WO2021147342A1 - 废线路板全组分微波快速消解与贵金属离子液体萃取方法 - Google Patents

废线路板全组分微波快速消解与贵金属离子液体萃取方法 Download PDF

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WO2021147342A1
WO2021147342A1 PCT/CN2020/114544 CN2020114544W WO2021147342A1 WO 2021147342 A1 WO2021147342 A1 WO 2021147342A1 CN 2020114544 W CN2020114544 W CN 2020114544W WO 2021147342 A1 WO2021147342 A1 WO 2021147342A1
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leaching
liquid
waste circuit
circuit boards
extraction
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French (fr)
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吴玉锋
焉杰文
李彬
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Beijing University of Technology
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Beijing University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/36—Heterocyclic compounds
    • C22B3/362—Heterocyclic compounds of a single type
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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 invention relates to a method for rapid microwave digestion of all components of waste circuit boards and extraction of precious metal ionic liquids, in particular to a microwave-assisted method for high-efficiency separation of precious metals from waste circuit boards and clean and efficient extraction of ionic liquids.
  • Waste circuit boards are commonly used components of electronic and electrical equipment, and are also the core components of electronic waste.
  • the circuit board is composed of an insulating substrate made of glass fiber and epoxy resin, a copper foil used for conductive paths, and electronic components soldered on its surface.
  • the contacts and special positions are usually plated with precious metals such as gold and nickel to form copper-nickel and gold-nickel alloys. Due to the existence of hazardous substances, the disposal of electronic waste is a serious problem worldwide.
  • the waste circuit board contains about 40% metal, 30% organic resin and 30% ceramic [1]. Among them, there are 100-270kg copper and 80g-1kg gold in the average 1t circuit board [2], which has rich resource value. At the same time, a large number of heavy metals and benzene-like toxic and harmful substances, improper handling will produce harmful substances such as dioxins and furans, which will seriously endanger the environment and human health, and cause environmental hazards. Therefore, the study of clean and efficient waste circuit board separation and recycling technology has very important practical significance for reducing environmental hazards and improving resource recovery and utilization.
  • pyrometallurgical technology is mainly concentrated on pyrolysis technology.
  • the waste circuit boards are crushed and sent to the reactor for pyrolysis to carbonize the non-metals in them, crush and sort the solid products, and recover metals and non-metals (CN109252051A).
  • Patent CN110004299A discloses a method for comprehensive recovery of waste circuit board pyrolysis polymetallic products.
  • the polymetallic product obtained by pyrolysis of waste circuit board at a certain temperature is added to a smelting furnace for smelting and blending to obtain alloy liquid, and then atomizing it After that, it is dissolved in an acid solution, and the filtered acid hydrolysis residue is recovered for rare and precious metals.
  • a smelting furnace for smelting and blending to obtain alloy liquid, and then atomizing it After that, it is dissolved in an acid solution, and the filtered acid hydrolysis residue is recovered for rare and precious metals.
  • the method of hydrometallurgical recovery of precious metals from waste circuit boards is usually to mechanically break the waste circuit boards into fine particles, physically separate the metals and precious metals, and select strong oxidizing acids and alkalis (or strong oxidants) to transfer the valuable leaching to the solution Among them, after filtration, electrolysis and other technologies are used to obtain precious metals (such as patent numbers CN104328281A, CN105755289A).
  • the process mainly involves complicated processes and long processes, large amounts of reagents, and more toxic waste liquids.
  • Patent CN109609767A developed an ultrasonic-assisted technology for preferential separation of precious metals based on the characteristics of precious metals existing on the surface of circuit boards.
  • the purpose of the present invention is to solve the problems of rapid microwave digestion of all components of waste circuit boards and extraction of precious metal ionic liquids. Because microwave can penetrate the leaching medium and directly heat the circuit board, microwave-assisted leaching can enhance the mass and heat transfer in the traditional leaching process, greatly shorten the leaching time and improve the leaching efficiency. There is no need to crush waste circuit boards before leaching, which saves energy and protects the environment.
  • the reaction can control its heating process and reaction time. The whole process is carried out under closed conditions to avoid heat loss during the leaching process.
  • the valuable leaching leaching rate is high, the selectivity is strong, and the efficient leaching of valuable metals can be realized.
  • the precious metal leaching solution is extracted with imidazole ionic liquid, which has strong selectivity to gold, and there is no co-extraction phenomenon with nickel and copper ions.
  • imidazole ionic liquid As a new type of extractant, compared with traditional organic extractants, it has the advantages of non-volatile, high ignition point, wide liquid range, stable physical and chemical properties, etc.
  • the extraction of precious metal leachate by ionic liquid is a clean and green recovery method.
  • the method for realizing the full-component microwave rapid digestion of waste circuit boards and the extraction of precious metal ionic liquids described in the present invention includes the following steps:
  • waste circuit boards Cut waste circuit boards into small pieces, each weighing between 0.1 and 0.2g, to obtain waste circuit boards to be leached.
  • Precious metal leaching solution configuration for waste circuit boards add pure water, thiourea, sulfuric acid, and sodium peroxide to the beaker, and stir quickly until all are dissolved to obtain the leaching solution.
  • concentration of the extract is: thiourea: 1.5-4mol/L, sulfuric acid 0.5-2mol/L, sodium peroxide 1-3mol/L.
  • Microwave-assisted leaching of waste circuit boards Put the pre-processed circuit boards in the digestion tank, and pour the extract into the digestion tank at the same time, set the microwave digestion instrument's heating time 1 ⁇ 1.5h, and the heating temperature 180 ⁇ 200°C.
  • the cooling time is 15-30 minutes, and the temperature is cooled to 60°C to obtain the precious metal leachate and resin-containing waste residue.
  • Step (4) Add an oxalic acid solution to the organic phase at a volume ratio of the organic phase to the oxalic acid solution at a volume ratio of 1:1 to 1:10.
  • the concentration of the oxalic acid solution is 1 to 3 mol/L for back extraction. Stir thoroughly for 5-15 minutes to make the two phases of oil and liquid fully mixed. After centrifuging and separating the obtained mixed phase, a stripping raffinate and a pure ionic liquid are obtained. The organic phase ionic liquid is recycled to step (4) to repeat the extraction.
  • step (6) Filter the step (5) back extraction liquid to obtain the first tail liquid and crude gold powder.
  • the first tail liquid undergoes evaporation and crystallization to recover sodium chloride.
  • Second tail liquid treatment Add sulfuric acid, thiourea, and sodium peroxide to step (7) tail liquid 2 to make the sulfuric acid, thiourea, and sodium peroxide in the second tail liquid meet the concentration of step (2).
  • concentration standard of the leaching solution in the middle, repeated cycles, when the sulfate reaches saturation, the second tailing solution will not return to the leaching process.
  • the microwave-assisted leaching process can control the heating process and reaction time.
  • the whole process is carried out under closed conditions to avoid heat loss during the leaching process.
  • the valuable leaching has high leaching rate and strong selectivity, which can realize the efficient leaching of valuable metals.
  • the ionic liquid extraction process has strong selectivity to gold, and there is no co-extraction phenomenon with nickel and copper ions.
  • As a new type of extractant compared with traditional organic extractants, it has the advantages of non-volatile, high ignition point, wide liquid range, stable physical and chemical properties, and strong extraction capacity.
  • the recovery rate of gold is as high as 98.5%
  • nickel is as high as 99%
  • copper is as high as 99.5%.
  • the tail liquid can be recycled, and the extraction reagents leached in the process are green and clean, without secondary pollution, and are environmentally friendly.
  • Figure 1 shows the technology roadmap for the rapid microwave digestion of waste circuit boards and the extraction of precious metal ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

废线路板全组分微波快速消解与贵金属离子液体萃取方法属于湿法冶金领域。基于微波可以穿透浸出介质，直接加热线路板，所以微波辅助浸出可以强化传统浸出过程中的传质、传热，大幅缩短浸出时间，提高浸出效率。在浸出前无需对废线路板进行破碎处理，节省能源的同时保护环境。反应可以控制其升温过程及反应时间，全过程在密闭条件下进行，避免浸出过程中热量的损失，有价金属浸出率高、选择性强，可实现有价金属的高效浸出。对贵金属浸出液采取咪唑类离子液体进行萃取，其对金选择性强，不存在与镍、铜等离子的共萃现象。通过离子液体萃取贵金属浸出液是一种清洁绿色回收方法，金、镍、铜的整体回收率可达99％以上。

Description

废线路板全组分微波快速消解与贵金属离子液体萃取方法 技术领域
本发明涉及废线路板全组分微波快速消解与贵金属离子液体萃取方法，特别是涉及微波辅助的废线路板贵金属高效分离及离子液体清洁高效萃取方法。
背景技术
近年来，随着人口的增长，以及经济的快速增长，技术的不断创新，生活水平的提高，电子电器设备寿命的缩短以及消费者态度的改变，需要安全管理的废旧电子废弃物数量显著增加。废弃线路板是电子电器设备的常用组件，也是电子废弃物的核心组件。线路板是由玻璃纤维及环氧树脂构成的绝缘基板，和用于导电通路的铜箔以及在其表面焊接的电子元器件组成。为增加其导电性，通常在触点及特殊位置镀有金、镍等贵金属，形成铜-镍，金-镍合金。由于有害物质的存在，电子废弃物的处理处置是一个世界性的严重问题。废弃线路板中大约含有40％金属、30％的有机树脂和30％陶瓷[1]。其中平均1t线路板中有100-270kg铜，80g-1kg金[2]，具有丰富的资源价值。同时，大量的重金属和苯类有毒有害物质，处理不当会产生二噁英、呋喃等有害物，严重危害环境和人类健康，造成环境危害。因此，研究清洁，高效的废线路板分离回收技术对于降低环境危害、提升资源回收利用率有非常重要的现实意义。
目前，对于废线路板回收主要分为火法冶金和湿法冶金技术。其中火法冶金技术主要集中为热解技术。将废线路板经过粉碎送入反应釜中热解，使其中的非金属碳化，对固体产物进行破碎分选，回收金属与非金属(CN109252051A)。专利CN110004299A公开了一种废线路板热解多金属产物综合回收的方法，将废线路板在一定温度下热解得到的多金属加入到熔炼炉中进行熔炼调配得到合金液，再将其雾化后通过酸液进行溶解，将过滤后 的酸解渣进行稀贵金属的回收。但由于热解工艺对温度控制较为严格以及热解产物呋喃、二噁英等会环境造成污染，使其在应用中存在一定难度。湿法冶金回收废线路板贵金属方法通常为通过机械破碎将废弃线路板破碎为细小颗粒，物理分选出金属与贵金属，选取强氧化性酸、碱(或强氧化剂)将有价浸出转移至溶液中，过滤后再采用电解等技术得到贵金属(如专利号CN104328281A、CN105755289A)，其工艺主要存在工艺复杂流程长，消耗试剂量大，易产生较多有毒废液。
由此可见，无论火法或湿法回收废线路板中有价金属都具有其优点或缺点，针对湿法回收线路板工艺流程长、回收效率低等缺点，近年来有研究通过外场辅助手段强化浸出过程弥补湿法冶金过程中的不足。专利CN109609767A针对贵金属在线路板中存在于表面的特性，开发了一种超声辅助贵金属优先分离技术。
发明内容
本发明的目的主要解决废线路板全组分微波快速消解与贵金属离子液体萃取问题。基于微波可以穿透浸出介质，直接加热线路板，所以微波辅助浸出可以强化传统浸出过程中的传质、传热，大幅缩短浸出时间，提高浸出效率。在浸出前无需对废线路板进行破碎处理，节省能源的同时保护环境。反应可以控制其升温过程及反应时间，全过程在密闭条件下进行，避免浸出过程中热量的损失，有价浸出浸出率高、选择性强，可实现有价金属的高效浸出。
对贵金属浸出液采取咪唑类离子液体进行萃取，其对金选择性强，不存在与镍、铜等离子的共萃现象。作为一种新型的萃取剂，与传统的有机萃取剂相比，其具有不易挥发、燃点高、液程宽、物理化学性能稳定等优点，通过离子液体萃取贵金属浸出液是一种清洁绿色回收方法。
实现本发明所叙述一种废线路板全组分微波快速消解与贵金属离子液体萃取方法，包括如下步骤：
(1)废线路板预处理：将废线路板剪切成小块，每块重量为0.1～0.2g之 间，得到待浸出废线路板。
(2)废线路板贵金属浸提液配置：烧杯中加入纯水、硫脲、硫酸、过氧化钠，快速搅拌至全部溶解，得到浸提液。浸提液的浓度为：硫脲：1.5～4mol/L、硫酸0.5～2mol/L、过氧化钠1～3mol/L。
(3)废线路板微波辅助浸出：将预处理线路板置于消解罐中，同时将浸提液倒入消解罐，设定微波消解仪升温时间1～1.5h，升温温度180～200℃，冷却时间15～30min，冷却至60℃，得到贵金属浸出液和含树脂废渣。
(4)过滤后，将含步骤(3)贵金属浸出液置于萃取罐中，按离子液体与贵金属浸出液体积比1:1～1:5加入咪唑离子液体[BMIM][NTF2]，充分搅拌5～15min，使得油液两相充分混合。将得到的混合相离心、分液后得到有机相和萃余液。
(5)步骤(4)有机相中按有机相与草酸溶液体积比1:1～1:10加入草酸溶液，草酸溶液浓度1～3mol/L,进行反萃取。充分搅拌5～15min，使得油液两相充分混合。将得到的混合相离心、分液后得到反萃余液及纯净离子液体。有机相离子液体循环至步骤(4)重复萃取。
(6)将步骤(5)反萃余液过滤，得到第一尾液及粗金粉。第一尾液进行蒸发结晶回收氯化钠。
(7)萃余液贵金属分离：向步骤(4)萃余液中加入氢氧化钠，调节pH值为6.7～7.0，水解沉淀并过滤，得到氢氧化铜沉淀和脱铜液；向脱铜液中加入固体氢氧化钠，调节pH值为9.5～10.0，水解沉淀并过滤，得到氢氧化镍沉淀和第二尾液。
(8)第二尾液处理：向步骤(7)尾液2中加入硫酸、硫脲、过氧化钠，使第二尾液中硫酸、硫脲、过氧化钠，使其浓度满足步骤(2)中浸提液浓度标准，多次循环，硫酸盐达到饱和时，第二尾液不再返回浸出过程。
微波辅助浸出过程可以控制其升温过程及反应时间，全过程在密闭条件 下进行，避免浸出过程中热量的损失，有价浸出浸出率高、选择性强，可实现有价金属的高效浸出。离子液体萃取过程，对金选择性强，不存在与镍、铜等离子的共萃现象。作为一种新型的萃取剂，与传统的有机萃取剂相比，其具有不易挥发、燃点高、液程宽、物理化学性能稳定、萃取能力强等优点。整体回收过程金的回收率高达98.5％以上，镍高达99％以上，铜高达99.5％以上。尾液可循环利用，过程中浸出萃取试剂绿色清洁，无二次污染，对环境友好。
附图说明
图1表示废线路板全组分微波快速消解与贵金属离子液体萃取技术路线图
具体实施方式
实例1
将废线路板剪切成小块，每块重量为0.1g，得到预处理废线路板；在烧杯中配置贵金属浸提溶液，浓度为硫脲：1.5mol/L、硫酸1.5mol/L、过氧化钠2mol/L；将预处理线路板置于消解罐中，同时将浸提液倒入消解罐，设定微波消解仪升温至185℃，时间1h，保温时间20min，冷却时间15min，冷却至60℃，待冷却结束，过滤，得到贵金属浸出液和含树脂废渣；将贵金属浸出液置于萃取罐中，按离子液体与贵金属浸出液体积比1:1加入咪唑离子液体[BMIM][NTF2]，充分搅拌5min，使油液两相充分混合，得到油液混合相。向有机相中按有机相与草酸溶液体积比1:2加入草酸溶液，草酸溶液浓度1.5mol/L,充分搅拌10min，使得油液两相充分混合，反萃取得到纯净有机相和反萃余液。将反萃余液过滤，得到第一尾液及粗金粉；第一尾液进行蒸发结晶回收氯化钠。向萃余液中加入氢氧化钠，调节pH值为6.7，水解沉淀并过滤，得到氢氧化铜沉淀和脱铜液；向脱铜液中加入氢氧化钠，调节pH值为9.6，水解沉淀并过滤，得到氢氧化镍沉淀和第二尾液。向第二尾液中加入硫酸、硫脲、过氧化钠，使其浓度满足浸提液浓度标准，返回配置贵金属浸出溶液；整体工艺流程金的回收率达到99％,镍浸出率达到99.5％，铜浸出率达 到99.3％。
实例2
将废线路板剪切成小块，每块重量为0.15g，得到预处理废线路板；在烧杯中配置贵金属浸提溶液，浓度为硫脲：2mol/L、硫酸1.8mol/L、过氧化钠1.5mol/L；将预处理线路板置于消解罐中，同时将浸提液倒入消解罐，设定微波消解仪升温至180℃，时间1.2h，保温时间20min，冷却时间25min，冷却至60℃，待冷却结束，过滤，得到贵金属浸出液和含树脂废渣；将贵金属浸出液置于萃取罐中，按离子液体与贵金属浸出液体积比1:2加入咪唑离子液体[BMIM][NTF2]，充分搅拌8min，使油液两相充分混合，得到油液混合相。向有机相中按有机相与草酸溶液体积比1:5加入草酸溶液，草酸溶液浓度2mol/L,充分搅拌12min，使得油液两相充分混合，反萃取得到纯净有机相和反萃余液。将反萃余液过滤，得到第一尾液及粗金粉；第一尾液进行蒸发结晶回收氯化钠。向萃余液中加入氢氧化钠，调节pH值为6.9，水解沉淀并过滤，得到氢氧化铜沉淀和脱铜液；向脱铜液中加入氢氧化钠，调节pH值为9.5，水解沉淀并过滤，得到氢氧化镍沉淀和第二尾液。向第二尾液中加入硫酸、硫脲、过氧化钠，使其浓度满足浸提液浓度标准，返回配置贵金属浸出溶液；整体工艺流程金的回收率达到99.6％,镍浸出率达到99.2％，铜浸出率达到99.5％。
实例3
将废线路板剪切成小块，每块重量为0.18g，得到预处理废线路板；在烧杯中配置贵金属浸提溶液，浓度为硫脲：3.5mol/L、硫酸2mol/L、过氧化钠2.5mol/L；将预处理线路板置于消解罐中，同时将浸提液倒入消解罐，设定微波消解仪升温至190℃，时间1.5h，保温时间20min，冷却时间20min，冷却至60℃，待冷却结束，过滤，得到贵金属浸出液和含树脂废渣；将贵金属浸出液置于萃取罐中，按离子液体与贵金属浸出液体积比1:3加入咪唑离子液体[BMIM][NTF2]，充分搅拌12min，使油液两相充分混合，得到油液混合相。向有机相中按有机相与草酸溶液体积比1:8加入草酸溶液，草酸溶液浓度2.8mol/L,充分搅拌12min，使得油液两相充分混合，反萃取得到纯净有机相 和反萃余液。将反萃余液过滤，得到第一尾液及粗金粉；第一尾液进行蒸发结晶回收氯化钠。向萃余液中加入氢氧化钠，调节pH值为6.8，水解沉淀并过滤，得到氢氧化铜沉淀和脱铜液；向脱铜液中加入氢氧化钠，调节pH值为9.9，水解沉淀并过滤，得到氢氧化镍沉淀和第二尾液。向第二尾液中加入硫酸、硫脲、过氧化钠，使其浓度满足浸提液浓度标准，返回配置贵金属浸出溶液；整体工艺流程金的回收率达到99.7％,镍浸出率达到99.4％，铜浸出率达到99.6％。
实例4
将废线路板剪切成小块，每块重量为0.2g，得到预处理废线路板；在烧杯中配置贵金属浸提溶液，浓度为硫脲：3.8mol/L、硫酸1.6mol/L、过氧化钠2.8mol/L；将预处理线路板置于消解罐中，同时将浸提液倒入消解罐，设定微波消解仪升温至195℃，时间1.2h，保温时间20min，冷却时间25min，冷却至60℃，待冷却结束，过滤，得到贵金属浸出液和含树脂废渣；将贵金属浸出液置于萃取罐中，按离子液体与贵金属浸出液体积比1:4加入咪唑离子液体[BMIM][NTF2]，充分搅拌15min，使油液两相充分混合，得到油液混合相。向有机相中按有机相与草酸溶液体积比1:10加入草酸溶液，草酸溶液浓度2.5mol/L,充分搅拌15min，使得油液两相充分混合，反萃取得到纯净有机相和反萃余液。将反萃余液过滤，得到第一尾液及粗金粉；第一尾液进行蒸发结晶回收氯化钠。向萃余液中加入氢氧化钠，调节pH值为7.0，水解沉淀并过滤，得到氢氧化铜沉淀和脱铜液；向脱铜液中加入氢氧化钠，调节pH值为9.8，水解沉淀并过滤，得到氢氧化镍沉淀和第二尾液。向第二尾液中加入硫酸、硫脲、过氧化钠，使其浓度满足浸提液浓度标准，返回配置贵金属浸出溶液；整体工艺流程金的回收率达到99.9％,镍浸出率达到99.1％，铜浸出率达到99.5％。
实例5
将废线路板剪切成小块，每块重量为0.18g，得到预处理废线路板；在烧杯中配置贵金属浸提溶液，浓度为硫脲：3.2mol/L、硫酸1.2mol/L、过氧化钠 3.0mol/L；将预处理线路板置于消解罐中，同时将浸提液倒入消解罐，设定微波消解仪升温至200℃，时间1.3h，保温时间20min，冷却时间30min，冷却至60℃，待冷却结束，过滤，得到贵金属浸出液和含树脂废渣；将贵金属浸出液置于萃取罐中，按离子液体与贵金属浸出液体积比1:5加入咪唑离子液体[BMIM][NTF2]，充分搅拌10min，使油液两相充分混合，得到油液混合相。向有机相中按有机相与草酸溶液体积比1:8加入草酸溶液，草酸溶液浓度3mol/L,充分搅拌12min，使得油液两相充分混合，反萃取得到纯净有机相和反萃余液。将反萃余液过滤，得到第一尾液及粗金粉；第一尾液进行蒸发结晶回收氯化钠。向萃余液中加入氢氧化钠，调节pH值为6.8，水解沉淀并过滤，得到氢氧化铜沉淀和脱铜液；向脱铜液中加入氢氧化钠，调节pH值为10.0，水解沉淀并过滤，得到氢氧化镍沉淀和第二尾液。向第二尾液中加入硫酸、硫脲、过氧化钠，使其浓度满足浸提液浓度标准，返回配置贵金属浸出溶液；整体工艺流程金的回收率达到99.5％,镍浸出率达到99.4％，铜浸出率达到99.7％。

Claims (4)

  1. 一种废线路板全组分微波快速消解与贵金属离子液体萃取方法，其特征在于以下步骤：
    (1)废线路板预处理：将废线路板剪切成小块，得到待浸出废线路板；
    (2)废线路板贵金属浸提液配置：烧杯中加入纯水、硫脲、硫酸、过氧化钠，搅拌至全部溶解，得到浸提液；浸提液的浓度为：硫脲：1.5～4mol/L、硫酸0.5～2mol/L、过氧化钠1～3mol/L；
    (3)废线路板微波辅助浸出：将预处理线路板置于消解罐中，同时将浸提液倒入消解罐，设定微波消解仪升温时间1～1.5h，升温至180～200℃，保温时间20min，冷却时间15～30min，冷却至60℃，得到贵金属浸出液和含树脂废渣；
    (4)过滤后，将步骤(3)贵金属浸出液置于萃取罐中，按离子液体与贵金属浸出液体积比1:1～1:5加入咪唑离子液体[BMIM][NTF2]，充分搅拌5～15min，使得油液两相充分混合；将得到的混合相离心、分液后得到有机相和萃余液；
    (5)步骤(4)有机相中按有机相与草酸溶液体积比1:1～1:10加入草酸溶液，草酸溶液浓度1～3mol/L,进行反萃取；充分搅拌5～15min，使得油液两相充分混合；将得到的混合相离心、分液后得到反萃余液及纯净离子液体；
    (6)将步骤(5)反萃余液过滤，得到第一尾液及粗金粉；
    (7)萃余液贵金属分离：向步骤(4)萃余液中加入氢氧化钠，调节pH值为6.7～7.0，水解沉淀并过滤，得到氢氧化铜沉淀和脱铜液；向脱铜液中加入固体氢氧化钠，调节pH值为9.5～10.0，水解沉淀并过滤，得到氢氧化镍沉淀和第二尾液。
  2. 如权利要求1所述的一种废线路板全组分微波快速消解与贵金属离子液体萃取方法，其特征在于：步骤(5)将纯净离子液体循环至步骤(4)重复萃取。
  3. 如权利要求1所述的一种废线路板全组分微波快速消解与贵金属离子液体萃取方法，其特征在于：步骤(6)第一尾液通过蒸发结晶回收氯化钠。
  4. 如权利要求1所述的一种废线路板全组分微波快速消解与贵金属离子液体萃取方法，其特征在于：步骤(7)得到的第二尾液中加入硫酸、硫脲、过氧化钠，使第二尾液中硫酸、硫脲、过氧化钠，使其浓度满足步骤(2)中浸提液浓度标准，多次循环，硫酸盐达到饱和时，第二尾液不再返回浸出过程。
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CN119607618A (zh) * 2024-12-17 2025-03-14 东北电力大学 一种离子液体提取变压器油中金属及循环使用方法

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