high content of valuable metals is recycled and reused as a plating solution, while recycled waste liquid with a low content of valuable metals has a lot of impurities, so it is disposed of outside the system. In this way, valuable metals that were conventionally discarded outside the system can be recovered, so the recovery efficiency is significantly increased, as shown in the Examples below.
さらに、本発明は、前記公報例の設備が設置されている
もとでは、その設備をそのまま利用できるとともに、不
純物の再生にあたり、単に純水を不純物除去材に通水す
るのみで格別の操作を必要とせず簡易な運転が可能であ
る。Furthermore, the present invention allows the equipment described in the above-mentioned publication to be used as is, and requires special operation by simply passing pure water through the impurity removal material when regenerating impurities. Easy operation is possible without the need for
しかも、前記の再生廃液を新たなメッキ液としてメッキ
液循環サイクルに戻すので、再生廃液処理量が低減し、
廃液濃度も低下でき、再生廃液処理装置の負担およびラ
ンニングコストが低減する。Moreover, since the recycled waste liquid is returned to the plating liquid circulation cycle as a new plating liquid, the amount of recycled waste liquid to be processed is reduced.
The concentration of waste liquid can also be reduced, reducing the burden on the recycled waste liquid treatment equipment and the running costs.
また、本発明では、不純物除去材の再生用水として純水
を使用し、工業用水を使用しないため、そこに含まれる
Ｃｌイオン等の混入を避けることができ、メッキ性状の
悪化を防止できる。Further, in the present invention, since pure water is used as the water for recycling the impurity removal material and industrial water is not used, it is possible to avoid contamination of Cl ions, etc. contained therein, and it is possible to prevent deterioration of the plating properties.
［発明の具体的構成］ 以下本発明を図面等に基づきさらに具体的に説明する。[Specific structure of the invention] The present invention will be explained in more detail below based on the drawings and the like.
まず従来のメッキ廃液処理法、すなわち前記公報技術を
基礎とした方法を第５図により説明すると、メッキ廃液
１０１は前処理として、ＰＨ調整・酸化処理工程１０２
において、ＰＨを約５に調整し、Ｆｅ”イオンをＦｅ（
ＯＨ）、としてフロック化させた後、濾過工程１０３に
おいて、フィルターで濾過することによってＦｅ３＋を
除去する。続いて、以上の前処理後の廃液を陽イオン交
換樹脂・キレート樹脂１０４中に通し、さらに陰イオン
交換樹脂１０５により不純物を除去して濃縮（１次濃縮
）する。次いでこの廃液を蒸発濃縮１０６（２次濃縮）
し、２０〜３０倍の濃縮液を得る。その後、金属有価物
を多く含む液を回収１０７シ、これをメッキ液１０８と
して再利用するものである。First, a conventional plating waste liquid treatment method, that is, a method based on the above-mentioned publication technique, will be explained with reference to FIG.
, the pH was adjusted to about 5, and the Fe'' ions were changed to Fe(
After flocculating as OH), in a filtration step 103, Fe3+ is removed by filtering with a filter. Subsequently, the waste liquid after the above pretreatment is passed through a cation exchange resin/chelate resin 104, and further impurities are removed by an anion exchange resin 105 and concentrated (primary concentration). Next, this waste liquid is evaporated and concentrated 106 (secondary concentration)
to obtain a 20- to 30-fold concentrated solution. Thereafter, the liquid containing a large amount of metal valuables is collected 107 and reused as a plating liquid 108.
これに対して、本発明に係る回収方法を第１図に示した
。In contrast, a recovery method according to the present invention is shown in FIG.
すなわち、少なくともメッキ液の再生過程で、メッキセ
ル（メッキライン）ｌからのメッキ液の一部をメッキ液
タンク２に導入し、このメッキ液を除鉄サイクル３を通
じて、除鉄設備４に供給する。除鉄設備４は濾過塔４１
およびキレート塔４２を含み、濾過塔４１では、適宜の
濾過材料たとえば濾過砂によりメッキ液中の８８分を除
去し、キレート塔４２では、キレート樹脂によりＦｅ’
＋イオンを除去する。除鉄後のＮｉ、Ｚｎに富むメッキ
液は再びメッキ液タンク２に返送し、さらにその一部を
メッキセル１に返送して、鋼板処理などのメッキ処理に
供される。また、メッキ処理過程でメッキ液は希釈され
るので、適宜の時期において濃縮サイクル５を通して蒸
発塔６に導き、濃縮処理してメッキ液タンク２に戻し濃
縮メッキ液をメッキセル１に供給する。That is, at least in the process of regenerating the plating solution, a part of the plating solution from the plating cell (plating line) 1 is introduced into the plating solution tank 2, and this plating solution is supplied to the iron removal equipment 4 through the iron removal cycle 3. Iron removal equipment 4 is a filtration tower 41
In the filtration tower 41, 88% of the plating solution is removed using a suitable filtration material such as filter sand, and in the chelate tower 42, Fe' is removed using a chelate resin.
+ Removes ions. After iron removal, the plating solution rich in Ni and Zn is returned to the plating solution tank 2, and a part of it is returned to the plating cell 1, where it is used for plating processing such as steel plate processing. Furthermore, since the plating solution is diluted during the plating process, it is led to an evaporation tower 6 through a concentration cycle 5 at an appropriate time, subjected to concentration treatment, and returned to the plating solution tank 2 to supply the concentrated plating solution to the plating cell 1.
他方、本発明では、メッキ液として混入すると不適な８
８分やＦｅ３＋イオンなどの不純物を除去するための不
純物除去材、すなわち上記例では濾過砂およびキレート
樹脂の再生過程で、これを純水タンク７からの純水を通
水することにより再生する。純水を用いるのは、工業用
水を用いると、再生廃液中に多量のＣｌイオンが含まれ
ることになり、このＣ１イオンが循環されてメッキ液中
に混入され、メッキ性状を悪化させることを防止するた
めである。On the other hand, in the present invention, 8
In the process of regenerating the impurity removing material for removing impurities such as 8 min and Fe3+ ions, that is, the filter sand and chelate resin in the above example, this is regenerated by passing pure water from the pure water tank 7 through it. Purified water is used because if industrial water is used, a large amount of Cl ions will be included in the recycled waste liquid, and this prevents these Cl ions from being circulated and mixed into the plating solution and deteriorating the plating properties. This is to do so.
さらに、除鉄設備４において、メッキ液を再生して新メ
ッキ液として再利用を図る運転期間と、純水を用いての
不純物除去の再生期間とを定めそれら期間の間欠的操業
を行う。例えば、メッキ液再生再利用期間を２０時間、
不純物除去材の再生時間８時間で、交互に繰り返しなが
ら運転される。Further, in the iron removal equipment 4, an operation period for regenerating the plating solution and reusing it as a new plating solution and a regeneration period for removing impurities using pure water are determined, and intermittent operation is performed during these periods. For example, if the plating solution reuse period is 20 hours,
The regeneration time of the impurity removal material is 8 hours, and the operation is repeated alternately.
上記再生工程は、第２図および第３図の横軸に示す各段
階を有するが、その各段階の一部を第５図（ａｌ〜（ｆ
ｌにより詳説すると、まず（ａ）濾過塔４１にメッキ液
Ｅを供給し、原液置換を行うとともに、排水Ｅｕを回収
しメッキ液として再利用を図る。キレート塔４２では待
機状態である。次に、（ｂｌ濾過塔４１をメッキ液Ｅに
よる通液状態とし、キレート塔４２に原液充填を行い、
さらに（Ｃ）原液置換して排水Ｅｕを回収してメッキ液
として再利用を図る。（ｄｌその後、濾過塔４１．キレ
ート塔４２の両塔にメッキ液を通液して、メッキ液の洗
浄を行う。所定時間経過後、濾過材、キレート材の再生
のため、（ｅｌ濾過塔４１に純水Ｗを供給し、濾過塔４
１およびキレート塔４２の原液押出しをする。排出され
るメッキ液Ｅはメッキ液貯蔵タンクへ供給し、廃棄用と
する。The above-mentioned regeneration process has each stage shown on the horizontal axis in FIGS. 2 and 3, and a part of each stage is shown in FIG.
Specifically, (a) plating solution E is supplied to the filtration tower 41 to replace the stock solution, and the waste water Eu is recovered and reused as a plating solution. The chelate tower 42 is in a standby state. Next, (the BL filtration tower 41 is brought into a state where the plating solution E is passed through, the chelate tower 42 is filled with the stock solution,
Furthermore, (C) the undiluted solution is replaced and the wastewater Eu is recovered and reused as a plating solution. (dl) After that, the plating solution is passed through both the filter tower 41 and the chelate tower 42 to wash the plating solution. Pure water W is supplied to the filtration tower 4.
1 and the chelate tower 42 are extruded. The discharged plating solution E is supplied to a plating solution storage tank for disposal.
最後に＋ｆ）濾過塔４１およびキレート塔４２内からの
水抜きをし、排水Ｅｕを回収してメッキ液として再利用
を図る。Finally, +f) Water is drained from the filtration tower 41 and the chelate tower 42, and the waste water Eu is recovered and reused as a plating solution.
本発明では、不純物除去材の再生過程で前述のように、
純水を濾過塔４１の濾過材およびキレート塔４２のキレ
ート樹脂に通水しその再生を図る。In the present invention, as described above, in the regeneration process of the impurity removal material,
Pure water is passed through the filter material of the filter tower 41 and the chelate resin of the chelate tower 42 to regenerate them.
この再生過程の金属有価物含有量が多い段階（ａｌ、（
Ｃ１および（ｆｌにおいては、バルブ８Ａを開、バルブ
８Ｂを閉とし、通水後の液をメッキ液タンク２に供給し
、Ｎ１、Ｚｎ等の有価金属を多く含む液を回収しメッキ
液として再利用を図る。また、再生過程の金属有価物含
有量の少ないその他の段階では、バルブ８Ａを閉、バル
ブ８Ｂを開とし、Ｎｉ１Ｚｎ等の金属有価物濃度が低下
し、不純物含量が多くなった再生廃液を系外へ排出する
。この場合、具体的には、Ｎｉａ度が １２００〜１４
００ｍｇ／ ｆ ＸＺ ｎ濃度が５００〜７００■／１
の範囲以下になった時に排出するのが好ましい。This regeneration process is at a stage where the content of valuable metals is high (al, (
In C1 and (fl), valve 8A is opened and valve 8B is closed, and the liquid after passing water is supplied to plating liquid tank 2, and the liquid containing a large amount of valuable metals such as N1 and Zn is recovered and reused as plating liquid. In addition, in other stages of the regeneration process where the content of valuable metals is low, valve 8A is closed and valve 8B is opened, so that the concentration of valuable metals such as Ni1Zn decreases and the content of impurities increases. The waste liquid is discharged to the outside of the system.In this case, specifically, the Nia degree is 1200 to 14.
00mg/f XZ n concentration is 500~700■/1
It is preferable to discharge the water when it falls below the range of .
上記した再生過程の主に前半におけるＮｉ、 Ｚｎを高
濃度に含む再生廃液は、前述したように、メッキ液タン
ク２に供給されるが、他のメッキ液と同様、蒸発塔６へ
導入され所定濃度まで濃縮される。The recycled waste liquid containing a high concentration of Ni and Zn mainly in the first half of the above-mentioned regeneration process is supplied to the plating liquid tank 2 as described above, but like other plating liquids, it is introduced into the evaporation tower 6 and is heated to a predetermined level. concentrated to a certain concentration.
また再生廃液のメッキ液タンク２への移行により、再生
廃液中に混入する少量の不純物は、再生廃液を他のメッ
キ液と一緒にして再び除鉄サイクル３を循環させること
で除去する。Further, a small amount of impurities mixed in the recycled waste liquid by transferring it to the plating liquid tank 2 is removed by circulating the recycled waste liquid together with other plating liquid through the iron removal cycle 3 again.
本発明法は、メッキ液に限らず、原液をイオン交換、キ
レート樹脂処理、濾過処理して不純物を除去する工程で
あれば応用可能である。The method of the present invention is applicable not only to plating solutions but also to any process in which impurities are removed by ion exchange, chelate resin treatment, and filtration treatment of a stock solution.
［実施例］ 次に実施例により本発明の効果を明らかにする。[Example] Next, the effects of the present invention will be clarified through examples.
第２図および第３図は、除鉄設備の不純物再生過程での
洗浄廃液中のＮ１、Ｚｎ濃度の分析結果を示すものであ
り、第２図はキレート塔での結果、第３図は濾過塔での
結果を示している。再生工程は両図の横軸に記載したよ
うに、前述の第４図で説明した原液充填、原液置換、水
抜、水押等の諸工程からなる。第２図および第３図から
一見して明らかなように、廃液中のＮｉ、Ｚｎ濃度の特
に高いのは、キレート塔では原液置換段階と水抜段階で
ある。また、濾過塔では原液置換段階である。Figures 2 and 3 show the analysis results of N1 and Zn concentrations in the washing waste liquid during the impurity regeneration process of iron removal equipment. Showing the results in the tower. As shown on the horizontal axes of both figures, the regeneration process consists of various processes such as filling the undiluted solution, replacing the undiluted solution, draining water, and pressing water as explained in FIG. 4 above. As is clear at first glance from FIGS. 2 and 3, the Ni and Zn concentrations in the waste liquid are particularly high in the stock solution replacement stage and the water removal stage in the chelate tower. Furthermore, the filtration tower is in the stage of replacing the raw solution.
そこで本発明にしたがって、これらの各段階から廃液を
回収して、メッキ液タンクに供給してメッキ液として回
収した。Therefore, in accordance with the present invention, the waste liquid was collected from each of these stages, supplied to a plating liquid tank, and recovered as a plating liquid.
かかる本発明法の適用の条件、効果を従来法と比較して
第１表に示す。なお、ここで従来法とは、前記特開昭６
２−２３５４９９号公報記載技術をいう。The conditions and effects of applying the method of the present invention are shown in Table 1 in comparison with the conventional method. Note that the conventional method here refers to
Refers to the technology described in Publication No. 2-235499.
第１表
第１表から明らかなように、本発明によれば、Ｎｉ、Ｚ
ｎの回収効率を大幅に向上させつつ、設備費をも大幅に
低減させることができる。Table 1 As is clear from Table 1, according to the present invention, Ni, Z
It is possible to significantly improve the recovery efficiency of n and also significantly reduce equipment costs.
［発明の効果］
以上の通り、本発明法によれば、回収効率がきわめて高
く、かつたとえば前述の設備を有効に活用でき、高い回
収効率を示すことに鑑みれば、設備費およびランニング
コストがきわめて低く、有価金属を効率的に回収し再利
用を図ることができる。[Effects of the Invention] As described above, according to the method of the present invention, the collection efficiency is extremely high, and for example, the above-mentioned equipment can be used effectively, and in view of the high collection efficiency, the equipment cost and running cost are extremely low. It is possible to efficiently recover and reuse valuable metals.
第１図は本発明法を示す処理工程図、第２図および第３
図はそれぞれキレート塔および濾過塔における不純物除
去材の再生過程で発生する洗浄廃液のＮｉＸＺｎ濃度を
示すグラフで、第４図（ａ）〜（ｆ）は本発明の再生工
程の一部の詳細を順に示す概要説明図、第５図は従来法
に係る処理工程図である。
１・・・メッキセル（メッキライン）、２・・・メッキ
液タンク、４・−・除鉄設備、７・・・純水タンク、４
１・・・濾過塔、４２・・・キレート塔。
第
図
第
２
図
第
図
（α）
（ｄ）
第
図
匡０木
［＝＝コメー／キ哀
（ｂｌ
（Ｃ）
（ｅ）
（ｆ）
手続補正書
（方式）
％式％
事件の表示
平成１年
特許願
第１２
８７９号
２゜
発明の名称
メッキ廃液からの金属有価物の回収方法３゜
補正をする者
事件との関係Figure 1 is a process diagram showing the method of the present invention, Figures 2 and 3 are
The figures are graphs showing the NiXZn concentration of the washing waste liquid generated during the regeneration process of the impurity removal material in the chelate tower and the filtration tower, respectively, and Figures 4(a) to 4(f) show details of part of the regeneration process of the present invention. The schematic explanatory diagrams shown in order and FIG. 5 are treatment process diagrams according to the conventional method. 1... Plating cell (plating line), 2... Plating liquid tank, 4... Iron removal equipment, 7... Pure water tank, 4
1...filtration tower, 42...chelate tower. Figure 2 Figure Figure (α) (d) Figure 2 Figure 0 Tree [==Kome/Ki Ai (bl (C) (e) (f) Procedural amendment (method) % formula % Display of the case Heisei 1 Patent Application No. 12 879 2゜Name of the inventionMethod for recovering metal valuables from plating waste liquid 3゜Relationship with the amended case
Claims (1)
のうち少なくとも一方の不純物除去材に前記メッキ液を
通すことで除去した後、メッキ槽へ戻し再利用を図ると
ともに、前記不純物除去材の能力低下時水を通してその
再生を図る方法において、再利用のための運転期間と前
記不純物除去材へ純水を通水する段階を含む不純物除去
材の再生運転期間とを交互に定め、再生運転期間中にお
いて、その再生期間の金属有価物含有量が多い段階にお
いて前記不純物除去材を通って排出される高濃度の金属
有価物を含有する廃液を系外に排出せずにメッキ液の一
部として使用するとともに、前記再生期間の金属有価物
含有量が少ない段階において排出される廃液を系外に排
出することを特徴とするメッキ廃液からの金属有価物の
回収方法。(1) After removing impurities in the plating solution by passing the plating solution through an impurity removing material, which is at least one of a filter medium and a chelate resin, the plating solution is returned to the plating tank for reuse, and the capacity of the impurity removing material is In the method of regenerating the water when it is degraded, an operation period for reuse and a regeneration operation period of the impurity removal material including a step of passing pure water through the impurity removal material are alternately determined, and during the regeneration operation period The waste liquid containing a high concentration of valuable metals discharged through the impurity removal material during the regeneration period when the content of valuable metals is high is used as part of the plating solution without being discharged outside the system. At the same time, a method for recovering metal valuables from plating waste liquid, characterized in that the waste liquid discharged at a stage in which the content of metal valuables is low during the regeneration period is discharged outside the system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12187989A JPH03130400A (en) | 1989-05-16 | 1989-05-16 | Method for recovering valuable metallic matter from waste plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12187989A JPH03130400A (en) | 1989-05-16 | 1989-05-16 | Method for recovering valuable metallic matter from waste plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03130400A true JPH03130400A (en) | 1991-06-04 |
Family
ID=14822187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12187989A Pending JPH03130400A (en) | 1989-05-16 | 1989-05-16 | Method for recovering valuable metallic matter from waste plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03130400A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008045187A (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Kk | Apparatus for regenerating plating solution and method for regenerating plating solution |
| JP2008045188A (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Kk | Apparatus for regenerating plating solution and method for regenerating plating solution |
| WO2008023778A1 (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Corporation | Plating solution regenerating apparatus and method of regenerating plating solution |
| JP2008045186A (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Kk | Apparatus for regenerating plating solution and method for regenerating plating solution |
| JP2014214320A (en) * | 2013-04-23 | 2014-11-17 | Ｊｆｅスチール株式会社 | Device and method for manufacturing chromium electroplated steel strip |
-
1989
- 1989-05-16 JP JP12187989A patent/JPH03130400A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008045187A (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Kk | Apparatus for regenerating plating solution and method for regenerating plating solution |
| JP2008045188A (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Kk | Apparatus for regenerating plating solution and method for regenerating plating solution |
| WO2008023778A1 (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Corporation | Plating solution regenerating apparatus and method of regenerating plating solution |
| JP2008045186A (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Kk | Apparatus for regenerating plating solution and method for regenerating plating solution |
| JP2014214320A (en) * | 2013-04-23 | 2014-11-17 | Ｊｆｅスチール株式会社 | Device and method for manufacturing chromium electroplated steel strip |
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