WO2017041472A1 - 一种零排放酸性蚀刻废液循环再生方法及*** - Google Patents

一种零排放酸性蚀刻废液循环再生方法及*** Download PDF

Info

Publication number
WO2017041472A1
WO2017041472A1 PCT/CN2016/077066 CN2016077066W WO2017041472A1 WO 2017041472 A1 WO2017041472 A1 WO 2017041472A1 CN 2016077066 W CN2016077066 W CN 2016077066W WO 2017041472 A1 WO2017041472 A1 WO 2017041472A1
Authority
WO
WIPO (PCT)
Prior art keywords
etching
liquid
tank
zero
solution
Prior art date
Application number
PCT/CN2016/077066
Other languages
English (en)
French (fr)
Inventor
韦建敏
吴梅
赵兴文
Original Assignee
成都虹华环保科技股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from CN201520694083.9U external-priority patent/CN204982052U/zh
Priority claimed from CN201510569200.3A external-priority patent/CN105177583B/zh
Application filed by 成都虹华环保科技股份有限公司 filed Critical 成都虹华环保科技股份有限公司
Publication of WO2017041472A1 publication Critical patent/WO2017041472A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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

Definitions

  • the present invention relates to a waste liquid processing system, and more particularly to a zero-emission acid etching waste liquid recycling method and system.
  • the acidic etching solution is an etching liquid for fine circuit fabrication of a printed circuit board and fabrication of an inner layer of a multilayer board.
  • the regeneration of acid etching old liquid is mainly converted into an acidic solution of suitable specific gravity, transparency and high oxidation-reduction potential by chemical and electrochemical methods to maintain stable and rapid etching of the printed circuit board.
  • Chemical regeneration is the main method for the regeneration of acidic copper chloride etching solution. The principle is to discharge a certain proportion of the old liquid (high specific gravity), add a certain amount of liquid (low specific gravity), or add a certain amount of water. , to adjust the specific gravity of the etching solution.
  • the oxidizing agent in the same sputum liquid oxidizes the monovalent copper ion to the divalent copper ion, or the oxidizing agent is separately added to increase the oxidation-reduction potential of the etching liquid, thereby restoring the original performance of the etching liquid.
  • Common oxidants are air, oxygen, chlorine, ozone, sodium hypochlorite, sodium chlorate, hydrogen peroxide, and the like.
  • electrochemical regeneration method is an online regeneration method.
  • Metallic copper with commercial value can be produced by electrolysis, but chlorine gas is generated at the same time to form a polluted exhaust gas, which not only pollutes the environment but also causes waste.
  • Chinese Patent Application No. 201020567155.0 discloses a copper ion acid etching solution regeneration system, which is used for online processing of an acidic etching solution, which is limited by the etching line production, and can only be etched with Simultaneous production, and the exhaust gas treatment device inside the system consumes the chlorine inside the system. Although it is environmentally friendly, it causes waste of resources, causing the loss of chlorine inside the system, and additional acid solution is needed to ensure the efficiency of the etching solution. technical problem
  • An object of the present invention is to overcome the disadvantages of the prior art and to provide an acid etching waste liquid recycling system for recycling resources and a method for recycling etching liquid.
  • a zero-emission acid etching waste liquid recycling method comprising electrolyzing metal copper in an etching waste liquid in an electrolytic cell and generating exhaust gas at the same time, after electrolysis
  • the etching waste liquid is recycled as a regenerating liquid, and the regenerating liquid is separated into a high acidity solution and a low acidity solution by an acid concentration technique, and the high acidity solution is directly returned to the etching line for recycling, and the low acidity solution is formulated into an oxidizing agent.
  • the exhaust gas is processed to produce a valuable product containing chlorine. No waste liquid is generated during the whole cycle to achieve true zero emissions.
  • Electrolytic treatment is used to electrolyze the acid etching waste liquid, and the cathode tank in the electrolytic tank is electrochemically reduced to obtain electrolytic copper, and the anode tank in the electrolytic tank is electrochemically oxidized to regenerate the etching liquid to be regenerated. Liquid, and some chlorine is produced;
  • etching production is not running online, the chlorine gas generated in the anode tank is processed to form a chlorine-containing product;
  • etching production online operation ⁇ chlorine gas and etching waste liquid to generate a new etching liquid, direct circulation application To the etching line;
  • regeneration liquid treatment the regeneration liquid enters the regeneration liquid circulation system, is concentrated to separate the high acidity liquid and the low acidity liquid, the high acidity liquid enters the etching production line as the etching liquid, and the low acidity liquid is used to prepare the oxidant .
  • a zero-emission acid etching waste liquid circulation device system comprising an etching liquid processing system, a regeneration liquid circulation system, a liquid distribution system, and a chlorine gas recovery system, wherein the etching liquid processing system includes an etching production line, a mother liquid storage tank, an electrolytic tank, and a dissolution
  • the electrolytic cell comprises a cathode tank, a membrane and an anode tank, the mother liquor storage tank, the cathode tank, the anode tank, and the dissolution absorption system are sequentially connected, and the etching production line is respectively connected with the mother liquid storage tank and the dissolution absorption system, and the dissolution absorption system is connected with the etching production line.
  • the regenerating liquid circulation system includes a regenerating liquid storage tank and a regenerating liquid processing system, and the anode tank, the regenerating liquid storage tank, the regenerating liquid processing system, and the etching production line are sequentially connected;
  • the dosing system includes a regenerating liquid processing system and a dosing device, and the rehydrating liquid treatment System, with The liquid device and the etching production line are sequentially connected;
  • the chlorine gas recovery system includes a gas scrubbing system and an exhaust gas treatment system, and the anode tank, the scrubbing system, and the exhaust gas treatment system are sequentially connected.
  • the membrane is a membrane, a cationic membrane or an anionic membrane.
  • the cathode tank is connected to a copper washing device.
  • An ion concentration detecting device is disposed in the electrolytic cell.
  • the apparatus and piping within the system are all made of an acid, alkali, and corrosion resistant material.
  • the regenerative liquid processing system is provided with an acidity detecting device, and an acidity detecting device is disposed in the liquid dispensing device.
  • the present invention has the following advantages:
  • the system is used for processing acidic etching waste liquid, and the etching liquid can be recycled and recycled in the same manner as the metal copper is extracted, so that the etching liquid processing can be performed offline, the processing efficiency is improved, and the reasonable distribution is facilitated.
  • Resources enable dynamic balancing of etching and etching solutions, avoiding waste of resources and achieving sustainable production
  • the electrolytic chlorine gas can be recovered, and the chlorine gas is dissolved in the production line to react with the cuprous ions to form divalent copper ions, and the regenerated etching liquid is directly returned to the production line for recycling, if not and etching.
  • the electrolyzed chlorine gas can be washed and further processed to produce a valuable product containing chlorine, which can be used in the dosing system to prepare acid or as a commodity, thereby avoiding environmental pollution, wasting resources, and realizing chlorine.
  • the circulation of water in the system reducing the addition of additives or oxidants, reducing production costs and saving resources.
  • FIG. 1 is a schematic structural view of an acid etching waste liquid recycling system for recycling resources
  • a zero-emission acid etching waste liquid circulation device system includes an etching liquid processing system, a regenerating liquid circulation system, a dosing system, and a chlorine gas recovery system, and the etching liquid processing system includes an etching production line 1 and a mother liquid.
  • the storage tank 2, the electrolysis tank and the dissolution absorption system 6, the electrolysis tank comprises a cathode tank 3, a membrane 4 and an anode tank 5, the mother liquor storage tank 2, the cathode tank 3, the anode tank 5, the dissolution absorption system 6 are sequentially connected, and the etching production line 1 respectively Interconnected with the mother liquor storage tank 2 and the dissolution absorption system 6, and the dissolution absorption system 6 is in communication with the etching line 1;
  • the regeneration liquid circulation system includes a regeneration liquid storage tank 10 and a regeneration liquid treatment system 11, and the anode tank 5, the regeneration liquid storage tank 10, the regeneration liquid treatment system 11 and the etching production line 1 are sequentially connected;
  • the dosing system includes a regenerant treatment system 11 and a dosing device 12, and the reconditioning solution processing system 11, the dosing device 12, and the etching line 1 are sequentially connected;
  • the chlorine gas recovery system includes a scrubbing system 7 and an exhaust gas treatment system 8, and the anode tank 5, the scrubbing system 7, and the exhaust gas treatment system 8 are sequentially connected.
  • the membrane 4 is a membrane, a cation membrane or an anion membrane, and different membranes can be used to control the flow rate of ions according to production needs.
  • the cathode tank 3 is connected to the copper washing device 9, and the electrolytic copper obtained by electrolysis in the cathode tank 3 is treated by the copper washing device 9, whereby copper metal having commercial value can be obtained.
  • an ion concentration detecting device is disposed in the electrolytic cell, so that the concentration of each ion in the electrolytic cell can be detected, thereby controlling the flow rate of the liquid, thereby facilitating rational utilization and resource allocation.
  • the device and the pipeline in the system are made of acid-proof, alkali-resistant and corrosion-resistant materials, thereby prolonging the service life of the system.
  • the regeneration liquid processing system 11 is provided with an acidity detecting device, and the liquid adjusting device 12 is provided with an acidity detecting device, so that the detection of the acidity can be performed, thereby controlling the flow rate of the liquid. It is conducive to rational use and allocation of resources to achieve sustainable production.
  • a zero-emission acid etching waste liquid recycling method comprises: electrolytically recovering metallic copper in an etching waste liquid in a cathode tank 3 of an electrolytic cell and generating exhaust gas in the anode tank 5, and etching waste liquid after electrolysis
  • the regeneration liquid is recycled, the regeneration liquid is separated into a high acidity solution and a low acidity solution in the regeneration liquid treatment system 11 by acid concentration technology, and the high acidity solution is directly returned to the etching line for recycling, and the low acidity solution is used. It can be added into the etchant in the liquid-dispensing device 12 and then added back to the etching line.
  • the exhaust gas is washed by the scrubbing system 7 and then enters the exhaust gas treatment system 8 to produce a valuable product containing chlorine. There is no waste liquid increase during the whole cycle. Produce and achieve true zero emissions.
  • a zero-emission acid etching waste liquid recycling method comprises the following steps:
  • etching production is not online operation ⁇ , the chlorine gas generated in the anode tank 5 is washed by the scrubbing system 7 and then enters the tail gas treatment system 8 to produce a valuable product containing chlorine; etching production online operation ⁇ , chlorine gas Entering the dissolution absorption system 6 and the acidic etching waste liquid to regenerate a new etching liquid, and directly applying it to the etching production line 1;
  • the regeneration liquid can be stored in the regeneration liquid storage tank 10, and the regeneration liquid enters the regeneration liquid circulation system 11 and is concentrated to separate a high acidity liquid and a low acidity liquid, and the high acidity liquid is used as an etching.
  • the liquid enters the etching line 1, and the low acidity liquid enters the dosing device 12 for preparing the oxidant;
  • the working process of the present invention is as follows:
  • the etching liquid flowing out of the etching production line 1 is partially stored in the dissolution absorption system 6 for storage, and the other portion is stored in the mother liquid storage tank 2, and the flow rate is controlled by the mother liquid storage tank 2 to make the mother liquid storage tank 2
  • the etching solution enters the cathode tank 3.
  • cuprous ions are reduced to divalent copper ions, and the divalent copper ions are reduced to electrolytic copper.
  • the remaining unreduced copper ions and other ions enter the anode tank 5 through the membrane 4.
  • Chloride ions are oxidized under the action of electrolysis in the anode tank 5 to form chlorine gas.
  • chlorine gas enters the solvent absorption system 6, and undergoes redox reaction with cuprous ions to obtain copper ions and an acidic liquid.
  • the liquid can be used as an etchant to enter the etching line 1 to complete the production; when the etching line 1 is not produced ⁇ , the chlorine gas enters the scrubbing system 7 to obtain pure chlorine gas after the impurity removal, and the pure chlorine gas enters the exhaust gas treatment system 8 and is reacted to form a valuable chlorine-containing product.
  • the liquid remaining after the electrolysis contains ions such as copper ions, chloride ions, and hydrogen ions as the regenerating liquid, and the regenerating liquid has weak acidity, and the regenerating liquid enters the regenerating liquid storage tank 10 to be stored, and is regenerated.
  • the storage tank 10 controls the flow rate to be delivered to the regenerating liquid processing system 11, and the regenerating liquid is concentrated in the regenerating liquid processing system 11 to separate the high acidity liquid and the low acidity liquid, and the high acidity liquid is stored as the etching liquid and the low acidity liquid separately.
  • the high acidity liquid can be transported to the etching line 1 for production, and the low acidity liquid is transported into the dosing system 12, and is formulated into a new liquid together with the oxidant, the additive, etc., and is slowly added back to the etching line to control the etching liquid.
  • ORP value Dynamic balancing can be achieved by controlling the degree of electrolysis and the flow of liquid, facilitating automated production and off-line processing of acid etching waste.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

一种零排放酸性蚀刻废液循环再生方法及***，该方法包括电解、氯气处理和再生液处理等步骤，采用酸浓缩技术和尾气回收再利用技术，有效解决废液中的金属铜并使蚀刻液再生循环回用，无废液增量产生，实现零排放，该零排放酸性蚀刻废液循环再生***包括蚀刻液处理***、再生液循环***、配液***和氯气回收***，蚀刻液处理***包括蚀刻生产线(1)、母液储存罐(2)、电解槽和溶解吸收***(6)，电解槽包括阴极槽(3)和阳极槽(5)，再生液循环***包括再生液储罐(10)和再生液处理***(11)。该零排放酸性蚀刻废液循环再生***用于处理酸性蚀刻废液，能提取金属铜，可离线生产、节约成本、节约资源、防止环境污染。

Description

说明书 发明名称：一种零排放酸性蚀刻废液循环再生方法及*** 技术领域
[0001] 本发明涉及废液处理***， 特别是一种零排放酸性蚀刻废液循环再生方法及系 统。
背景技术
[0002] 酸性蚀刻液是一种用于印制电路板精细线路制作、 多层板内层制作的蚀刻液。
现代电子工业的高速发展， 电路板生产企业迅猛增加， 此类企业的工业废水对 环境污染比较严重， 而此类工业废水中铜离子含量很高， 因此由线路板生产企 业产生的废水、 废液所造成严重的环境污染和资源浪费问题日益受到社会的普 遍关注。 为了避免浪费以及保护环境， 需要对酸性蚀刻液进行回收再利用。
[0003] 酸性蚀刻旧液的再生主要通过化学、 电化学方法将其转变为合适比重、 透明和 高氧化还原电位的酸性溶液， 以维持印制电路板的稳定、 快速的蚀刻。 其中化 学再生是酸性氯化铜蚀刻液再生的主要方法， 其原理是通过排放一定比例的蚀 刻旧液 （高比重） ， 加入一定量的子液 （低比重） ， 或者在补加一定量的水， 来调节蚀刻液的比重。 同吋子液中的氧化剂将一价铜离子氧化为二价铜离子， 或者单独加入氧化剂， 提高蚀刻液氧化还原电位， 从而恢复蚀刻液的原有性能 。 常见的氧化剂有空气、 氧气、 氯气、 臭氧、 次氯酸钠、 氯酸钠、 双氧水等。 但是总铜不断增加， 最终需要对外排除一部分的酸性蚀刻液以维持一定的总铜 浓度， 不仅污染环境， 还会造成大量铜和酸的浪费； 电化学再生法， 是一种在 线的再生方法， 通过电解可以产出具有商业价值的金属铜， 但同吋会产生氯气 ， 形成具有污染的尾气， 不仅污染环境还造成浪费。
[0004] 中国专利申请号为 201020567155.0的专利， 公幵了一种含铜离子酸性蚀刻液再 生***， 该***用于在线处理酸性蚀刻液， 受到蚀刻线生产吋间的限制， 只能 与蚀刻线同步生产， 并且其***内部的废气处理装置， 消耗了***内部的氯元 素， 虽然实现了环保， 但导致资源的浪费， 使得***内部氯元素流失， 需要额 外添加酸液以保证蚀刻液的效益。 技术问题
[0005] 本发明的目的在于克服现有技术的缺点， 提供一种资源循环利用的酸性蚀刻废 液循环再生***以及蚀刻液再利用的方法。
问题的解决方案
技术解决方案
[0006] 本发明的目的通过以下技术方案来实现： 一种零排放酸性蚀刻废液循环再生方 法， 包括将蚀刻废液中的金属铜在电解槽内电解回收并同吋产生尾气， 电解之 后的蚀刻废液作为再生液循环利用， 采用酸浓缩技术将再生液分离成高酸度的 溶液和低酸度的溶液， 高酸度的溶液直接回到蚀刻线上循环再用， 低酸度的溶 液配制成氧化剂后回到蚀刻线上添加， 尾气经过处理后再制成含氯的有价产品 ， 整个循环过程中无废液增量产生， 实现真正的零排放。
[0007] 包括如下几个步骤：
[0008] Sl、 电解： 使用电解槽对酸性蚀刻废液进行电解处理， 电解槽内的阴极槽发生 电化学还原反应得到电解铜， 电解槽内的阳极槽发生电化学氧化将蚀刻液再生 得到再生液， 并有部分氯气产生；
[0009] S2、 氯气处理： 蚀刻生产未在线运行吋， 阳极槽产生的氯气经过处理后制成含 氯产品； 蚀刻生产在线运行吋， 氯气与蚀刻废液再生成新的蚀刻液， 直接循环 应用到蚀刻生产线；
[0010] S3、 再生液处理： 再生液进入再生液循环***， 被浓缩分离出高酸度的液体和 低酸度的液体， 高酸度的液体作为蚀刻液进入蚀刻生产线， 低酸度的液体用来 配制氧化剂。
[0011] 一种零排放酸性蚀刻废液循环装置***， 包括蚀刻液处理***、 再生液循环 ***、 配液***和氯气回收***， 蚀刻液处理***包括蚀刻生产线、 母液储存 罐、 电解槽和溶解吸收***， 电解槽包括阴极槽、 膜和阳极槽， 母液储存罐、 阴极槽、 阳极槽、 溶解吸收***依次连通， 蚀刻生产线分别与母液储存罐和溶 解吸收***连通， 溶解吸收***与蚀刻生产线连通； 再生液循环***包括再生 液储罐和再生液处理***， 阳极槽、 再生液储罐、 再生液处理***和蚀刻生产 线依次连通； 配液***包括再生液处理***和配液装置， 再生液处理***、 配 液装置和蚀刻生产线依次连通； 氯气回收***包括洗气***和尾气处理***， 阳极槽、 洗气***和尾气处理***依次连通。
[0012] 所述的膜为隔膜、 阳离子膜或阴离子膜。
[0013] 所述的阴极槽与洗铜装置连接。
[0014] 所述的电解槽内设有离子浓度检测装置。
[0015] 所述的该***内的装置以及管道都使用耐酸、 耐碱、 耐腐蚀的材料制成。
[0016] 所述的再生液处理***内设有酸度检测装置， 配液装置内设有酸度检测装置。
发明的有益效果
有益效果
[0017] 本发明具有以下优点：
[0018] 1.该***用于处理酸性蚀刻废液， 能够在提取金属铜的同吋使蚀刻液再生循环 回用， 实现蚀刻液处理能够离线进行， 提高了处理效率， 有利于通过合理地分 配资源使得蚀刻与蚀刻液处理达到动态平衡， 避免资源浪费， 实现可持续生产
[0019] 2.通过采用酸浓缩技术将再生液分离成高酸度的溶液和低酸度的溶液， 高酸度 的溶液直接回到蚀刻线上循环再用， 低酸度的溶液配制成氧化剂后回到蚀刻线 上添加， 整个循环过程中无废液增量产生， 实现真正的零排放。
[0020] 3.通过本发明可以回收电解氯气， 与产线联动吋氯气去溶解吸收***与亚铜离 子发生反应生成二价铜离子， 再生蚀刻液直接回到产线循环利用， 若没有与蚀 刻产线联动， 电解氯气可以通过水洗和进一步处理， 制成含氯的有价产品， 并 将之用于配液***配制酸液或作为商品， 以此可以避免污染环境、 浪费资源， 实现氯元素和水在***内的循环， 减少额外添加添加剂或氧化剂， 降低了生产 成本， 节约了资源。
对附图的简要说明
附图说明
[0021] 图 1为一种资源循环利用的酸性蚀刻废液循环再生***的结构示意图；
[0022] 图中， 1-蚀刻生产线， 2-母液储存罐， 3-阴极槽， 4-膜， 5-阳极槽， 6-溶解吸收 ***， 7-洗气***， 8-尾气处理***， 9-洗铜装置， 10-再生液储罐， 11-再生液 处理***， 12-配液装置。
本发明的实施方式
[0023] 下面结合附图对本发明做进一步的描述， 本发明的保护范围不局限于以下所述
[0024] 如图 1所示， 一种零排放酸性蚀刻废液循环装置***， 包括蚀刻液处理***、 再生液循环***、 配液***和氯气回收***， 蚀刻液处理***包括蚀刻生产线 1 、 母液储存罐 2、 电解槽和溶解吸收*** 6， 电解槽包括阴极槽 3、 膜 4和阳极槽 5 ， 母液储存罐 2、 阴极槽 3、 阳极槽 5、 溶解吸收*** 6依次连通， 蚀刻生产线 1分 别与母液储存罐 2和溶解吸收*** 6连通， 溶解吸收*** 6与蚀刻生产线 1连通；
[0025] 再生液循环***包括再生液储罐 10和再生液处理*** 11， 阳极槽 5、 再生液储 罐 10、 再生液处理*** 11和蚀刻生产线 1依次连通；
[0026] 配液***包括再生液处理*** 11和配液装置 12， 再生液处理*** 11、 配液装置 12和蚀刻生产线 1依次连通；
[0027] 氯气回收***包括洗气*** 7和尾气处理*** 8， 阳极槽 5、 洗气*** 7和尾气处 理*** 8依次连通。
[0028] 本实施例中， 所述的膜 4为隔膜、 阳离子膜或阴离子膜， 可以根据生产需要来 选用不同的膜控制离子的流量。
[0029] 本实施例中， 所述的阴极槽 3与洗铜装置 9连接， 通过洗铜装置 9对阴极槽 3内电 解得到的电解铜进行处理， 可以得到具有商业价值的铜金属。
[0030] 本实施例中， 所述的电解槽内设有离子浓度检测装置， 以此可以使实施检测到 电解槽内各离子的浓度， 从而控制液体的流量， 有利于合理的利用、 分配资源
， 实现可持续生产。
[0031] 本实施例中， 所述的该***内的装置以及管道都使用耐酸、 耐碱、 耐腐蚀的材 料制成， 以此可以延长***的使用寿命。
[0032] 本实施例中， 所述的再生液处理*** 11内设有酸度检测装置， 配液装置 12内设 有酸度检测装置， 以此可以使实施检测到酸度的大小， 从而控制液体的流量， 有利于合理的利用、 分配资源， 实现可持续生产。 [0033] 一种零排放酸性蚀刻废液循环再生方法， 包括将蚀刻废液中的金属铜在电解槽 的阴极槽 3内电解回收并同吋在阳极槽 5产生尾气， 电解之后的蚀刻废液作为再 生液循环利用， 采用酸浓缩技术将再生液在再生液处理*** 11内分离成高酸度 的溶液和低酸度的溶液， 高酸度的溶液直接回到蚀刻线上循环再用， 低酸度的 溶液可以在配液装置 12内配制成氧化剂后回到蚀刻线上添加， 尾气经过洗气系 统 7水洗后再进入尾气处理*** 8制成含氯的有价产品， 整个循环过程中无废液 增量产生， 实现真正的零排放。
[0034] 一种零排放酸性蚀刻废液循环再生方法， 包括如下几个步骤：
[0035] Sl、 电解： 酸性蚀刻废液从蚀刻生产线 1进入母液储存罐 2和溶解吸收*** 6， 使用电解槽对母液储存罐 2流出的酸性蚀刻废液进行电解处理， 电解槽内的阴极 槽 3发生电化学还原反应得到电解铜， 电解铜经过洗铜装置 9清洗之后回收利用 ， 电解槽内的阳极槽 5发生电化学氧化将酸性蚀刻废液再生得到再生液， 并有部 分氯气产生；
[0036] S2、 氯气处理： 蚀刻生产未在线运行吋， 阳极槽 5产生的氯气经过洗气*** 7水 洗后再进入尾气处理*** 8制成含氯的有价产品； 蚀刻生产在线运行吋， 氯气进 入溶解吸收*** 6与酸性蚀刻废液再生成新的蚀刻液， 直接循环应用到蚀刻生产 线 1 ;
[0037] S3、 再生液处理： 再生液可以存储在再生液储罐 10内， 再生液进入再生液循环 *** 11后被浓缩分离出高酸度的液体和低酸度的液体， 高酸度的液体作为蚀刻 液进入蚀刻生产线 1， 低酸度的液体进入配液装置 12用来配制氧化剂；
[0038] 本发明的工作过程如下： 蚀刻生产线 1上流出的蚀刻液部分进入溶解吸收*** 6 进行储存， 另一部分进入母液储存罐 2进行储存， 由母液储存罐 2控制流量使母 液储存罐 2内的蚀刻液进入阴极槽 3， 在阴极槽 3内的电解作用下， 亚铜离子被还 原成二价铜离子， 二价铜离子被还原成电解铜。 剩余的未被还原的铜离子以及 其他离子通过膜 4进入阳极槽 5。
[0039] 氯离子在阳极槽 5内的电解作用下被氧化形成氯气， 当蚀刻生产线 1在生产吋， 氯气进入溶剂吸收*** 6， 与亚铜离子发生氧化还原反应得到铜离子以及酸性液 体， 该液体能够作为蚀刻液进入蚀刻生产线 1完成生产； 当蚀刻生产线 1未生产 吋， 氯气进入洗气*** 7内除杂后得到纯氯气， 纯氯气进入尾气处理*** 8后经 过反应制成有价的含氯产品。
由于电解槽内的电解反应未完全进行， 电解后剩余的液体作为再生液包含铜离 子、 氯离子、 氢离子等离子， 再生液具有弱酸性， 再生液进入再生液储罐 10储 存， 并被再生液储罐 10控制流量输送到再生液处理*** 11内， 再生液在再生液 处理*** 11被浓缩分离出高酸度的液体和低酸度的液体， 高酸度的液体作为蚀 刻液与低酸度的液体分别储存， 高酸度的液体可以输送到蚀刻生产线 1用于生产 ， 低酸度的液体输送到配液*** 12内， 与氧化剂、 添加剂等一起配制成新液， 回到蚀刻线上缓慢添加以控制蚀刻液的 ORP值。 通过控制电解的程度以及液体的 流量可以实现动态平衡， 有利于实现自动化生产以及酸性蚀刻废液离线处理。

Claims

权利要求书
[权利要求 1] 一种零排放酸性蚀刻废液循环再生方法， 其特征在于： 将蚀刻废液中 的金属铜在电解槽内电解回收并产生尾气， 电解之后的蚀刻废液作为 再生液循环利用， 采用酸浓缩技术将再生液分离成高酸度的溶液和低 酸度的溶液， 高酸度的溶液直接回到蚀刻线上循环再用， 低酸度的溶 液配制成氧化剂后回到蚀刻线上添加， 尾气经过处理后再制成含氯的 有价产品， 整个循环过程中无废液增量产生， 实现真正的零排放。
[权利要求 2] 根据权利要求 1所述的一种零排放酸性蚀刻废液循环再生方法， 其特 征在于： 包括如下几个步骤：
51、 电解： 使用电解槽对酸性蚀刻废液进行电解处理， 电解槽内的阴 极槽发生电化学还原反应得到电解铜， 电解槽内的阳极槽发生电化学 氧化将蚀刻液再生得到再生液， 并有部分氯气产生；
52、 氯气处理： 蚀刻生产未在线运行吋， 阳极槽产生的氯气经过处理 后制成含氯产品； 蚀刻生产在线运行吋， 氯气与蚀刻废液再生成新的 蚀刻液， 直接循环应用到蚀刻生产线；
53、 再生液处理： 再生液进入再生液循环***， 被浓缩分离出高酸度 的液体和低酸度的液体， 高酸度的液体作为蚀刻液进入蚀刻生产线， 低酸度的液体用来配制氧化剂。
[权利要求 3] —种零排放酸性蚀刻废液循环***， 其特征在于： 包括蚀刻液处理系 统、 再生液循环***、 配液***和氯气回收***， 蚀刻液处理***包 括蚀刻生产线 （1) 、 母液储存罐 （2) 、 电解槽和溶解吸收*** （6 ) ， 电解槽包括阴极槽 （3) 、 膜 （4) 和阳极槽 （5) ， 母液储存罐 (2) 、 阴极槽 （3) 、 阳极槽 （5) 、 溶解吸收*** （6) 依次连通， 蚀刻生产线 （1) 分别与母液储存罐 （2) 和溶解吸收*** （6) 连通 ， 溶解吸收*** （6) 与蚀刻生产线 （1) 连通； 再生液循环***包括再生液储罐 （10) 和再生液处理*** （11) ， 阳 极槽 （5) 、 再生液储罐 （10) 、 再生液处理*** （11) 和蚀刻生产 线 （1) 依次连通； 配液***包括再生液处理*** （11) 和配液装置 （12) ， 再生液处理 *** （11) 、 配液装置 （12) 和蚀刻生产线 （1) 依次连通； 氯气回收***包括洗气*** （7) 和尾气处理*** （8) ， 阳极槽 （5
) 、 洗气*** （7) 和尾气处理*** （8) 依次连通。
根据权利要求 3所述的一种零排放酸性蚀刻废液循环***， 其特征在 于： 所述的膜 （4) 为隔膜、 阳离子膜或阴离子膜。
根据权利要求 3所述的一种零排放酸性蚀刻废液循环***， 其特征在 于： 所述的阴极槽 （3) 与洗铜装置 （9) 连接。
根据权利要求 3所述的一种零排放酸性蚀刻废液循环***， 其特征在 于： 所述的电解槽内设有离子浓度检测装置。
根据权利要求 3所述的一种零排放酸性蚀刻废液循环***， 其特征在 于： 所述的该***内的装置以及管道都使用耐酸、 耐碱、 耐腐蚀的材 料制成。
根据权利要求 3所述的一种零排放酸性蚀刻废液循环***， 其特征在 于： 所述的再生液处理*** （11) 内设有酸度检测装置， 配液装置 ( 12) 内设有酸度检测装置。
PCT/CN2016/077066 2015-09-09 2016-03-23 一种零排放酸性蚀刻废液循环再生方法及*** WO2017041472A1 (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201520694083.9U CN204982052U (zh) 2015-09-09 2015-09-09 一种零排放酸性蚀刻废液循环再生***
CN201510569200.3 2015-09-09
CN201520694083.9 2015-09-09
CN201510569200.3A CN105177583B (zh) 2015-09-09 2015-09-09 一种零排放酸性蚀刻废液循环再生方法及***

Publications (1)

Publication Number Publication Date
WO2017041472A1 true WO2017041472A1 (zh) 2017-03-16

Family

ID=58239107

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/077066 WO2017041472A1 (zh) 2015-09-09 2016-03-23 一种零排放酸性蚀刻废液循环再生方法及***

Country Status (1)

Country Link
WO (1) WO2017041472A1 (zh)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008139021A1 (en) * 2007-05-16 2008-11-20 Pp Recycling Ltd. Metthod of regeneration method of acid cupper(ii)chloride etching waste
CN101805083A (zh) * 2010-03-26 2010-08-18 南通市申海特种镀饰有限责任公司 一种从电镀废水中回收贵金属的工艺方法
CN104152905A (zh) * 2014-06-24 2014-11-19 深圳市新锐思环保科技有限公司 酸性氯化铜蚀刻液电解再生循环及铜板回收装置及方法
CN104630825A (zh) * 2015-01-20 2015-05-20 昆山美源达环保科技有限公司 一种酸性蚀刻液电解提铜装置及其工艺
CN104911596A (zh) * 2015-06-01 2015-09-16 深圳中能润德环保有限公司 一种蚀刻液循环再生及提铜装置及方法
CN105002501A (zh) * 2015-09-09 2015-10-28 成都虹华环保科技股份有限公司 一种可节约资源的酸性蚀刻废液循环再生***
CN105039989A (zh) * 2015-06-26 2015-11-11 无锡市瑞思科环保科技有限公司 一种酸性氯化体系含铜蚀刻废液电积脱铜及再生的方法
CN204779821U (zh) * 2015-06-01 2015-11-18 深圳中能润德环保有限公司 一种蚀刻液循环再生及提铜装置
CN105177581A (zh) * 2015-09-09 2015-12-23 成都虹华环保科技股份有限公司 一种具有尾气处理功能的酸性蚀刻废液循环再生***
CN204898084U (zh) * 2015-09-09 2015-12-23 成都虹华环保科技股份有限公司 一种可节约资源的酸性蚀刻废液循环再生***
CN105177583A (zh) * 2015-09-09 2015-12-23 成都虹华环保科技股份有限公司 一种零排放酸性蚀刻废液循环再生方法及***
CN204982052U (zh) * 2015-09-09 2016-01-20 成都虹华环保科技股份有限公司 一种零排放酸性蚀刻废液循环再生***
CN204982053U (zh) * 2015-09-09 2016-01-20 成都虹华环保科技股份有限公司 一种具有尾气处理功能的酸性蚀刻废液循环再生***

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008139021A1 (en) * 2007-05-16 2008-11-20 Pp Recycling Ltd. Metthod of regeneration method of acid cupper(ii)chloride etching waste
CN101805083A (zh) * 2010-03-26 2010-08-18 南通市申海特种镀饰有限责任公司 一种从电镀废水中回收贵金属的工艺方法
CN104152905A (zh) * 2014-06-24 2014-11-19 深圳市新锐思环保科技有限公司 酸性氯化铜蚀刻液电解再生循环及铜板回收装置及方法
CN104630825A (zh) * 2015-01-20 2015-05-20 昆山美源达环保科技有限公司 一种酸性蚀刻液电解提铜装置及其工艺
CN104911596A (zh) * 2015-06-01 2015-09-16 深圳中能润德环保有限公司 一种蚀刻液循环再生及提铜装置及方法
CN204779821U (zh) * 2015-06-01 2015-11-18 深圳中能润德环保有限公司 一种蚀刻液循环再生及提铜装置
CN105039989A (zh) * 2015-06-26 2015-11-11 无锡市瑞思科环保科技有限公司 一种酸性氯化体系含铜蚀刻废液电积脱铜及再生的方法
CN105002501A (zh) * 2015-09-09 2015-10-28 成都虹华环保科技股份有限公司 一种可节约资源的酸性蚀刻废液循环再生***
CN105177581A (zh) * 2015-09-09 2015-12-23 成都虹华环保科技股份有限公司 一种具有尾气处理功能的酸性蚀刻废液循环再生***
CN204898084U (zh) * 2015-09-09 2015-12-23 成都虹华环保科技股份有限公司 一种可节约资源的酸性蚀刻废液循环再生***
CN105177583A (zh) * 2015-09-09 2015-12-23 成都虹华环保科技股份有限公司 一种零排放酸性蚀刻废液循环再生方法及***
CN204982052U (zh) * 2015-09-09 2016-01-20 成都虹华环保科技股份有限公司 一种零排放酸性蚀刻废液循环再生***
CN204982053U (zh) * 2015-09-09 2016-01-20 成都虹华环保科技股份有限公司 一种具有尾气处理功能的酸性蚀刻废液循环再生***

Similar Documents

Publication Publication Date Title
CN105177583B (zh) 一种零排放酸性蚀刻废液循环再生方法及***
CN105039989B (zh) 一种酸性氯化体系含铜蚀刻废液电积脱铜及再生的方法
CN204982052U (zh) 一种零排放酸性蚀刻废液循环再生***
CN105177581A (zh) 一种具有尾气处理功能的酸性蚀刻废液循环再生***
CN201834972U (zh) 一种含铜离子酸性蚀刻液再生***
CN104152905A (zh) 酸性氯化铜蚀刻液电解再生循环及铜板回收装置及方法
CN105177584A (zh) 一种具有再生液处理功能的酸性蚀刻废液循环再生***
CN103757664B (zh) 电解槽、使用该电解槽的蚀刻液再生设备及再生方法
CN105002501A (zh) 一种可节约资源的酸性蚀刻废液循环再生***
CN102732888A (zh) 酸性蚀刻废液的再生回收方法及***
CN202492581U (zh) 一种用于印制线路板酸性蚀刻液循环再生装置
CN208279686U (zh) 酸性蚀刻液循环再生***
CN202492580U (zh) 一种印制线路板酸性蚀刻液循环再生装置
CN204898084U (zh) 一种可节约资源的酸性蚀刻废液循环再生***
CN107012466A (zh) 一种酸性蚀刻液再生循环方法及***
CN102560499A (zh) 一种印制线路板酸性蚀刻液循环再生装置
CN204982053U (zh) 一种具有尾气处理功能的酸性蚀刻废液循环再生***
CN106637216A (zh) 一种酸性蚀刻液再生循环使用铜回收设备
CN104562015A (zh) 酸性蚀刻液在线循环的铜回收***
CN114318372B (zh) 一种循环电解三氯化铁吸收氯气的装置及方法
CN208087748U (zh) 双组份酸性蚀刻液循环再生装置
WO2017041472A1 (zh) 一种零排放酸性蚀刻废液循环再生方法及***
WO2017041471A1 (zh) 一种可节约资源的酸性蚀刻废液循环再生***
CN205974669U (zh) 一种高含铜蚀刻液再生循环***
WO2017041470A1 (zh) 一种具有尾气处理功能的酸性蚀刻废液循环再生***

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16843412

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16843412

Country of ref document: EP

Kind code of ref document: A1