WO2020233104A1 - 一种pcb硝酸型退锡废液的再生回用方法 - Google Patents

一种pcb硝酸型退锡废液的再生回用方法 Download PDF

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WO2020233104A1
WO2020233104A1 PCT/CN2019/123786 CN2019123786W WO2020233104A1 WO 2020233104 A1 WO2020233104 A1 WO 2020233104A1 CN 2019123786 W CN2019123786 W CN 2019123786W WO 2020233104 A1 WO2020233104 A1 WO 2020233104A1
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tin
waste liquid
copper
nitric acid
stripping waste
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PCT/CN2019/123786
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English (en)
French (fr)
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高东瑞
刘剑锋
李强
黄坚渤
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惠州市臻鼎环保科技有限公司
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Publication of WO2020233104A1 publication Critical patent/WO2020233104A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/10—Halides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • 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
    • C25C1/24—Alloys obtained by cathodic reduction of all their ions
    • 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

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  • the invention relates to the technical field of regeneration of PCB tin stripping waste liquid, in particular to a method for recycling PCB nitric acid type tin stripping waste liquid.
  • PCB printed Circuit Board
  • PCB Printed Circuit Board
  • PCB (Printed Circuit Board) industry is the pillar industry of China's electronic information industry, and its growth rate is comparable to that of electronic information industry. Shows a year-on-year growth rate.
  • the method of drawing circuit diagrams on the circuit board still uses the method of chemical liquid etching.
  • the nitric acid type tin stripper is the leading dosage form for PCB production.
  • nitric acid usually contains nitric acid as the main component, as well as nitric acid stabilizers, nitrogen oxide inhibitors, and slow-release agents such as sulfonates and ferric nitrate. Dissolve tin on the surface to avoid corrosion of the copper surface of the pattern.
  • the tin stripping capacity decreases and it is discharged from the tin stripping equipment to become a tin stripping waste liquid.
  • the tin stripping waste liquid is a kind of dangerous waste liquid with very high acidity generated in the PCB production process, and contains a large amount of tin, copper, iron and other metal compounds, stabilizers, corrosion inhibitors and other organic substances. The composition is complex and comprehensive recovery is difficult. Big.
  • ZL101497458A and ZL1569644A mention the addition of surfactants, flocculants, sodium hydroxide and barium chloride to obtain barium stannate
  • ZL101918133A mentions the addition of electrolytes + distillation The method to obtain sodium stannate and tin dioxide
  • ZL102086073A mentioned adding lime slurry + evaporation concentration method to separate metal oxygen ions, and adding additives to achieve full recovery and zero-emission resource treatment method
  • ZL1288075 mentioned the use of boiling + Extraction separation, ion adsorption + chemical reduction precipitation + boiling and other physical + chemical separation and recovery methods of metal ions, add a certain amount of additives at the back end to realize the recycling of tin stripping waste liquid
  • ZL202080977, CN102766883A and ZL202499890 mentioned a kind of additive Sodium hydroxide precipitation + plate filtration + electrolytic copper extraction
  • the main purpose is to recover the valuable metals in the tin stripping waste liquid, such as adding chemical substances such as electrolytes, flocculants, alkali neutralization, extraction agents, etc. to recover tin and copper in the tin stripping waste liquid ,iron.
  • the concentration of nitric acid in the tin stripping waste liquid is 4.0-4.5 mol/L (the concentration of nitric acid in the new tin stripping solution is 5.5-6.0 mol/L).
  • the traditional treatment method will nitrate the nitrate into nitrate and discharge it, and use the nitric acid in the tin stripping solution. The rate is less than 35%.
  • the regenerated tin stripping liquid will produce a large amount of tin mud and deposit on the bottom of the tank during work. Blocking the tin stripping nozzle seriously affects the production efficiency of PCBs. It is not feasible in production and application.
  • the valuable metals recovered from the tin stripping waste liquid are mixed compounds, which need to be further separated from tin, copper, and iron by pyro smelting. The recovery cost is high, and there is inevitably the risk of secondary pollution to the environment during the smelting process.
  • the present invention provides a method for recycling PCB nitric acid type tin stripping waste liquid.
  • the method uses a metal ion trapping agent to separate metal ions from the tin stripping waste liquid to separate the tin stripping of metal ions.
  • the waste liquid is further purified to remove impurities, and then supplemented with nitric acid, copper protective agent, and tin complexing agent to configure the regenerated tin stripping liquid to be reused in the PCB stripping production line, and the separated metal ion precipitates are dissolved with hydrochloric acid, and then double membranes are used
  • the three-chamber electrolyzer performs electrolytic deposition and recovery of the metal ion solution to obtain metal tin, metal copper, ferric chloride solution, and hydrochloric acid solution.
  • the hydrochloric acid solution is reused to the process of dissolving the metal ion precipitate; this method not only separates the tin stripping waste liquid
  • Metal ions are used to obtain metal tin, copper and iron trichloride water purifiers through electrolytic deposition, and the tin stripping waste liquid is further purified and purified, and the effective ingredients are added to the PCB tin stripping production line to realize the nitric acid type Regeneration and reuse of tin stripping waste liquid.
  • the regeneration and reuse method of the nitric acid type tin stripping waste liquid of the present invention includes the following steps:
  • the metal ion trapping agent in this step is an organic acid and organic acid salt that can form a precipitate with tin and copper in a nitric acid system, including oxalic acid, acetic acid, lactic acid, ammonium oxalate, ammonium acetate, and lactic acid.
  • Ammonium in order to effectively precipitate and separate tin and copper without affecting the quality of the regeneration and reuse of the tin stripping waste liquid, the addition amount of the trapping agent is 1% to 6% of the volume of the tin stripping waste liquid. After the addition of the trapping agent, stir and react for 2 hours- 6 hours to make the reaction more complete. After the stirring is stopped, let it stand for 12-24 hours (for aging, making it easier to separate the tin, copper and iron precipitates), and then perform solid-liquid separation to obtain tin, copper, and iron precipitates With filtrate;
  • step (2) Deep impurity removal and purification of the tin stripping waste liquid filtrate:
  • the filtrate obtained in step (1) is added to the impurity removal agent for deep impurity removal and purification. Due to the residual and invalid copper protection agent, tin complexing agent, and excess in the tin stripping waste liquid Metal ion trapping agents are all organic matter.
  • the impurity removal agent that has adsorption effect on organic matter is preferred, including activated carbon, sawdust residue, and diatomaceous earth.
  • the addition ratio of the impurity removal agent is 0.5%-2% of the filtrate volume, and stir after adding 2-6 hours, then stand for 12-24 hours, filter to obtain the purified tin-removing waste liquid;
  • Step (3) Preparing the nitric acid type tin stripping regenerating solution: add the purified tin stripping waste liquid obtained in step (2) to the blending tank, add nitric acid, accelerator, tin complexing agent, copper protection agent, etc. to prepare a regenerated tin stripping solution.
  • nitric acid is preferably nitric acid with a mass concentration of 62% or more.
  • the accelerator Ferric nitrate or iron trichloride is preferred.
  • a tin complexing agent preferably benzofluorenone, should be added to the regenerated tin stripping solution. The addition amount is the volume of the regenerated tin stripping solution.
  • a copper protection agent In order to slow down the corrosion of the regenerated tin stripping solution on the copper surface after tin stripping, a copper protection agent needs to be added to the regenerated tin stripping solution.
  • the copper protection agent is preferably thiourea and benzotriazine, and the addition amount is regeneration 0.05%-0.15% of the volume of the tin stripping solution;
  • Dissolution of tin-copper-iron precipitates first add a certain amount of hydrochloric acid to the reactor, the amount of hydrochloric acid added is 1.1-1.2 times the stoichiometric amount required for complete dissolution of tin-copper-iron precipitates, turn on the stirring, and then add steps (1)
  • the obtained tin-copper-iron mixed precipitate is heated to 90-100 degrees Celsius to completely dissolve the precipitate, and pure water is added to obtain a tin-copper-iron hydrochloric acid solution whose tin ion concentration is maintained at a concentration of 6%-9%;
  • the tin-copper-iron chloride solution obtained in step (4) is injected into the cathode compartment of the double-membrane three-chamber electrolytic cell, and 0.5%-1% by mass hydrochloric acid is injected into the intermediate isolation chamber Solution, the anode chamber is injected with a sulfuric acid solution with a concentration of 0.5% to 5% by mass.
  • the cathode uses a titanium plate, and the anode uses a titanium insoluble anode coated with precious metals. Electrolysis is carried out at room temperature. The cathode produces copper and tin metals in sequence.
  • the chloride ions generated in the cathode compartment enter the middle compartment through the anion ion exchange membrane, the anode produces oxygen and hydrogen ions, and the hydrogen ions pass through the cation exchange membrane into the middle compartment.
  • the hydrochloric acid solution in the middle compartment is extracted and reused to step (4 1)
  • the dissolution process of tin, copper and iron precipitates, the mixed solution of ferric chloride and ferrous chloride is obtained after the electrolytic precipitation of copper and tin in the cathode chamber is completed;
  • the anode compartment and the middle compartment of the double-membrane three-compartment electrolyzer are separated by a cation ion exchange membrane, and the middle compartment and the cathode compartment are separated by an anion ion exchange membrane;
  • the main electrochemical reactions in this process are:
  • Cathode chamber SnCl 4 ⁇ Sn + 4Cl - CuCl 2 ⁇ Cu + 2Cl -
  • the ferric chloride ferrous chloride solution obtained in step (5) is passed through the oxygen generated in the anode chamber of step (5) to further oxidize the ferrous iron to obtain a ferric chloride solution.
  • the ferric chloride solution obtained in this step can be used as sewage Processed flocculant.
  • the tin-copper-iron mixed compound obtained from the recovery of tin stripping waste liquid is further processed to recover metallic tin-copper and ferric chloride water purifying agent, avoiding the high energy consumption and air pollution problems of traditional pyrotechnical separation of tin, copper and iron.
  • Figure 1 is a process flow diagram of the PCB nitric acid type tin stripping waste recycling method of the present invention
  • Figure 2 is a schematic diagram of the structure of the double-membrane three-chamber electrolytic cell of the present invention.
  • a PCB factory tin stripping waste liquid contains 6% tin, 0.5% copper, and 4.5 mol/L nitric acid.
  • 2000L tin stripping waste liquid into the reactor, turn on the stirring, add 20Kg oxalic acid (1% waste liquid volume ratio), and stir for 5 Hour, stop stirring, let stand for 12 hours, solid-liquid separation, get tin-copper-iron mixed precipitate and filtrate;
  • pump 1500L filtrate into the reactor add 30Kg (2% filtrate volume ratio) diatomaceous earth and stir for 2 hours , Stand for 24 hours, and filter to obtain the purified tin stripping waste liquid;
  • the concentration is 6mol/L, add 0.5Kg tin complexing agent benzofluorenone (the waste liquid
  • a PCB factory tin stripping waste liquid contains 8% tin, 0.2% copper, and 4.1 mol/L nitric acid.
  • 2000L tin stripping waste liquid into the reactor, turn on the stirring, add 120Kg oxalic acid (6% by volume of the waste liquid), and stir for 5 After hours, stop stirring, let stand for 24 hours, and separate solid-liquid to obtain tin-copper-iron mixed precipitate and filtrate; pump 1500L filtrate into the reactor, add 7.5Kg (0.5% filtrate volume ratio) activated carbon and stir for 2 hours, Let stand for 12 hours and filter to obtain the purified tin stripping waste liquid; pump 1000L of the purified tin stripping waste liquid into the regenerated tin stripping solution mixing tank, turn on the stirring, add nitric acid with a mass concentration of 68% to adjust to the acid concentration of the regenerated tin stripping solution 6mol/L, add 0.05Kg tin complexing agent benzofluorenone (waste liquid volume
  • the anode In the middle compartment 3, the anode generates oxygen and hydrogen ions, and the hydrogen ions pass through the cation exchange membrane 5 into the middle compartment 3.
  • the hydrochloric acid solution in the middle compartment 3 is extracted and reused in the process of dissolving tin, copper and iron precipitates.
  • the electrolytic lean solution of Example 4 is oxidized to oxidize the ferrous chloride solution into a ferric chloride solution.
  • the middle compartment 3 is enriched with hydrochloric acid, and the cathode plate obtains metal copper and tin. After the electrolytic deposition of tin and copper is completed, the cathode chambers are drawn out respectively 1
  • the electrolytic lean solution and the hydrochloric acid solution in the middle compartment are reserved;
  • the hydrochloric acid solution in the middle compartment 3 is extracted and reused to the process of dissolving tin, copper and iron precipitates.
  • Oxygen generated by the anode is fed into the electrolytic lean solution in Example 4 to oxidize the ferrous chloride solution into a ferric chloride solution, the middle compartment 3 is enriched with hydrochloric acid, and the cathode plate obtains metallic copper and tin.
  • the electrolytic deposition of tin and copper is completed.
  • the electrolytic lean solution in the cathode compartment 1 and the hydrochloric acid solution in the middle compartment 3 are respectively drawn out for use.
  • the present invention has the following advantages:

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Abstract

一种PCB硝酸型退锡废液再生回用方法用金属离子捕获剂将金属离子从退锡废液中分离出去，分离金属离子的退锡废液进一步净化除杂，然后补加硝酸、铜保护剂、锡络合剂配置成再生退锡液回用到PCB退锡生产线，用盐酸将分离得到的金属离子沉淀物溶解，然后用双膜三室电解槽对金属离子溶液进行电解沉积回收得到金属锡、金属铜、三氯化铁溶液、盐酸溶液，盐酸溶液回用至金属离子沉淀物溶解工序；该方法不但从退锡废液中分离出金属离子并通过电解沉积方法得到金属锡、铜与三氯化铁净水剂，而且还对退锡废液进一步除杂净化，补加有效成分后回用至PCB退锡生产线，实现了硝酸型退锡废液再生回用，不仅仅对环境友好，而且可以大幅降低成本。

Description

一种PCB硝酸型退锡废液的再生回用方法 技术领域
本发明涉及PCB退锡废液再生技术领域，具体地，涉及一种PCB硝酸型退锡废液的再生回用方法。
背景技术
PCB(印制线路板)是电子产品元器件的支撑体，是当今信息社会最基础的硬件载体，PCB(印制线路板)产业是中国电子信息产业的支柱产业，其增长率与电子信息产业呈同比率增长。几十年的PCB生产实践，生产工艺有了很大的改进，但在线路板上画出线路图的方法仍使用化学药水蚀刻的方法。外层正片制作时需在图形表面镀上一层厚度为5-8μm的锡，蚀刻成型后再把表层的锡溶解。目前硝酸型退锡剂是PCB生产的主导剂型，一般以硝酸为主成分，还有硝酸稳定剂、氮氧化物抑制剂、以及磺酸盐、硝酸铁等缓释剂，其作用是选择性地溶解表层锡而避免腐蚀图形铜面。
退锡过程中，当溶液的锡含量达到一定浓度(通常高100g/L)后，退锡能力下降，从退锡设备中排出而成为退锡废液。退锡废液是PCB生产过程中产生的一种酸度非常高，且含有大量锡、铜、铁等金属化合物和稳定剂、缓蚀剂等多种有机物的危险废液，成份复杂，综合回收难度大。
据统计目前国内PCB企业年产生5万吨以上的退锡废液，目前，处理退锡废液专利方法很多，中国发明专利ZL101532096A和ZL 102775197A中提到了往退锡废液中添加碳酸钠、氢氧化钠、氨水沉淀结合加热煮沸的方法分离锡的方法；ZL101497458A和ZL1569644A中提到了添加表面活性剂、絮凝剂、氢氧化钠和氯化钡等获得锡酸钡；ZL101918133A中提到了添加电解质+蒸馏的方法获得锡酸钠和二氧化锡的方法；ZL102086073A中提到了添加石灰浆+蒸发浓缩方法分离金属氧离子，并添加添加剂实现全回收和零排放的资源化处 理方法；ZL1288075中提到了用煮沸+萃取分离，离子吸附+化学还原沉淀+煮沸等物理+化学分离回收金属离子的方法，后端添加一定量的添加剂实现退锡废液的循环利用；ZL202080977、CN102766883A和ZL202499890中提到了一种加氢氧化钠沉淀+板式过滤+电解提铜+补加一定原料实现分离金属阳离子和循环利用退锡水的方法和设备；专利CN102492860A和CN102515259A中提到了通过添加电解质、絮凝剂等化学物质分离得到锡泥的方法。
从以上的处理方法可以发现，主要是针对性地回收退锡废液中有价金属，比如添加化学物质如电解质、絮凝剂、碱中和、萃取剂等回收退锡废液中的锡、铜、铁。退锡废液硝酸浓度为4.0-4.5mol/L(新配退锡溶液中硝酸浓度为5.5-6.0mol/L)，传统的处理方法将硝酸化为硝酸盐排放，退锡液中硝酸的利用率不足35％，虽然有公开专利介绍通过蒸发或是萃取方法回收硝酸，但因操作成本高昂或是回收的硝酸浓度太低而鲜有工业化的报道。CN 103436885 A通过在退锡废液中添加有机酸来使得锡沉淀，然后加絮凝剂后进行固液分离，分离所得滤液补加硝酸等使得退锡废液恢复退锡能力，但从实际经验来看，因因有机酸、絮凝剂在滤液中的残留会影响退锡后铜表面的品质，同时再生退锡液与新退锡液相比，在工作中会产生大量锡泥沉淀在缸底，堵塞退锡喷嘴，严重影响PCB生产效率，在生产应用中可行性不高，另外从退锡废液中回收的有价金属为混合化合物，需要通过火法冶炼进一步分离锡、铜、铁，不但回收成本高，而且在冶炼过程中不可避免地存在二次污染环境的风险。
发明内容
为克服以上存在的问题，本发明提供一种PCB硝酸型退锡废液的再生回用方法，该方法用金属离子捕获剂将金属离子从退锡废液中分离出去，分离金属离子的退锡废液进一步净化除杂，然后补加硝酸、铜保护剂、锡络合剂配置成 再生退锡液回用到PCB退锡生产线，用盐酸将分离得到的金属离子沉淀物溶解，然后用双膜三室电解槽对金属离子溶液进行电解沉积回收得到金属锡、金属铜、三氯化铁溶液、盐酸溶液，盐酸溶液回用至金属离子沉淀物溶解工序；该方法不但从退锡废液中分离出金属离子并通过电解沉积方法得到金属锡、铜与三氯化铁净水剂，而且还对退锡废液进一步除杂净化，补加有效成分后回用至PCB退锡生产线，实现了硝酸型退锡废液再生回用。
为实现以上目的，本发明硝酸型退锡废液再生回用方法，包括如下步骤：
(1)硝酸型退锡废液中锡铜金属离子的沉淀分离：将一定量的退锡废液加入反应槽，开启搅拌，加入金属离子捕获剂使得锡、铜、二价铁离子沉淀，过滤得到锡铜铁混合沉淀物和滤液；
为了使得锡铜有效得沉淀分离，本步骤所述金属离子捕获剂为能与锡铜在硝酸体系下形成沉淀的有机酸、有机酸盐，包括草酸、醋酸、乳酸、草酸铵，醋酸铵、乳酸铵，为了使得锡铜有效沉淀分离而又不影响退锡废液再生回用的品质，捕获剂的添加量为退锡废液体积的1％-6％，捕获剂加入后搅拌反应2小时-6小时，使得反应更充分，停止搅拌后，静置12-24小时(起到陈化作用，使得锡铜铁沉淀物更容易进行固液分离)后进行固液分离，得到锡铜铁沉淀物与过滤液；
(2)退锡废液滤液深度除杂净化：将步骤(1)所得滤液加入除杂剂进行深度除杂净化，因退锡废液中残留失效的护铜剂、锡络合剂、过量的金属离子捕获剂均属于有机物，本步骤优选对有机物具有吸附作用的除杂剂，包括活性炭、锯末渣、硅藻土，除杂剂添加的比例为滤液体积的0.5％-2％，添加后搅拌2-6小时，然后静置12-24小时后，过滤得到净化后退锡废液；
(3)调配硝酸型退锡再生液：将步骤(2)所得净化后退锡废液加入调配槽，补加硝酸、促进剂、锡络合剂、护铜剂等调配成再生退锡液，
为了使得再生退锡液不增量(即再生后的退锡废液与新配退锡子夜体积相 当)，硝酸优选质量浓度为62％以上的硝酸，为了加快再生液的退锡速度，促进剂优选硝酸铁或三氯化铁，为了使得退锡后的退锡液不产生锡泥沉淀，需要在再生退锡液中加入锡络合剂，优选苯芴酮，添加量为再生退锡液体积的0.005％-0.05％，为了减缓再生退锡液对退锡后铜面的腐蚀，再生退锡液中需要添加护铜剂，护铜剂优选硫脲、苯并三氮莝，添加量为再生退锡液体积的0.05％-0.15％；
(4)锡铜铁沉淀物的溶解：先在反应釜中加入一定量的盐酸，盐酸的添加量为锡铜铁沉淀物完全溶解所需化学计量的1.1-1.2倍，开启搅拌，然后加入步骤(1)所得的锡铜铁混合沉淀物，升温至90-100摄氏度，使得沉淀物完全溶解，补加纯水得到锡离子浓度维持在6％-9％浓度的氯化锡铜铁盐酸溶液；
(5)利用双膜三室电解槽电解沉积回收锡铜：将步骤(4)所得氯化锡铜铁溶液注入双膜三室电解槽的阴极室，中间隔离室注入0.5％-1％质量浓度的盐酸溶液，阳极室注入0.5％-5％质量浓度的硫酸溶液，阴极采用钛板，阳极采用涂布贵金属的钛不溶阳极，在室温的条件下电解，阴极产板上依次电解沉积铜、锡金属，阴极室产生的氯离子通过阴离子离子交换膜进入中间隔室，阳极产生氧气与氢离子，氢离子透过阳离子交换膜进入中间隔室，电解结束将中间隔室盐酸溶液抽出回用至步骤(4)锡铜铁沉淀物的溶解工序，阴极室铜锡电解沉淀结束后得到氯化铁氯化亚铁的混合溶液；
双膜三室电解槽阳极室与中间隔室用阳离子离子交换膜分隔，中间隔室与阴极室用阴离子离子交换膜分隔；
本工序主要发生的电化学反应是：
阳极室：2H 2O→4H ++O 2
阴极室：SnCl 4→Sn+4Cl - CuCl 2→Cu+2Cl -
中隔室：H ++Cl -→HCl
(6)制备三氯化铁：
将步骤(5)所得氯化铁氯化亚铁溶液通入步骤(5)阳极室所产生的氧气使得亚铁进一步氧化得到三氯化铁溶液，本步骤所得三氯化铁溶液可以用作污水处理的絮凝剂。
本发明区别于现有技术的有益效果是：
1、通过对分离沉淀锡铜亚铁后的退锡废液的深度净化，解决了残留失效添加剂对退锡后表面的影响，进一步，深度净化也去除了过量金属捕获剂对退锡效果的影响，再生液补加锡络合剂、护铜剂等使得再生液退锡速度、蚀铜速度、退锡后铜表面与新退锡液无差别，使得退锡废液再生工艺在工业上可行，避免了退锡废液转移二次污染环境的风险；
2、退锡废液回收所得锡铜铁混合化合物进一步处理，回收得到金属锡铜与三氯化铁净水剂，避免了传统火法分离锡铜铁的高能耗、空气污染问题。
附图说明
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本发明的PCB硝酸型退锡废液再生回用方法的工艺流程图；
图2为本发明的双膜三室电解槽的结构示意图。
具体实施方式
实施例1
某PCB厂退锡废液含锡6％，铜0.5％，硝酸4.5mol/L，将2000L退锡废液加入反应釜，开启搅拌，加入20Kg草酸(1％废液体积比)，搅拌反应5小时，停止搅拌，静置沉淀12小时，固液分离，得到锡铜铁混合沉淀物与过滤液；将1500L过滤液抽入反应釜，加入30Kg(2％滤液体积比)硅藻土搅拌2小时，静 置24小时，过滤得到净化后的退锡废液；将1000L净化后退锡废液抽入再生退锡液调配槽，开启搅拌，加入质量浓度为68％的硝酸调配至再生退锡液酸浓度为6mol/L，加入0.5Kg锡络合剂苯芴酮(废液体积比0.05％)，5Kg护铜剂苯并三氮莝，50公斤退锡促进剂九水合硝酸铁配置成再生硝酸型退锡液回用至PCB退锡生产线；
实施例2
将1000L实施例1的再生硝酸型退锡液回用生产线后所得退锡废液加入反应釜，开启搅拌，加入60Kg草酸铵(2％废液体积比)，搅拌反应5小时，停止搅拌，静置沉淀15小时，固液分离，得到锡铜铁混合沉淀物与过滤液；将800L过滤液抽入反应釜，加入8Kg(1％滤液体积比)锯末渣搅拌2小时，静置15小时，过滤得到净化后的退锡废液；将800L净化后退锡废液抽入再生退锡液调配槽，开启搅拌，加入质量浓度为68％的硝酸调配至再生退锡液酸浓度为6mol/L，加入0.08Kg锡络合剂苯芴酮(废液体积比0.01％)，8Kg护铜剂硫脲，40公斤退锡促进剂三氯化铁配置成再生硝酸型退锡液回用至PCB退锡生产线；
实施例3
某PCB厂退锡废液含锡8％，铜0.2％，硝酸4.1mol/L，将2000L退锡废液加入反应釜，开启搅拌，加入120Kg草酸(6％废液体积比)，搅拌反应5小时，停止搅拌，静置沉淀24小时，固液分离，得到锡铜铁混合沉淀物与过滤液；将1500L过滤液抽入反应釜，加入7.5Kg(0.5％滤液体积比)活性炭搅拌2小时，静置12小时，过滤得到净化后的退锡废液；将1000L净化后退锡废液抽入再生退锡液调配槽，开启搅拌，加入质量浓度为68％的硝酸调配至再生退锡液酸浓度为6mol/L，加入0.05Kg锡络合剂苯芴酮(废液体积比0.005％)，15Kg护铜剂苯并三氮莝，30公斤退锡促进剂九水合硝酸铁，20公斤三氯化铁配置成再生硝酸型退锡液回用至PCB退锡生产线；
实施例4
请参阅附图1-2，取一定量的实施例1-3所得锡铜铁沉淀物，按化学计量比 1.1倍加入盐酸，在90摄氏度的条件下搅拌溶解，加纯水调配成锡离子质量浓度为6％的氯化锡铜铁的盐酸溶液，将该溶液注入双膜三室电解槽的阴极室1内，中间隔室3注入0.5％质量浓度的盐酸溶液，阳极室2注入0.5％质量浓度的硫酸溶液，室温(25摄氏度左右)开启电解沉积金属铜锡，阴极室1产生的氯离子通过阴离子离子交换膜4进入中间隔室3，阳极产生氧气与氢离子，氢离子透过阳离子交换膜5进入中间隔室3，电解结束将中间隔室3的盐酸溶液抽出回用至锡铜铁沉淀物的溶解工序，阴极室铜锡电解沉淀结束后得到氯化铁氯化亚铁的混合溶液中的间隔室3富集盐酸，阴极板上得到金属铜与锡，锡铜电解沉积结束，分别抽出阴极室1电解贫液(氯化亚铁溶液)与中间隔室3盐酸溶液备用；
实施例5
请参阅附图1-2，取一定量的实施例1-3所得锡铜铁沉淀物，按化学计量比1.2倍加入盐酸(优先使用实施例4中间隔室收集的盐酸溶液，不足部分另外补加)在100摄氏度的条件下搅拌溶解，加纯水调配成锡离子质量浓度为9％的氯化锡铜铁的盐酸溶液，将该溶液注入双膜三室电解槽的阴极室1内，中间隔室3注入1％质量浓度的盐酸溶液，阳极室2注入1％质量浓度的硫酸溶液，室温(25摄氏度左右)开启电解沉积金属铜锡，阴极室1产生的氯离子通过阴离子离子交换膜4进入中间隔室3，阳极产生氧气与氢离子，氢离子透过阳离子交换膜5进入中间隔室3，电解结束将中间隔室3的盐酸溶液抽出回用至锡铜铁沉淀物的溶解工序，氧气通入实施例4电解贫液氧化使得氯化亚铁溶液氧化成三氯化铁溶液，中间隔室3富集盐酸，阴极板上得到金属铜与锡，锡铜电解沉积结束，分别抽出阴极室1电解贫液与中间隔室盐酸溶液备用；
实施例6
请参阅附图1-2，取一定量的实施例1-3所得锡铜铁沉淀物，按化学计量比1.15倍加入盐酸(优先使用实施例4中间隔室收集3的盐酸溶液，不足部分另外补加)在95摄氏度的条件下搅拌溶解，加纯水调配成锡离子质量浓度为8％的氯化锡铜铁的盐酸溶液，将该溶液注入双膜三室电解槽的阴极室1内，中间 隔室3注入0.8％质量浓度的盐酸溶液，阳极室2注入5％质量浓度的硫酸溶液，室温(25摄氏度左右)开启电解沉积金属铜锡，阴极室1产生的氯离子通过阴离子离子交换膜4进入中间隔室3，阳极产生氧气与氢离子，氢离子透过阳离子交换膜5进入中间隔室3，电解结束将中间隔室3的盐酸溶液抽出回用至锡铜铁沉淀物的溶解工序，阳极产生的氧气通入实施例4电解贫液氧化使得氯化亚铁溶液氧化成三氯化铁溶液，中间隔室3富集盐酸，阴极板上得到金属铜与锡，锡铜电解沉积结束，分别抽出阴极室1电解贫液与中间隔室3盐酸溶液备用。
综上所述，本发明具有以下优点：
1、不但有效分离出退锡废液中的锡铜，进一步对退锡废液滤液的处理，使得退锡废液回用达到了与新退锡液一样的效果；
2、危险废物实现厂区循环利用，无增量废液外排，对环境友好；
3、不更改现有PCB生产线现有蚀刻生产方式，易实现推广；
4、通过双膜三室电解沉积回收金属铜锡，降低了传统火法冶炼分离锡铜工艺污染环境的风险。
上所述仅为本发明的实施方式而已，并不用于限制本发明。对于本领域技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原理内所作的任何修改、等同替换、改进等，均应包括在本发明的权利要求范围之内。

Claims (10)

  1. 一种PCB硝酸型退锡废液再生回用方法,其特征在于，包括以下步骤:
    (1)硝酸型退锡废液中锡铜金属离子的沉淀分离：将一定量的退锡废液加入反应槽，开启搅拌，加入金属离子捕获剂使得锡、铜、二价铁离子沉淀，过滤得到锡铜铁混合沉淀物和滤液；
    (2)退锡废液滤液深度除杂净化：将步骤(1)所得滤液加入除杂剂进行深度除杂净化；
    (3)调配硝酸型退锡再生液：将步骤(2)所得净化后退锡废液加入调配槽，补加硝酸、促进剂、锡络合剂、护铜剂调配成再生退锡液；
    (4)锡铜铁沉淀物的溶解：先在反应釜中加入一定量的盐酸，盐酸的添加量为锡铜铁沉淀物完全溶解所需化学计量的1.1-1.2倍，开启搅拌，然后加入步骤(1)所得的锡铜铁混合沉淀物，升温至90-100摄氏度，使得沉淀物完全溶解，补加纯水得到锡离子浓度维持在6％-9％浓度的氯化锡铜铁盐酸溶液；
    (5)利用双膜三室电解槽电解沉积回收锡铜：将步骤(4)所得氯化锡铜铁溶液注入双膜三室电解槽的阴极室，在室温的条件下电解，阴极产板上依次电解沉积铜、锡金属，阴极室产生的氯离子通过阴离子离子交换膜进入中间隔室，阳极产生氧气与氢离子，氢离子透过阳离子交换膜进入中间隔室，电解结束将中间隔室盐酸溶液抽出回用至步骤(4)锡铜铁沉淀物的溶解工序，阴极室铜锡电解沉淀结束后得到氯化铁氯化亚铁的混合溶液；
    (6)制备三氯化铁：将步骤(5)所得氯化铁氯化亚铁溶液通入步骤(5)阳极室所产生的氧气使得亚铁进一步氧化得到三氯化铁溶液。
  2. 根据权利要求1所述的PCB硝酸型退锡废液再生回用方法,其特征在于：所述步骤1的金属离子捕获剂选自草酸、醋酸、乳酸、草酸铵、醋酸铵和乳酸铵中的任意一种或者几种的组合物。
  3. 根据权利要求1或2所述的PCB硝酸型退锡废液再生回用方法,其特征在于：所述步骤(1)的金属离子捕获剂的添加量为退锡废液体积的1％-6％，捕获 剂加入后搅拌反应2小时-6小时，使得反应更充分，停止搅拌后，静置12-24小时。
  4. 根据权利要求1所述的PCB硝酸型退锡废液再生回用方法,其特征在于：所述步骤(2)的除杂剂选自活性炭、锯末渣和硅藻土中任意一种或者几种的组合物。
  5. 根据权利要求4所述的PCB硝酸型退锡废液再生回用方法,其特征在于：，所述除杂剂添加的比例为滤液体积的0.5％-2％，添加后搅拌2-6小时，然后静置12-24小时后，过滤得到净化后退锡废液。
  6. 根据权利要求1所述的PCB硝酸型退锡废液再生回用方法,其特征在于：所述步骤(3)中的硝酸的质量浓度为62％以上。
  7. 根据权利要求1所述的PCB硝酸型退锡废液再生回用方法,其特征在于：所述步骤(3)中的促进剂选自硝酸铁和三氯化铁中的任意一种或者两种的组合物。
  8. 根据权利要求1所述的PCB硝酸型退锡废液再生回用方法,其特征在于：所述步骤(3)中的锡络合剂为苯芴酮，所述锡络合剂的添加量为再生退锡液体积的0.005％-0.05％。
  9. 根据权利要求1所述的PCB硝酸型退锡废液再生回用方法,其特征在于：所述步骤(3)中的护铜剂选自硫脲和苯并三氮莝中的任意一种或者两种的组合物，所述护铜剂添加量为再生退锡液体积的0.05％-0.15％。
  10. 根据权利要求1所述的PCB硝酸型退锡废液再生回用方法,其特征在于：所述步骤(5)中，所述双膜三室电解槽的阳极室与中间隔室用阳离子离子交换膜分隔，中间隔室与阴极室用阴离子离子交换膜分隔，中间隔离室注入0.5％-1％质量浓度的盐酸溶液，阳极室注入0.5％-5％质量浓度的硫酸溶液，阴极采用钛板，阳极采用涂布贵金属的钛不溶阳极。
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CN113754130A (zh) * 2021-09-30 2021-12-07 广东中奕环保科技有限公司 退锡废液回收再生处理系统及方法
CN114369831A (zh) * 2021-12-27 2022-04-19 广东臻鼎环境科技有限公司 一种可循环再生硝酸型退锡废液用添加剂及其应用
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