WO2023097924A1 - 一种低成本高效的线路板元器件中贵金属回收方法 - Google Patents

一种低成本高效的线路板元器件中贵金属回收方法 Download PDF

Info

Publication number
WO2023097924A1
WO2023097924A1 PCT/CN2022/080536 CN2022080536W WO2023097924A1 WO 2023097924 A1 WO2023097924 A1 WO 2023097924A1 CN 2022080536 W CN2022080536 W CN 2022080536W WO 2023097924 A1 WO2023097924 A1 WO 2023097924A1
Authority
WO
WIPO (PCT)
Prior art keywords
concentration
hydrochloric acid
circuit board
precious metals
chloride
Prior art date
Application number
PCT/CN2022/080536
Other languages
English (en)
French (fr)
Inventor
俞嘉梅
郭嘉琪
Original Assignee
北京工业大学
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
Application filed by 北京工业大学 filed Critical 北京工业大学
Priority to US17/975,606 priority Critical patent/US11753699B2/en
Publication of WO2023097924A1 publication Critical patent/WO2023097924A1/zh

Links

Images

Classifications

    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated 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
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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 belongs to the technical field of recycling waste resources, and relates to a method for recycling precious metals in circuit board components.
  • Circuit boards are the core components of electronic products, and they exist in mobile phone boards, computer boards, audio equipment boards, LED boards and other equipment, and there are many types and huge quantities.
  • the amount of scrap is also increasing day by day.
  • the waste of electronic products in my country will exceed 27 million tons.
  • the production and sales of electronic products continue to increase, a large number of waste components will be produced. If these electronic wastes are not properly and effectively disposed of, they will cause environmental pollution and cause environmental problems to become more prominent.
  • the components on the waste circuit board are mainly composed of polymers, resins, glass fibers and various metal components. According to statistics, the total metal content in waste circuit board components accounts for about 40%, and the non-metal content accounts for about 60%.
  • the metal part mainly contains common metals such as aluminum, copper, nickel, iron, zinc, tin, etc., and contains gold, Precious metals such as silver, platinum, and palladium.
  • the content of precious metals in circuit board components is very high, especially the content of precious metal gold can be as high as 80g/t, which is much higher than the grade of 3-5g/t in domestic primary gold ores, and has a very high economic value. If the waste circuit board components are effectively recycled and the precious metals are extracted efficiently, it will not only alleviate the resource shortage problem caused by the small amount of mineral resources per capita in our country, but also bring considerable economic benefits.
  • Mechanical method use mechanical methods to dismantle waste circuit boards to separate the components and substrates, and then completely dissociate different metals and non-metals into powders by impact, shearing, extrusion and other crushing methods. According to the differences in physical properties such as density, conductivity, and magnetism of each component, the separation of metal and non-metal substances is realized.
  • the advantages of this method are simple process flow, low cost and environmental friendliness. It is used by 75% of circuit board processing companies in China. selected. But the disadvantage is that the product purity is not high.
  • Wet leaching technology mainly uses nitric acid, hydrochloric acid, etc. as oxidants, and utilizes the characteristics that metals can dissolve in these strong oxidizing media to achieve the separation of metals and non-metals.
  • Wet treatment has the advantages of wide adaptability, high metal recovery rate and high product purity, but the disadvantages are also more prominent, the treatment process is longer, and a large amount of acid and alkali are added in the process, including highly toxic cyanide. substances, causing environmental pollution.
  • Fire treatment is a traditional method for extracting metals. Under anaerobic or anoxic conditions, the temperature is controlled at 350-900°C, and the circuit board is heated to separate metals and non-metals.
  • the advantage is that it can handle all forms of electronic waste, but the incineration process may produce toxic waste gases such as dioxins. Therefore, this method has higher requirements on the incinerator.
  • the investment in pyrometallurgy is high, especially in equipment investment and environmental protection investment.
  • the invention solves the problem of selective recovery of precious metals in the chlorination solution of circuit board components through a low-cost and high-efficiency method, and the recovery process avoids generating a large amount of tail liquid and polluting the environment.
  • the present invention has the characteristics of short treatment process, simple equipment, high recovery rate of precious metals, low price of reducing agent, recycling of tail liquid and the like.
  • Precious metal recovery method of the present invention is as follows:
  • (1) Leaching add the metal powder of components after crushing and magnetic separation to the mixture of sulfuric acid and hydrogen peroxide and react at 70-90°C for 2-3 hours; the liquid-solid ratio is 4:1-8:1; sulfuric acid and peroxide
  • the preparation of the mixed liquid of hydrogen oxide is: the concentration of sulfuric acid is 1.5mol/L ⁇ 3mol/L, the mass percentage concentration of hydrogen peroxide is 20% ⁇ 30%, the volume ratio of the two solutions of sulfuric acid and hydrogen peroxide is 2: 1 ⁇ 4:1;
  • After filtering add the mixed solution of hydrochloric acid, sodium chloride and sodium chlorate to the filter residue and react at 70 ⁇ 90°C for 2 ⁇ 3 hours to obtain metal chloride leaching solution, the liquid-solid ratio is 5:1 ⁇ 9:1 , the concentration of hydrochloric acid in the mixture of hydrochloric acid, sodium chloride and sodium chlorate is 0.5-1.5mol/L, the concentration of sodium chloride is 120-190g/L, and the concentration of sodium chlorate is 6.82-20.46g/L
  • the metal chloride leach solution of step (1) is cooled to room temperature and filtered to obtain solid silver chloride, and the solid silver chloride wherein is added with ammonia and formaldehyde to obtain silver element; the metal chloride leach solution is cooled to the filtrate obtained by room temperature filtration
  • Add an organic reducing agent to react, keep warm at 50-70°C for 6-10 hours, filter out the precipitated substance, the precipitated substance is gold element, palladium element and tin dioxide, add hydrochloric acid to wash the precipitated substance to obtain gold element, palladium element
  • organic reducing agent Refers to one or more of amide organic compounds (such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), etc.);
  • step (2) metal chlorination leaching liquid adds organic reductant to filter filtrate after adding organic reductant reaction and adds extraction agent and extracts, and organic phase separates extraction agent and organic reductant by rectification under reduced pressure, and organic reductant continues in step ( 2) used in; extractant refers to one or more in dichloromethane, trichloromethane, benzene;
  • extractant refers to one or more in dichloromethane, trichloromethane, benzene;
  • water phase add hydrochloric acid, sodium chlorate, make hydrochloric acid, sodium chlorate, sodium chloride concentration meet The concentration of hydrochloric acid, sodium chloride, sodium chlorate mixed solution in the step (1); the water phase after the extraction after all circulations are finished, i.e. the final tail liquid, reclaims sodium chloride by evaporative crystallization.
  • the beneficial effect of the present invention is that most gold, silver and palladium in the leaching solution of the metal powder of components and parts after crushing and magnetic separation can be separated for recycling.
  • this method not only greatly shortens the process flow of precious metal recovery, but also has good economic benefits due to the low price of the reducing agent, which is conducive to industrialization.
  • the recycling of the tail liquid is realized in the recovery process to avoid a large amount of environmental pollution.
  • the recovery rate of gold can reach 96.7%
  • the recovery rate of palladium can reach 91.2%
  • the recovery rate of silver can reach 98.2%.
  • Fig. 1 is a schematic flowchart of the steps of the method for recovering precious metals from circuit board components in a preferred embodiment of the present invention.
  • the method for recovering precious metals from the metal powder of circuit board components after crushing and magnetic separation in the present invention recovers gold, silver and palladium in the metal powder of circuit board components through the steps of leaching ⁇ precipitation ⁇ circulation.
  • the present invention reclaims the method for noble metal from the circuit board component metal powder after crushing magnetic separation and comprises the following steps:
  • (1) Leaching add the metal powder of components after crushing and magnetic separation to the mixture of sulfuric acid and hydrogen peroxide and react at 70-90°C for 2-3 hours; the liquid-solid ratio is 4:1-8:1; sulfuric acid and peroxide
  • the preparation of the mixed liquid of hydrogen oxide is: the concentration of sulfuric acid is 1.5mol/L ⁇ 3mol/L, the mass percentage concentration of hydrogen peroxide is 20% ⁇ 30%, the volume ratio of the two solutions of sulfuric acid and hydrogen peroxide is 2: 1 ⁇ 4:1;
  • After filtering add the mixed solution of hydrochloric acid, sodium chloride and sodium chlorate to the filter residue and react at 70 ⁇ 90°C for 2 ⁇ 3 hours to obtain metal chloride leaching solution, the liquid-solid ratio is 5:1 ⁇ 9:1
  • the concentration of hydrochloric acid in the mixture of hydrochloric acid, sodium chloride and sodium chlorate is 0.5-1.5mol/L, the concentration of sodium chloride is 120-190g/L, and the concentration of sodium chlorate is 6.82-20.46g/L
  • the metal chloride leach solution of step (1) is cooled to room temperature and filtered to obtain solid silver chloride, and the solid silver chloride wherein is added with ammonia and formaldehyde to obtain silver element; the metal chloride leach solution is cooled to the filtrate obtained by room temperature filtration
  • Add an organic reducing agent to react, keep warm at 50-70°C for 6-10 hours, filter out the precipitated substance, the precipitated substance is gold element, palladium element and tin dioxide, add hydrochloric acid to wash the precipitated substance to obtain gold element, palladium element
  • organic reducing agent Refers to one or more of amide organic compounds (such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), etc.);
  • the principle of silver, gold and palladium precipitation is: silver chloride and ammonia water form a soluble complex, which is reduced to simple silver by formaldehyde.
  • the oxidation-reduction potentials of gold and palladium in precious metals are higher than those of common metals, such as copper, aluminum, nickel, tin, etc. The higher the potential, the stronger the oxidation and the easier the redox reaction.
  • amide organic compounds such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), etc.
  • DMF N,N-dimethylformamide
  • DMA N,N-dimethylacetamide
  • step (2) metal chlorination leaching liquid adds organic reductant to filter filtrate after adding organic reductant reaction and adds extraction agent and extracts, and organic phase separates extraction agent and organic reductant by rectification under reduced pressure, and organic reductant continues in step ( 2) used in; extractant refers to one or more in dichloromethane, trichloromethane, benzene;
  • extractant refers to one or more in dichloromethane, trichloromethane, benzene;
  • water phase add hydrochloric acid, sodium chlorate, make hydrochloric acid, sodium chlorate, sodium chloride concentration meet The concentration of hydrochloric acid, sodium chloride, sodium chlorate mixed solution in the step (1); the water phase after the extraction after all circulations are finished, i.e. the final tail liquid, reclaims sodium chloride by evaporative crystallization.
  • Example 1 Crushing the component metal powder after magnetic separation Add sulfuric acid and hydrogen peroxide to react at 70°C for 2 hours.
  • the liquid-solid ratio is 5:1, the concentration of sulfuric acid is 2mol/L, the mass percent concentration of hydrogen peroxide is 25%, and the volume ratio of the two is 4:1. Filter to get the filtrate. The filter residue was taken, the liquid-solid ratio was 6:1, the hydrochloric acid concentration was 0.5mol/L, the sodium chloride concentration was 120g/L, and the sodium chlorate concentration was 6.82g/L for leaching, and placed at 70°C for 3 hours.
  • the composition of the solution after leaching is Au concentration 260.16mg/L, Ag concentration 693.8mg/L, Pd concentration 73.18mg/L, Cu concentration 203.52mg/L, Ni concentration 180.83mg/L, Al concentration 187.83mg/L, Sn concentration 198.04mg/L.
  • Cool to room temperature filter to obtain silver chloride precipitate, add ammonia water and formaldehyde to obtain simple silver.
  • Put the filtered solution into a bottle add DMF with 40% of the filtrate volume, seal it, place it in a 50 degree oven and heat it for 7 hours. After 7 hours, a precipitate appears at the bottom of the bottle. After filtering, wash it with hydrochloric acid to obtain gold and palladium.
  • Example 2 Crushing and magnetically separating components and parts Metal powder raw materials were added sulfuric acid and hydrogen peroxide and reacted at 70°C for 2 hours.
  • the liquid-solid ratio is 5:1, the concentration of sulfuric acid is 2mol/L, the mass percent concentration of hydrogen peroxide is 25%, and the volume ratio of the two is 4:1. Filter to get the filtrate. The filter residue was taken, the liquid-solid ratio was 6:1, the concentration of hydrochloric acid was 0.5mol/L, the concentration of sodium chloride was 120g/L, and the concentration of sodium chlorate was 6.82g/L for leaching, and it was placed at 70°C for 3 hours.
  • the composition of the solution after leaching is Au concentration 260.16mg/L, Ag concentration 693.8mg/L, Pd concentration 73.18mg/L, Cu concentration 203.52mg/L, Ni concentration 180.83mg/L, Al concentration 187.83mg/L, Sn concentration 198.04mg/L.
  • Cool to room temperature filter to obtain silver chloride precipitate, add ammonia water and formaldehyde to obtain simple silver.
  • Put the filtered solution into a bottle add 50% DMA of the filtrate volume, seal it, place it in a 60-degree oven and heat it for 10 hours, and a precipitate appears at the bottom of the bottle. After filtering, wash it with hydrochloric acid to obtain gold and palladium.

Abstract

一种低成本高效的线路板元器件中贵金属回收方法，属于废弃物资源化回收技术领域。主要解决氯化浸出液中贵金属选择性回收的问题，利用了氧化还原反应的基本原理，采用硫酸和过氧化氢的混合液以及盐酸、氯化钠、氯酸钠的混合液进行，同时还采用氨水和甲醛进行还原银，基于在一般金属中，金钯离子的氧化还原电位更高这一特性，使用价格低廉且还原性适中的还原剂选择性将氯化浸出液中金钯离子还原为单质，进而通过过滤将其分离，实现资源回收利用，不仅极大缩短了贵金属回收的工艺流程，且由于还原剂价格低廉，具有良好经济效益，利于工业化。与此同时，在回收过程中避免产生大量的尾液污染环境。

Description

一种低成本高效的线路板元器件中贵金属回收方法 技术领域
本发明属于废弃物资源化回收技术领域，一种用于线路板元器件中贵金属回收的方法。
背景技术
线路板是电子产品的核心部件，存在于手机用板、计算机用板、音响设备用板、LED用板等设备中，种类繁多且数量巨大。随着电子信息工业的高速发展，在其生产量不断增加的同时，报废量也与日俱增。据统计，仅2020年我国线路板报废量达703.61万吨。有研究报告显示，预计到2030年，我国电子产品废弃量将超过2700万吨。随着电子产品产销量不断上升，会产生大量的废元器件，如果这些电子废弃物不经合理有效处置，会造成环境污染，致使环境问题将更加突出。
废旧线路板上的元器件主要由高分子聚合物、树脂、玻璃纤维和多类金属成分组成。据统计废旧线路板元器件中金属总含量约占40％，非金属含量约占60％，这其中金属部分主要含有金属铝、铜、镍、铁、锌、锡等普通金属，并且含有金、银、铂、钯等贵金属。在线路板元器件中贵金属含量很高，尤其贵金属金的含量可高达80g/t，远远高于国内原生金矿石中3-5g/t的品位，具有相当高的经济价值。如果将废旧线路板元器件进行有效的资源化处理，高效提取其中的贵金属，不但能够缓解我国因人均矿产资源量少导致的资源匮乏问题，还能带来可观的经济效益。
目前废弃线路板元器件的有价金属回收方法种类繁多，以机械法、湿法处理、火法处理三种方法为主，并且还有超临界流体法、微生物处理法这样的新兴方法。
机械法：采用机械的方法将废旧线路板进行拆解，使其中的元器件与基板分离，然后通过撞击、剪切、挤压等破碎方式使不同金属与非金属完全解离成粉末。根据各组分的密度、导电性、磁性等物理性质的差异，实现金属和非金属物质的分离，该方法优点是工艺流程简单，成本低且环境友好，在国内被75％的线路板处理公司所选择。但是缺点在于产物纯度不高。
湿法处理：湿法浸出技术主要通过用硝酸、盐酸等作为氧化剂，利用金属能够在这些强氧化介质溶解的特点实现金属和非金属的分离。还有一类方法利用某 些特定化合物的溶液作为溶剂，该物质一般具有对于特定金属的选择性，例如氰化法、硫脲法、硫代硫酸盐法等。湿法处理具有适应性广泛，金属回收率高且产物纯度较高的优势，但缺点也较为突出，处理流程较长，过程中加入了大量的酸以及碱，其中还有氰化物这种剧毒物质，会产生环境污染。
火法处理：火法处理是提取金属的传统方法，利用无氧或缺氧条件下，温度控制在350～900℃，加热处理线路板使金属和非金属分离。其优点在于可以处理所有形式的电子废弃物，但是焚烧过程中会有可能产生二噁英等有毒废气。因此该方法对焚烧炉要求较高，一般来说，火法冶炼的投资高，尤其是设备投资和环保投资。
超临界处理技术和生物冶金法虽然具有很好的效果，但是目前多用于实验室，尚不能开展大规模的推广应用。
发明内容
本发明通过一种低成本高效的方法解决线路板元器件氯化液中贵金属选择性回收的问题，且回收过程避免产生大量的尾液，污染环境。与传统的回收方法相比，本发明具有处理工艺流程短、设备简单、贵金属回收率高、还原剂价格低廉、尾液循环使用等特点。
本发明所述的贵金属回收方法如下:
(1)浸出：将破碎磁选后元器件金属粉末加入硫酸和过氧化氢的混合液中于70～90℃反应2～3小时；液固比为4∶1～8∶1；硫酸和过氧化氢的混合液的制备为：硫酸浓度为1.5mol/L～3mol/L，过氧化氢的质量百分浓度为20％～30％，硫酸和过氧化氢二者溶液的体积比为2∶1～4∶1；过滤后滤渣加入盐酸、氯化钠、氯酸钠的混合液于70～90℃反应2～3小时，得到金属氯化浸出液，液固比为5∶1～9∶1，盐酸、氯化钠、氯酸钠的混合液中盐酸浓度为0.5～1.5mol/L、氯化钠浓度为120～190g/L、氯酸钠浓度为6.82～20.46g/L；
(2)沉淀：将步骤(1)的金属氯化浸出液冷却到室温过滤得到固体氯化银，其中的固体氯化银加入氨水和甲醛得到银单质；金属氯化浸出液冷却到室温过滤得到的滤液加入有机还原剂反应，在50～70℃保温6～10小时，过滤取出沉淀物质，沉淀物质为金单质、钯单质和二氧化锡，沉淀物质加入盐酸洗涤得到金单质、钯单质；有机还原剂指酰胺类有机化合物(例如N,N-二甲基甲酰胺(DMF)、 N,N-二甲基乙酰胺(DMA)等)中的一种或几种；
(3)循环：步骤(2)金属氯化浸出液加有机还原剂反应后的过滤滤液加入萃取剂进行萃取，有机相通过减压精馏分离萃取剂和有机还原剂，有机还原剂继续在步骤(2)中使用；萃取剂是指二氯甲烷、三氯甲烷、苯中的一种或几种；萃取后水相，加入盐酸、氯酸钠，使盐酸、氯酸钠、氯化钠浓度满足步骤(1)中盐酸、氯化钠、氯酸钠混合液的浓度；所有循环完成后萃取后的水相即最后尾液通过蒸发结晶回收氯化钠。
本发明的有益效果：可以将破碎磁选后的元器件金属粉浸出液中大多数金银钯分离出来，做到回收利用。与传统湿法回收工艺相比，该方法不仅极大缩短了贵金属回收的工艺流程，且由于还原剂价格低廉，具有良好经济效益，利于工业化。与此同时，在回收过程中实现了尾液循环使用，避免产生大量的环境污染。金的回收率可达96.7％，钯的回收率可达91.2％，银的回收率可达98.2％，
附图说明
构成本申请的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中:
图1是本发明优选实施例从线路板元器件中贵金属回收的方法的方法的步骤流程示意图。
具体实施方式
下面结合实施例对本发明作进一步说明，但本发明可以由权利要求限定和覆盖的多种不同方式实施并不限于以下实例。
本发明从破碎磁选后的线路板元器件金属粉末中回收贵金属的方法通过浸出→沉淀→循环的步骤，来回收线路板元器件金属粉末中的金、银、钯。
参照图1，本发明从破碎磁选后的线路板元器件金属粉末中回收贵金属的方法包含以下步骤：
(1)浸出：将破碎磁选后元器件金属粉末加入硫酸和过氧化氢的混合液中于70～90℃反应2～3小时；液固比为4∶1～8∶1；硫酸和过氧化氢的混合液的制备为：硫酸浓度为1.5mol/L～3mol/L，过氧化氢的质量百分浓度为20％～30％，硫酸和过氧化氢二者溶液的体积比为2∶1～4∶1；过滤后滤渣加入盐酸、氯化钠、氯酸钠的混合液于70～90℃反应2～3小时，得到金属氯化浸出液，液固比为 5∶1～9∶1，盐酸、氯化钠、氯酸钠的混合液中盐酸浓度为0.5～1.5mol/L、氯化钠浓度为120～190g/L、氯酸钠浓度为6.82～20.46g/L
(2)沉淀：将步骤(1)的金属氯化浸出液冷却到室温过滤得到固体氯化银，其中的固体氯化银加入氨水和甲醛得到银单质；金属氯化浸出液冷却到室温过滤得到的滤液加入有机还原剂反应，在50～70℃保温6～10小时，过滤取出沉淀物质，沉淀物质为金单质、钯单质和二氧化锡，沉淀物质加入盐酸洗涤得到金单质、钯单质；有机还原剂指酰胺类有机化合物(例如N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMA)等)中的一种或几种；
银、金、钯沉淀的原理是：氯化银和氨水形成可溶性络合物，利用甲醛将其还原为银单质。贵金属中金、钯的氧化还原电位均高于一般金属，如铜、铝、镍、锡等。电位越高，氧化性越强，更容易发生氧化还原反应。在特定实验条件下，酰胺类有机化合物(例如N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMA)等)均具有还原性，可和贵金属发生氧化还原反应，因此能够将贵金属选择性沉淀出来。
(3)循环：步骤(2)金属氯化浸出液加有机还原剂反应后的过滤滤液加入萃取剂进行萃取，有机相通过减压精馏分离萃取剂和有机还原剂，有机还原剂继续在步骤(2)中使用；萃取剂是指二氯甲烷、三氯甲烷、苯中的一种或几种；萃取后水相，加入盐酸、氯酸钠，使盐酸、氯酸钠、氯化钠浓度满足步骤(1)中盐酸、氯化钠、氯酸钠混合液的浓度；所有循环完成后萃取后的水相即最后尾液通过蒸发结晶回收氯化钠。
实例1:破碎磁选后的元器件金属粉末原料加入硫酸和过氧化氢于70℃反应2小时。液固比为5:1，硫酸浓度为2mol/L，过氧化氢的质量百分浓度为25％，二者体积比为4∶1。过滤取滤液。取滤渣，液固比为6∶1盐酸浓度为0.5mol/L、氯化钠浓度为120g/L、氯酸钠浓度为6.82g/L的条件做浸出，放置于70℃反应3小时。浸出后溶液的成分为Au浓度260.16mg/L、Ag浓度693.8mg/L、Pd浓度73.18mg/L、Cu浓度203.52mg/L、Ni浓度180.83mg/L、Al浓度187.83mg/L、Sn浓度198.04mg/L。冷却至室温，过滤得到氯化银沉淀，加入氨水和甲醛得到银单质。将过滤后溶液放入瓶中，加入滤液体积40％的DMF，密封，放置于50 度烘箱中加热保温7小时后，瓶底出现沉淀物，过滤后使用盐酸进行洗，得到金钯单质。滤液加入二氯甲烷进行萃取，有机相通过减压精馏分离二氯甲烷和DMF。萃取后水相，加入盐酸、氯酸钠，使盐酸浓度为0.5mol/L、氯化钠浓度为120g/L、氯酸钠浓度为6.82g/L。取反应后上层清液进行电感耦合等离子光谱发生仪(ICP)测试，结果显示，金的回收率可达96.7％，钯的回收率可达91.2％，银的回收率可达98.2％。
实例2:破碎磁选后的元器件金属粉末原料加入硫酸和过氧化氢于70℃反应2小时。液固比为5:1，硫酸浓度为2mol/L，过氧化氢的质量百分浓度为25％，二者体积比为4∶1。过滤取滤液。取滤渣，液固比为6∶1盐酸浓度为0.5mol/L、氯化钠浓度为120g/L、氯酸钠浓度为6.82g/L的条件做浸出，放置于70℃反应3小时。浸出后溶液的成分为Au浓度260.16mg/L、Ag浓度693.8mg/L、Pd浓度73.18mg/L、Cu浓度203.52mg/L、Ni浓度180.83mg/L、Al浓度187.83mg/L、Sn浓度198.04mg/L。冷却至室温，过滤得到氯化银沉淀，加入氨水和甲醛得到银单质。将过滤后溶液放入瓶中，加入滤液体积50％的DMA，密封，放置于60度烘箱中加热保温10小时后，瓶底出现沉淀物，过滤后使用盐酸进行洗，得到金钯单质。滤液加入三氯甲烷进行萃取，有机相通过减压精馏分离三氯甲烷和DMA。萃取后水相，加入盐酸、氯酸钠，使盐酸浓度为1mol/L、氯化钠浓度为150g/L、氯酸钠浓度为6.82g/L。取反应后上层清液进行电感耦合等离子光谱发生仪(ICP)测试，结果显示，金的回收率可达95.3％，钯的回收率可达90.3％，银的回收率可达96.2％。
以上所述仅为本发明的优选实例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (5)

  1. 一种低成本高效的线路板元器件中贵金属回收方法，其特征在于，包括以下步骤：
    (1)浸出：将破碎磁选后的元器件金属粉末加入硫酸和过氧化氢的混合液中于70～90℃反应2～3小时；液固比为4∶1～8∶1；过滤后滤渣加入盐酸、氯化钠、氯酸钠的混合液于70～90℃反应2～3小时，得到金属氯化浸出液，液固比为5∶1～9∶1；
    (2)沉淀：将步骤(1)的金属氯化浸出液冷却到室温过滤得到固体氯化银，其中的固体氯化银加入氨水和甲醛得到银单质；金属氯化浸出液冷却到室温过滤得到的滤液加入有机还原剂反应，在50～70℃保温6～10小时，过滤取出沉淀物质，沉淀物质为金单质、钯单质和二氧化锡，沉淀物质加入盐酸洗涤得到金单质、钯单质；
    (3)循环：步骤(2)金属氯化浸出液加有机还原剂反应后的过滤滤液加入萃取剂进行萃取，有机相通过减压精馏分离萃取剂和有机还原剂，有机还原剂继续在步骤(2)中使用；萃取后水相，加入盐酸、氯酸钠，使盐酸、氯酸钠、氯化钠浓度满足步骤(1)中盐酸、氯化钠、氯酸钠混合液的浓度；所有循环完成后萃取后的水相即最后尾液通过蒸发结晶回收氯化钠。
  2. 按照权利要求1所述的一种低成本高效的线路板元器件中贵金属回收方法，其特征在于，步骤(1)硫酸和过氧化氢的混合液的制备为：硫酸浓度为1.5mol/L～3mol/L，过氧化氢的质量百分浓度为20％～30％，硫酸和过氧化氢二者溶液的体积比为2∶1～4∶1。
  3. 按照权利要求1所述的一种低成本高效的线路板元器件中贵金属回收方法，其特征在于，步骤(1)，盐酸、氯化钠、氯酸钠的混合液中盐酸浓度为0.5～1.5mol/L、氯化钠浓度为120～190g/L、氯酸钠浓度为6.82～20.46g/L。
  4. 按照权利要求1所述的一种低成本高效的线路板元器件中贵金属回收方法，其特征在于，步骤(2)有机还原剂指酰胺类有机化合物中的一种或几种，例如N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMA)等。
  5. 按照权利要求1所述的一种低成本高效的线路板元器件中贵金属回收方法，其特征在于，步骤(3)萃取剂是指二氯甲烷、三氯甲烷、苯中的一种或几种。
PCT/CN2022/080536 2021-12-03 2022-03-14 一种低成本高效的线路板元器件中贵金属回收方法 WO2023097924A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/975,606 US11753699B2 (en) 2021-12-03 2022-10-28 Cost-effective method for recovering precious metals in circuit board components

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111472243.1 2021-12-03
CN202111472243.1A CN114134337B (zh) 2021-12-03 2021-12-03 一种低成本高效的线路板元器件中贵金属回收方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/975,606 Continuation US11753699B2 (en) 2021-12-03 2022-10-28 Cost-effective method for recovering precious metals in circuit board components

Publications (1)

Publication Number Publication Date
WO2023097924A1 true WO2023097924A1 (zh) 2023-06-08

Family

ID=80388094

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/080536 WO2023097924A1 (zh) 2021-12-03 2022-03-14 一种低成本高效的线路板元器件中贵金属回收方法

Country Status (2)

Country Link
CN (1) CN114134337B (zh)
WO (1) WO2023097924A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114134337B (zh) * 2021-12-03 2023-04-28 北京工业大学 一种低成本高效的线路板元器件中贵金属回收方法
US11753699B2 (en) 2021-12-03 2023-09-12 Beijing University Of Technology Cost-effective method for recovering precious metals in circuit board components

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4662938A (en) * 1984-10-11 1987-05-05 Whitney John W Recovery of silver and gold
CN101928840A (zh) * 2010-08-02 2010-12-29 惠州市奥美特环境科技有限公司 一种从废旧电路板中回收金、银的方法
CN104532005A (zh) * 2014-12-23 2015-04-22 清远市东江环保技术有限公司 一种废弃印刷电路板资源化综合利用的方法
CN105755289A (zh) * 2016-04-28 2016-07-13 中南大学 一种废弃线路板有价金属综合回收的方法
WO2019229632A1 (en) * 2018-05-29 2019-12-05 Università Degli Studi Dell'aquila Hydrometallurgical method for the recovery of base metals and precious metals from a waste material
CN112695199A (zh) * 2020-12-15 2021-04-23 广东先导稀贵金属材料有限公司 从碲铜渣中提取碲和铜的方法
CN114134337A (zh) * 2021-12-03 2022-03-04 北京工业大学 一种低成本高效的线路板元器件中贵金属回收方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102277497B (zh) * 2011-08-05 2013-03-13 武汉格林美资源循环有限公司 一种从废旧电路板中回收金、钯、铂、银的方法
CN104411429B (zh) * 2012-09-12 2017-09-26 M技术株式会社 金属微粒的制造方法
CN105274337B (zh) * 2014-10-06 2017-11-03 建昇电子科技（惠州）有限公司 废旧电路板回收贵金属的方法
CN105132690A (zh) * 2015-09-20 2015-12-09 成都育芽科技有限公司 电子废弃物中提取金银铂钯的方法
CN105803206A (zh) * 2016-03-28 2016-07-27 河南工信环保科技有限公司 一种无害化深度处理废旧线路板回收金属的方法
CN105907976B (zh) * 2016-06-30 2017-09-26 华南理工大学 一种从废旧手机电子元器件中回收钯（Pd）的方法
CN111172398A (zh) * 2020-01-17 2020-05-19 广东华越环保科技有限公司 一种废旧手机线路板中金属的湿法无害化提取工艺
CN111139360B (zh) * 2020-01-17 2021-10-26 广东华越环保科技有限公司 一种废旧手机线路板中的ic芯片和元器件中金属的回收方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4662938A (en) * 1984-10-11 1987-05-05 Whitney John W Recovery of silver and gold
CN101928840A (zh) * 2010-08-02 2010-12-29 惠州市奥美特环境科技有限公司 一种从废旧电路板中回收金、银的方法
CN104532005A (zh) * 2014-12-23 2015-04-22 清远市东江环保技术有限公司 一种废弃印刷电路板资源化综合利用的方法
CN105755289A (zh) * 2016-04-28 2016-07-13 中南大学 一种废弃线路板有价金属综合回收的方法
WO2019229632A1 (en) * 2018-05-29 2019-12-05 Università Degli Studi Dell'aquila Hydrometallurgical method for the recovery of base metals and precious metals from a waste material
CN112695199A (zh) * 2020-12-15 2021-04-23 广东先导稀贵金属材料有限公司 从碲铜渣中提取碲和铜的方法
CN114134337A (zh) * 2021-12-03 2022-03-04 北京工业大学 一种低成本高效的线路板元器件中贵金属回收方法

Also Published As

Publication number Publication date
CN114134337A (zh) 2022-03-04
CN114134337B (zh) 2023-04-28

Similar Documents

Publication Publication Date Title
WO2023097924A1 (zh) 一种低成本高效的线路板元器件中贵金属回收方法
CN103397186B (zh) 一种从电子废弃物中回收稀贵金属的再生方法及工艺
US9114445B2 (en) Burning-free and non-cyanide method for recycling waste printed circuit board
CN101709382B (zh) 一种含锌物料中有价金属回收综合处理工艺
CN102952947B (zh) 一种废旧电路板中稀贵金属的综合回收方法
CN105132690A (zh) 电子废弃物中提取金银铂钯的方法
CN103667707A (zh) 废旧电路板中回收金银的方法
CN102747229B (zh) 分离回收废弃电路板多金属富集粉末中有价金属的方法
CN104775034A (zh) 一种采用离子液体浸出分步回收废旧印制线路板中金属的方法
CN104928478A (zh) 一种电镀污泥综合回收有价金属的方法
CN105886768A (zh) 一种从电子废料中高效富集贵金属的方法
CN111041207A (zh) 一种电化学浸金剂及从废旧镀金线路板中回收金的方法
CN111172398A (zh) 一种废旧手机线路板中金属的湿法无害化提取工艺
CN104630479A (zh) 一种从电子废弃物中回收多种金属的方法
CN104911366A (zh) 一种用王水回收银铋渣中有价金属的方法
CN103589873A (zh) 一种回收银锌渣中有价金属的方法
CN104263939A (zh) 一种从底层电镀铜/镍材料中回收稀贵/惰性金属的方法
US11753699B2 (en) Cost-effective method for recovering precious metals in circuit board components
CN111485110A (zh) 一种提高稀土中有价元素利用率的方法
CN104178629B (zh) 从废弃电子线路板多金属粉末中回收有价金属的方法
CN101864519A (zh) 一种选择性浸出分离废弃线路板中锡、铅和铜的方法
CN107841630B (zh) 线路板贵贱金属分离方法
CN1458291A (zh) 电子废料的贵金属再生回收方法
CN112458289B (zh) 一种从银镍合金铜基铆钉废料中选择性分离回收银的方法
CN111139360B (zh) 一种废旧手机线路板中的ic芯片和元器件中金属的回收方法

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: 22899747

Country of ref document: EP

Kind code of ref document: A1