CN105483386A - Method for leaching copper from single-layer waste circuit board - Google Patents

Method for leaching copper from single-layer waste circuit board Download PDF

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Publication number
CN105483386A
CN105483386A CN201510903412.0A CN201510903412A CN105483386A CN 105483386 A CN105483386 A CN 105483386A CN 201510903412 A CN201510903412 A CN 201510903412A CN 105483386 A CN105483386 A CN 105483386A
Authority
CN
China
Prior art keywords
circuit board
printed circuit
etching solution
copper
waste printed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510903412.0A
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Chinese (zh)
Inventor
李金惠
于淼
刘丽丽
邓超
王琎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
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 Tsinghua University filed Critical Tsinghua University
Priority to CN201510903412.0A priority Critical patent/CN105483386A/en
Publication of CN105483386A publication Critical patent/CN105483386A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • C22B7/007Wet processes by acid leaching
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0065Leaching or slurrying
    • C22B15/0067Leaching or slurrying with acids or salts thereof
    • C22B15/0069Leaching or slurrying with acids or salts thereof containing halogen
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0065Leaching or slurrying
    • C22B15/0078Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • C22B7/008Wet processes by an alkaline or ammoniacal leaching
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention discloses a method for leaching copper from a single-layer waste circuit board. The method comprises the following steps: (1) removing a green oil film on the surface of the waste circuit board with a diluted alkali solution, and then washing the waste circuit board with water; (2) immersing the waste circuit board treated by the step (1) in a waste etching solution for 20-60min, and thus completing the leaching of copper in the waste circuit board. Experiments prove that the method leaches the copper on the single-layer waste circuit board, utilizes the waste etching solution, and reduces the yield of waste liquid. The operation process is simple and feasible, the cost is low, and the method has great significance to environment protection.

Description

The method of lixiviate copper from individual layer waste printed circuit board
Technical field
The invention belongs to Material Field, be specifically related to a kind of method of lixiviate copper from individual layer waste printed circuit board.
Background technology
Along with electric equipment products production and scrap, the discarded amount of wiring board and day increase severely.In waste printed circuit board removal process, recovery for copper generally all adopts " fragmentation-sorting " or the method for " fragmentation-wet-leaching ", broken process not only needs to consume a large amount of electric energy, and the dust produced also can to environment, therefore find a kind of without the need to fragmentation directly efficiently the method for leaching and recoverying copper become the problem demanding prompt solution in waste printed circuit board removal process.
Printed-wiring board (PWB) (PCB) making processes has more than 20 procedures, wherein etch copper produces the larger operation of waste liquid amount in PCB enterprise, 1.5 cubic metres of etching solutions calculating are at least consumed by often producing 1000 square metres of wiring boards, the whole world consumes 3 billion cubic meter etching solutions year, and still with the speed increase of 15%-18%.Just spent etching solution is become after the erosion copper ability of etching solution declines, heavy metal concentration is wherein up to 80-120g/L (based on copper), widely used is at present cupric chloride etching solution, show that cupric chloride spent etching solution still has the ability continuing molten copper after tested, therefore spent etching solution " can be turned waste into wealth ", the copper in lixiviate waste printed circuit board is continued, to reach the object of the treatment of wastes with processes of wastes against one another as molten copper digestion agent.
At present, domestic research work of reclaiming about waste printed circuit board has had important progress, the existing multinomial patent about waste printed circuit board recovery technology.
Patent [200910009562.1] is broken by waste printed circuit board, then reclaims copper and gold, to obtain the resource recovery of valuable metal by the method for " acid-soluble erosion-displacement "; Waste printed circuit board is crushed to 40-200 order by patent [201310292820.8], uses organic solvent dissolution caking agent, then uses high pressure static electricity separating metal and nonmetal; Patent [201110092620.9] adopts the methods such as fragmentation, electrostatic separation, calcining, acidleach, achieves valuable metal resource regeneration.
Every technology that above patent adopts all needs to reclaim copper by after waste printed circuit board fragmentation, in recycling process, not only consume a large amount of electric energy, and the dust that also can produce because of shattering process causes secondary pollution to environment.
Summary of the invention
The object of this invention is to provide a kind of method of lixiviate copper from waste printed circuit board.
The method of lixiviate copper from waste printed circuit board provided by the invention, comprises the steps:
1), after being utilized by waste printed circuit board dilute alkaline soln to remove the green oil film on surface, rinse with water;
2) by step 1) process after waste printed circuit board be placed in spent etching solution soak 20-60min, complete the lixiviate of copper in described waste printed circuit board.
In aforesaid method, described waste printed circuit board is individual layer waste printed circuit board.
Described step 1) in, dilute alkaline soln is selected from least one in the aqueous solution of the aqueous solution of sodium hydroxide, the aqueous solution of potassium hydroxide and lithium hydroxide;
The mass percentage concentration of described dilute alkaline soln is 1%-8%.
Described step 1) remove in step, the temperature removed is 60 DEG C-90 DEG C;
Time is 1-3 hour, specifically can be 75min.
Described step 2) in, described spent etching solution is cupric chloride spent etching solution, is specially acidic copper chloride spent etching solution or alkaline cupric chloride spent etching solution.
Described step 2) in soaking step, the temperature of immersion is normal temperature; The time of soaking specifically can be 32min-40min;
Described step 1) waste printed circuit board after process and the solid-to-liquid ratio of described spent etching solution be 1g:2-36mL, specifically can be 1g:5ml-36mL.
The invention provides a kind of method of lixiviate copper from waste printed circuit board.The method is clean economical, and can carry out whole plate recovery to individual layer waste printed circuit board, without the need to fragmentation, etching solution used is cupric chloride spent etching solution, can realize the recycling to spent etching baths, reaches the object of the treatment of wastes with processes of wastes against one another.
Accompanying drawing explanation
Fig. 1 is schematic diagram before and after de-green oil film of the present invention; A is for before de-green oil film, and b is for after de-green oil film;
Fig. 2 is schematic diagram before and after copper of the present invention leaches; A is before copper leaches, and b is after copper leaches.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.The concrete composition of following embodiment acidic copper chloride used spent etching solution and alkaline cupric chloride spent etching solution is as shown in table 1:
The concrete composition (solvent is water) of table 1, acidic copper chloride spent etching solution and alkaline cupric chloride spent etching solution
Embodiment 1
1) the individual layer waste printed circuit board choosing cathode-ray tube display is test materials, be cut to 5*5cm box-shaped, configuration quality percentage concentration is that the NaOH aqueous solution 200ml of 1% is in 500ml small beaker, be positioned in 90 DEG C of water-baths, the wiring board of well cutting is soaked in 75min in this NaOH aqueous solution, then taking-up clear water rinses.
Test-results is that the green oil film on wiring board removes completely, exposes copper foil layer, and as shown in Figure 1, a is for before de-green oil film, and b is for after de-green oil film.
2) by step 1) gained is stripped of the waste printed circuit board after green oil film, and soak at room temperature is in acidic copper chloride spent etching solution, and solid-to-liquid ratio is 1g:5ml, and soak time is 40min, then takes out residual resin plate.
Test-results is that exposed copper foil layer is dissolved completely by spent etching solution, and a residual resin plate, completes the lixiviate of copper in individual layer waste printed circuit board, and as shown in Figure 2, a is before copper leaches, and b is after copper leaches.
Embodiment 2
1) the individual layer waste printed circuit board choosing cathode-ray tube display is test materials, be cut to 5*5cm box-shaped, configuration quality percentage concentration is that the KOH aqueous solution 200ml of 1% is in 500ml small beaker, be positioned in 90 DEG C of water-baths, the wiring board of well cutting is soaked in 75min in this KOH aqueous solution, then taking-up clear water rinses.
Test-results is that the green oil film on wiring board removes completely, exposes copper foil layer.
2) by step 1) gained is stripped of the waste printed circuit board after green oil film, and soak at room temperature is in alkaline cupric chloride spent etching solution, and solid-to-liquid ratio is 1g:36ml, and soak time is 32min, then takes out residual resin plate.
Test-results is that exposed copper foil layer is dissolved completely by spent etching solution, and a residual resin plate, completes the lixiviate of copper in individual layer waste printed circuit board.

Claims (10)

1. the method for lixiviate copper from waste printed circuit board, comprises the steps:
1), after being utilized by waste printed circuit board dilute alkaline soln to remove the oil film on surface, rinse with water;
2) by step 1) process after waste printed circuit board be placed in spent etching solution soak 20-60min, complete the lixiviate of copper in described waste printed circuit board.
2. method according to claim 1, is characterized in that: described waste printed circuit board is individual layer waste printed circuit board.
3. method according to claim 1 and 2, is characterized in that: described step 1) in, dilute alkaline soln is selected from least one in the aqueous solution of the aqueous solution of sodium hydroxide, the aqueous solution of potassium hydroxide and lithium hydroxide.
4., according to described method arbitrary in claim 1-4, it is characterized in that: the mass percentage concentration of described dilute alkaline soln is 1%-8%.
5., according to described method arbitrary in claim 1-4, it is characterized in that: described step 1) remove in step, the temperature removed is 60 DEG C-90 DEG C.
6., according to described method arbitrary in claim 1-5, it is characterized in that: described step 1) remove in step, the time removed is 1-3 hour, is specially 75min.
7., according to described method arbitrary in claim 1-6, it is characterized in that: described step 2) in, described spent etching solution is cupric chloride spent etching solution, is specially acidic copper chloride spent etching solution or alkaline cupric chloride spent etching solution.
8., according to described method arbitrary in claim 1-7, it is characterized in that: described step 2) in soaking step, the temperature of immersion is normal temperature.
9., according to described method arbitrary in claim 1-8, it is characterized in that: described step 2) in soaking step, the time of immersion is 32min-40min.
10., according to described method arbitrary in claim 1-9, it is characterized in that: described step 2) in soaking step, described step 1) solid-to-liquid ratio of waste printed circuit board after process and described spent etching solution is 1g:2-36mL.
CN201510903412.0A 2015-12-09 2015-12-09 Method for leaching copper from single-layer waste circuit board Pending CN105483386A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510903412.0A CN105483386A (en) 2015-12-09 2015-12-09 Method for leaching copper from single-layer waste circuit board

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510903412.0A CN105483386A (en) 2015-12-09 2015-12-09 Method for leaching copper from single-layer waste circuit board

Publications (1)

Publication Number Publication Date
CN105483386A true CN105483386A (en) 2016-04-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112939055A (en) * 2021-01-25 2021-06-11 湖北林泰环境科技有限公司 Method for producing copper chloride by using waste acidic etching solution

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05156375A (en) * 1991-12-05 1993-06-22 Taiyo Koukou Kk Method for leaching valuable metal from waste catalyst
CN1534111A (en) * 2003-03-28 2004-10-06 巫协森 Method of recovering copper metal from waste printed circuit board and copper containing waste liquid and its device
CN101665875A (en) * 2009-09-29 2010-03-10 刘景洋 Tin-lead recovery method in waste circuit board
CN101812591A (en) * 2009-02-20 2010-08-25 国立云林科技大学 Method for recovering gold, copper, copper sulfate and copper chloride waste liquid of waste circuit board
CN103614556A (en) * 2013-10-08 2014-03-05 大连东泰产业废弃物处理有限公司 Method for treating waste mobile phone circuit board and recovering precious metals
CN105002363A (en) * 2015-08-07 2015-10-28 珠海格力电器股份有限公司 Method for recovering gold from circuit board

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05156375A (en) * 1991-12-05 1993-06-22 Taiyo Koukou Kk Method for leaching valuable metal from waste catalyst
CN1534111A (en) * 2003-03-28 2004-10-06 巫协森 Method of recovering copper metal from waste printed circuit board and copper containing waste liquid and its device
CN101812591A (en) * 2009-02-20 2010-08-25 国立云林科技大学 Method for recovering gold, copper, copper sulfate and copper chloride waste liquid of waste circuit board
CN101665875A (en) * 2009-09-29 2010-03-10 刘景洋 Tin-lead recovery method in waste circuit board
CN103614556A (en) * 2013-10-08 2014-03-05 大连东泰产业废弃物处理有限公司 Method for treating waste mobile phone circuit board and recovering precious metals
CN105002363A (en) * 2015-08-07 2015-10-28 珠海格力电器股份有限公司 Method for recovering gold from circuit board

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112939055A (en) * 2021-01-25 2021-06-11 湖北林泰环境科技有限公司 Method for producing copper chloride by using waste acidic etching solution

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Application publication date: 20160413