CN1584129B - Method for separating copper from copper-containing waste liquid - Google Patents
Method for separating copper from copper-containing waste liquid Download PDFInfo
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- CN1584129B CN1584129B CN 03153657 CN03153657A CN1584129B CN 1584129 B CN1584129 B CN 1584129B CN 03153657 CN03153657 CN 03153657 CN 03153657 A CN03153657 A CN 03153657A CN 1584129 B CN1584129 B CN 1584129B
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Abstract
eparation of copper from waste liquid is carried out by: regulating parameters of copper-containing waste liquid in temperature, concentration, electric potential for oxidative reduction, and pH value; adding reducing agent containing -OH, -C(=O)H, -NH2 radicals and/or depositing agent containing -SH, -S-, -C(=S)S- radicals, reacting and extracting-out copper in elementary or solid form, solid-liquid separating, collecting copper and its compounds. The waste liquid can be treated to make it restored as its starting condition. An apparatus is disclosed herewith. The advantages include high recovering rate, less waste discharges, easy operation, simple apparatus, and low cost.
Description
Technical field
The present invention relates to the method for separating copper in a kind of copper waste etching solution that from the higher printed-wiring board (PWB) of contained waste liquid, especially copper content is produced, produces.
Background technology
Can use in the industries such as printed-wiring board (PWB) (PCB) is made, metal cleaning and surface treatment, production of inorganic, plating, sign manufacturing, copper hydrometallurgy copper bearing solution and (or) produce copper bearing waste liquid, the concrete copper content of waste liquid is between the 0.2-200 grams per liter, can be divided into two kinds of acid system and alkaline systems, shown in USP3999564 and USP4130454, the cuprammonia that the former promptly is commonly called as the copper solutions that contains ammonia and ammonium salt, the latter such as hydrochloric, vitriolic copper solutions etc.For printed-wiring board (PWB) (PCB) industry, there is the operation of copper-containing solution to comprise etching, microetch and three operations of plating, how the characteristics that the amount of having is big, pollute weight make its cyclic regeneration and realize that cleaner production is numerous scientific and technical personnel's a target always.Typical acid-based copper etchant is shown in USP5207867, USP5298117 and USP6322955, and typical alkaline-based copper etchant is shown in USP4784785, USP4915776 and USP5127991.USP 5524780 and USP5556553 have reported the method that adopts aluminium reducing copper and make the copper etchant solution cyclic regeneration, and USP5487842 has then reported and adopted solvent extraction to carry out the method for copper etchant solution cyclic regeneration.Equipment has high input, the process management difficulty is big, priming cost is high because they exist, the solution of separating copper is not easy to keep shortcomings such as its application performance when carrying out the cyclic regeneration use, fails to use and promote always.USP4436601, USP4545877, USP 4597842 and USP 5085730 reported and adopted electrolysis to carry out the method for copper etchant solution cyclic regeneration, owing to have chlorine to cause the chlorine effusion in the etching solution, and can't industrialization.
Summary of the invention
An object of the present invention is, provide a kind of from contained waste liquid the method for separating copper, it is higher that contained waste liquid refers in particular to copper content, as the copper waste etching solution that produces in producing from printed-wiring board (PWB).
The method of separating copper may further comprise the steps from contained waste liquid:
(1) the physical-chemical parameters such as the temperature of contained waste liquid, concentration, redox potential, pH value is regulated;
(2) to wherein adding reductive agent, or to wherein adding precipitation agent, or react, copper is separated out from waste liquid with the form of simple substance or other solid chemical compound to wherein adding the mixture that not only contains reductive agent but also contain precipitation agent;
(3) carry out solid-liquid and separate, collect solid copper and (or) other cupric solid chemical compound.
In aforesaid method, said contained waste liquid is the contained waste liquid after many industries generations or the use, printed-wiring board (PWB) (PCB) industry for example, copper etchant solution after especially using in the etching work procedure in the sector or that scrap, make etching performance (etching speed, lateral erosion etc.) variation owing to copper content wherein is higher and can only scrap, also comprise the contained waste liquid that industries such as other industry such as five metals plating, sign manufacturing, surface cleaning produce.
After pending contained waste liquid is collected, at first will be to it temperature, concentration, redox potential, pH value etc. of some relevant the physical-chemical parameters such as waste liquid carry out necessary adjusting so that carry out the processing that next step separates out the copper reaction.Can come attemperation to be advisable by heating, the type of cooling of routine to 20-95 ℃; The concentration that can adopt modes such as conventional evaporation concentration, dilution to regulate waste liquid is that 1.02-1.25 is advisable to be adjusted to proportion; The redox potential that can regulate waste liquid by the concentration that reduces or increase oxidizing substance in the solution or reducing substances, for example can gas be carried by adopting, chemical reaction, normal pressure or ordinary methods such as transformation evaporation, thermal degradation, making increases in the waste liquid or minimizing oxidisability or reducing substances; These materials can be solid, liquid, also can be gas.Regulating the pH value is the most conventional technological operation in this area, and those of ordinary skills can learn employed material and operation steps fully easily, are adjusted to 1.5-11 with the pH value with waste liquid and are advisable.
Adjusting by above-mentioned physico-chemical parameter, contained waste liquid has been adjusted to preferable operating mode, so that in next step reduction of copper and (or) precipitin reaction and solid phase separate out and can carry out effectively, also make the solid phase precipitate of generation such as copper simple substance and (or) physical parameter optimizations such as the granularity of copper compound, proportion, crystal formation, be convenient to next step solid-liquid separation.
The reductive agent that uses among the present invention is 2,4,6-trihydroxybenzoic acid or its salt, phenol, formaldehyde, oxalic dialdehyde, formic acid, oxammonium hydrochloride, phenylhydrazine etc.; The precipitation agent that uses among the present invention is sulfur alcohol, sulfur alcohol sodium, 1, Sodium sulfhydrate, sodium sulphite, sodium ethyl-xanthogenate etc.The effect of reductive agent is with the Cu in the waste liquid
2+Ion is reduced into elemental copper or water-fast monovalence copper compound such as Cu
2O, Cu
2I
2Deng, they can be separated out from solution with solid form; The effect of precipitation agent is that the cupric ion in the waste liquid can be combined with precipitation agent, forms to contain Cu
+Or Cu
2+Throw out, as Cu
2S, xanthogenic acid copper, CuS etc., they are separated out with solid form from waste liquid.Also can use the mixture of reductive agent and precipitation agent.The solid precipitate was exactly elemental copper and contained the sedimentary mixture of Cu this moment.
Add reductive agent and (or) in the process of precipitation agent, also can carry out dynamic adjustments in case of necessity to temperature, concentration, redox potential and the pH value of solution, with guarantee reduction and (or) precipitin reaction carries out most effectively, make the physical parameter optimization such as granularity, proportion, crystal formation of the solid matter of separating out, be convenient to subsequent disposal and use.
Can use conventional solid-liquid separation method to make copper and cupric precipitate and the liquid phase separation of separating out among the present invention, for example filter, centrifugal, press filtration etc., those of ordinary skills can adopt similar method to realize separating by the solid-liquid of the inventive method fully.Collected solid-state elemental copper and (or) copper-containing compound sends to copper smelting plant or inorganic copper salinization factory and makes raw material and use; The waste liquid that has separated copper or copper-containing compound can be sent to and recycle (as the copper etching) or handle the back through other and discharge.
A preferred embodiment by the inventive method, for make full use of separated the solid copper of separating out and (or) other composition in the waste liquid behind the cupric throw out, this waste liquid is sent into one form the adjusting treatment process, wherein by replenish comprise in some copper-containing solutions that are mixed with but the effective constituent of having lost in follow-up use, in handling, make waste liquid return to the preparation back, use preceding physical and chemical state, it can be recycled in industrial processes, in the processes such as for example copper etching, copper facing, surface cleaning.Different according to the contained waste liquid source, required additional effective constituent and content are also had nothing in common with each other, the state before will replenishing with the composition with waste liquid in a word and return to original used contained waste liquid preparation back, using.For example for copper etchant solution, need may comprise anti-lateral erosion agent, copper complexing agent, etching promotor, the pH that replenish to adjust compositions such as agent.Anti-lateral erosion agent includes but not limited to triazole compound and phosphoric acid salt etc., the copper complexing agent includes but not limited to ethylenediamine tetraacetic acid (EDTA) (EDTA), halide-ions, ammonia and organic amine etc., etching promotor includes but not limited to superoxide, oxygen, thiocyanate-, thiosulphate, sulfide etc., and pH adjusts agent and includes but not limited to caustic soda, ammonia, carbon ammonia, hydrochloric acid, sulfuric acid and phosphoric acid etc.
Embodiment
Embodiment 1:
Hunan circuit board plant alkaline etching liquid waste liquid closes copper 160 grams per liters after measured, free ammonia 8 grams per liters, chlorion 152 grams per liters.Get 1 liter of this waste liquid, add formaldehyde [HC (=O) H] 100 grams, in encloses container, reacted 2 hours under 80 ℃, filter afterwards, filter cake cupric 53%, gained filtrate copper content after measured is 0.5 grams per liter, to wherein dropping into 20 milliliter of 28% ammoniacal liquor, 15 gram ammonium chlorides, 2.5 gram ammonium persulphate, 0.1 gram ammonium thiocyanate, 0.3 behind the gram benzotriazole, through the etch application performance measurement, its erosion copper capacity restoration is to 160 grams per liters, and erosion copper speed (when being mixed into cupric 85 grams per liters with the etching mother liquor) reaches 40 μ m/ minutes, the lateral erosion coefficient has satisfied the technical requirements of etch process fully greater than 2.5.
Embodiment 2:
Guangdong circuit board plant acidic etching liquid waste liquid closes copper 132 grams per liters after measured.Get 1 liter of this waste liquid, add oxammonium hydrochloride 30 grams, in encloses container, reacted 2.5 hours under 65 ℃, be cooled to room temperature afterwards, add 120 gram sulfur alcohols again, filter, filter cake cupric 22%, gained filtrate copper content after measured are 0.8 grams per liter, to wherein dropping into 25 milliliters of technical hydrochloric acids, behind 50 gram sodium chlorate, 1.2 gram ammonium persulphates, the 0.5 gram benzotriazole, through the etch application performance measurement, its erosion copper capacity restoration is to 130 grams per liters, and erosion copper speed reaches 30 μ m/ minutes, the lateral erosion coefficient has satisfied the technical requirements of acid etching technology fully greater than 3.0.
Embodiment 3:
Zhejiang circuit board plant alkaline etching liquid waste liquid closes copper 154 grams per liters after measured, free ammonia 5 grams per liters, chlorion 154 grams per liters.Get 1 liter of this waste liquid, add phenylhydrazine 80 grams and dithioglycol 45 grams, in encloses container, reacted 1 hour under 38 ℃, filter afterwards, filter cake cupric 43%, gained filtrate copper content after measured is 0.2 grams per liter, to wherein dropping into 16 milliliter of 28% ammoniacal liquor, 10 gram ammonium chlorides, 2.8 gram ammonium persulphate, 0.2 gram ammonium thiocyanate, 0.1 behind the gram benzotriazole, through the etch application performance measurement, its erosion copper capacity restoration is to 160 grams per liters, and erosion copper speed (when being mixed into cupric 85 grams per liters with the etching mother liquor) reaches 40 μ m/ minutes, the lateral erosion coefficient has satisfied the technical requirements of etch process fully greater than 2.5.
Embodiment 4:
Jiangsu circuit board plant acidic etching liquid waste liquid closes copper 122 grams per liters after measured.Get 1 liter of this waste liquid, with pH regulator is 2, add oxammonium hydrochloride 24 grams, in encloses container, reacted 2 hours under 65 ℃, be cooled to room temperature afterwards, add 85 gram Sodium sulfhydrates again, filter filter cake cupric 28%, gained filtrate copper content after measured is 0.1 grams per liter, after wherein drop into 27 milliliters of technical hydrochloric acids, 35 gram sodium chlorate, 2 gram ammonium persulphates, 0.2 restrain benzotriazole, through the etch application performance measurement, its erosion copper capacity restoration is to 130 grams per liters, erosion copper speed reaches 30 μ m/ minutes, and the lateral erosion coefficient has satisfied the technical requirements of acid etching technology fully greater than 3.0.
Favourable technique effect of the present invention is conspicuous.At first be copper and (or) rate of recovery of copper-containing compound is higher; Next be reclaim behind the copper the waste liquid three wastes that utilize again, discharge capable of circulation seldom, favourable to environmental protection.
Claims (3)
1. the method for a separating copper from contained waste liquid is characterized in that, may further comprise the steps:
(1) temperature, concentration, redox potential, the pH value parameter of contained waste liquid are regulated;
(2) to wherein adding reductive agent or precipitation agent, or react, copper is separated out from waste liquid with the form of simple substance or solid chemical compound to wherein adding the mixture that not only contains reductive agent but also contain precipitation agent;
(3) carry out solid-liquid and separate, collect solid copper and/or copper compound;
Wherein, described reductive agent is to be selected from the following material one or more: 2,4, and 6-trihydroxybenzoic acid or its salt, phenol, formaldehyde, oxalic dialdehyde, formic acid, oxammonium hydrochloride, phenylhydrazine; Described precipitation agent is to be selected from the following material one or more: sulfur alcohol, sulfur alcohol sodium, 1, Sodium sulfhydrate, sodium sulphite, sodium ethyl-xanthogenate.
2. by the method for claim 1, it is characterized in that, also comprise a step: carried out the component adjusting to having separated the waste liquid behind the solid, made it to return to substantially its preparation back, use preceding situation.
3. by the method for claim 1 or 2, it is characterized in that said contained waste liquid is selected from the contained waste liquid that produces at industry of printed circuit boards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153657 CN1584129B (en) | 2003-08-20 | 2003-08-20 | Method for separating copper from copper-containing waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153657 CN1584129B (en) | 2003-08-20 | 2003-08-20 | Method for separating copper from copper-containing waste liquid |
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| CN1584129A CN1584129A (en) | 2005-02-23 |
| CN1584129B true CN1584129B (en) | 2010-11-24 |
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| CN 03153657 Expired - Fee Related CN1584129B (en) | 2003-08-20 | 2003-08-20 | Method for separating copper from copper-containing waste liquid |
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Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995015B (en) * | 2006-01-06 | 2010-11-10 | 深圳市危险废物处理站 | Method for preparing feed grade methionine copper chelate using waste etching liquor |
| CN102240814B (en) * | 2010-05-12 | 2013-09-25 | 陈卓贤 | Method for preparing superfine copper powder by utilizing environmentally-friendly recycled circuit board etching waste liquor |
| CN102807294A (en) * | 2011-05-31 | 2012-12-05 | 无锡尚德太阳能电力有限公司 | Recirculation system for treating used etching liquid |
| CN102373474A (en) * | 2011-10-31 | 2012-03-14 | 合肥晶澳太阳能科技有限公司 | Method for recycling wool making/etching solution |
| CN102409175A (en) * | 2011-11-09 | 2012-04-11 | 中南大学 | Method for treating purification copper-removing slag of nickel electrolysis anode solution |
| CN102603102B (en) * | 2012-03-30 | 2014-01-08 | 湖南万容科技股份有限公司 | Processing method of browning liquid |
| CN103028281B (en) * | 2012-11-12 | 2014-12-24 | 大连太平洋电子有限公司 | Copper removal technique for tin immersion bath solution of chemical tin immersion line |
| CN104342554A (en) * | 2013-07-24 | 2015-02-11 | 中国科学院沈阳应用生态研究所 | Method for removing and recovering copper in municipal excess sludge |
| CN104150666B (en) * | 2014-06-09 | 2015-09-02 | 煤科集团杭州环保研究院有限公司 | High ammonia nitrogen tail washings zero-discharge treatment system after a kind of alkaline etching waste liquid for producing process and method |
| CN103991935B (en) * | 2014-06-10 | 2015-10-21 | 四川农业大学 | A kind of method removing Copper in Electroplating Waste Water ion |
| CN106480473B (en) * | 2015-08-31 | 2019-08-13 | 广东德同环保科技有限公司 | A kind of method of electrolytic acid copper chloride |
| CN107055867A (en) * | 2017-04-20 | 2017-08-18 | 广东省博罗县湘澧精细化工有限公司 | A kind of copper-removing method of the waste liquid of copper containing low concentration |
| CN108913888A (en) * | 2018-08-01 | 2018-11-30 | 昆明理工大学 | A kind of cupric oxide ore leaching agent and its application method based on acid gangue |
| CN109293125A (en) * | 2018-10-30 | 2019-02-01 | 金川集团股份有限公司 | The method of copper removal is gone in a kind of desulfurization waste liquor |
| CN111304657B (en) * | 2019-02-12 | 2023-08-15 | 叶旖婷 | Method for electrolytic recycling of alkaline etching waste liquid |
| CN110040872A (en) * | 2019-04-11 | 2019-07-23 | 深圳市华星光电技术有限公司 | Copper ion processing system and its waste water treatment system |
| CN110387573B (en) * | 2019-07-04 | 2021-01-05 | 广州兴森快捷电路科技有限公司 | Multi-waste liquid shunting method and electroplating production system |
| CN114032550B (en) * | 2021-10-19 | 2023-03-24 | 深圳前海榕达创途化工科技股份有限公司 | Low-acid low-chlorine electrolysis method for on-site copper extraction of PCB and waste liquid regeneration and reuse method |
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