CN104060094B - A kind of method that reclaims gold and copper from discarded mobile phone - Google Patents
A kind of method that reclaims gold and copper from discarded mobile phone Download PDFInfo
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- CN104060094B CN104060094B CN201410254845.3A CN201410254845A CN104060094B CN 104060094 B CN104060094 B CN 104060094B CN 201410254845 A CN201410254845 A CN 201410254845A CN 104060094 B CN104060094 B CN 104060094B
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- 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
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Abstract
The invention discloses a kind of method that reclaims gold and copper from discarded mobile phone, comprise the following steps: 1) discarded cell phone mainboard is processed into the fragment that is less than 1cm; 2) fragment is added in supercritical water oxidation device, add the hydrogen peroxide of deionized water and 30%, sealing, controlling reactant solid-to-liquid ratio is 1:5 grams per milliliter-1:30 grams per milliliter; 3) heating, temperature starts timing after rising to 250 degree-400 degree, and manual pressure device is controlled at 12MPa-30MPa, reacts after 30-180 minute and stops heating; 4) reaction is opened reactor after finishing to be cooled to room temperature, after Separation of Solid and Liquid, solid phase is placed in to 0.5mol/L-3mol/L sulfuric acid solution and soaks 5-40 minute, filters, and filtrate evaporating, concentrating and crystallizing, reclaims CuSO4Crystal product; 5) dry being placed in KI-iodine solution of remaining solid residue thing soaked 30-180 minute, filters, and obtains golden concentrated solution and reclaims.
Description
Technical field
The present invention relates to discarded object recycle technical field, specifically, the present invention relates toA kind of and method that reclaims gold and copper from discarded mobile phone.
Background technology
At present the annual discarded mobile phone in the whole world approximately has 400,000,000, wherein in state-owned nearly 100,000,000,The rate of recovery is less than 1% but. The address prediction that United Nations Environment Programme issues in the recent period, to 2020Year, the discarded mobile phone quantity of China will increase by 7 times than 2007. In the wiring board of discarded mobile phoneContain the valuable metals such as gold, silver, palladium, copper, content is about respectively: golden 280g/t, silver-colored 2kg/t,Copper 200kg/t, palladium 100g/t, its gold content than high-quality Gold Concentrate under Normal Pressure (70g/t left and right) alsoWant high. In the wiring board of discarded mobile phone, also contain the multiple harmful substances such as brominated flame-retardant simultaneously,If directly abandon severe contamination soil and groundwater. Therefore, carry out metal in discarded mobile phoneRecovery and the research of harmless treatment organic pollution highly significant.
From discarded mobile phone wiring board, the key of selective recovery gold and copper is to make metal and otherSeparately, corresponding recovery process can be divided into pyrogenic process, wet method, biological skill to overwhelming majority materialArt three major types. Pyrogenic process easily causes a large amount of Air Pollutant Emission, even produces persistenceThe secondary pollutions such as organic matter. Because wet method mostly adopts at present chloroazotic acid or contains cyanogen process,Thereby unavoidably produce a large amount of toxic wastewaters. And the shortcoming of biotechnology be its leach timeBetween long, efficiency is lower.
Summary of the invention
The present invention is directed to backward in technique in the discarded mobile phone wiring board resource removal process of China,The present situation that the wasting of resources and environmental pollution are outstanding, has developed a set of environmental friendliness simultaneously innoxiousThe technological process of processing brominated flame-retardant and reclaiming golden in discarded mobile phone and copper.
The present invention is in conjunction with the shape of contained gold, copper and brominated flame-retardant in discarded mobile phone wiring boardState feature, the technique that adopts supercritical water oxidation to leach in conjunction with KI-iodine, bromo is fire-retardantAgent exhaustive oxidation resolves into eco-friendly CO2And H2O, reaches the object of harmless treatment,Meanwhile, realize the selective recovery of golden in discarded mobile phone wiring board and copper.
Technical scheme provided by the invention is: a kind of side that reclaims gold and copper from discarded mobile phoneMethod, comprises the following steps:
1) mainboard of discarded mobile phone is separated to otherwise processed after components and parts classification, mainboard with components and partsBe processed into the fragment that is less than 1cm with shear pulverizer;
2) fragment is added in supercritical water oxidation device, add the mistake of deionized water and 30%Hydrogen oxide, sealing, controlling reactant solid-to-liquid ratio is 1:5 grams per milliliter-1:30 grams per milliliter;
3) heating reactor, temperature starts timing, supercritical water oxidation after rising to 250 degree-400 degreeReaction unit internal pressure is controlled at 12MPa-30MPa by manual pressure device, reactionAfter 30-180 minute, stop heating;
4) reaction is opened reactor after finishing to be cooled to room temperature, after Separation of Solid and Liquid, solid phase is placed inIn 0.5mol/L-3mol/L sulfuric acid solution, soak 5-40 minute, filter, filtrate evaporation and concentration knotCrystalline substance, reclaims CuSO4Crystal product;
5) dry being placed on of remaining solid residue thing soaked 30-180 minute in KI-iodine solution,Filter, obtain golden concentrated solution and reclaim wherein KI concentration 280-360mM, iodine listMatter concentration=30-50mM.
Described step 2) in, controlling reactant solid-to-liquid ratio is 1:10 grams per milliliter.
Described step 3) in, temperature rises to 400 degree and starts timing, reacts 60 minutes.
Described step 2) in, can before sealing, pass into oxygen 1-5 minute to substitute peroxidatingHydrogen.
Described step 5) in, in KI-iodine solution, KI concentration is 320mM, iodine listMatter concentration is 40mM.
The invention has the beneficial effects as follows:
China leaches discarded hand about supercritical water oxidation pretreatment in conjunction with KI-iodine at presentIn machine circuit plate, the related data of metal is blank substantially. In the present invention based on supercritical water oxygenThe meaning of change and KI-iodine extract technology method is mainly manifested in: pre-at supercritical water oxidationIn processing, solve discarded at present to the harmless treatment of contained brominated flame-retardant in discarded mobile phoneThe urgent problem facing in mobile phone recovery process; This process has realized discarded handThe selective recovery of gold and copper in machine circuit plate.
Brief description of the drawings
When considered in conjunction with the accompanying drawings, by the detailed description with reference to below, can be more completeUnderstand well the present invention and easily learn wherein many advantages of following, but described hereinAccompanying drawing be used to provide a further understanding of the present invention, form a part of the present invention, thisThe schematic description and description of invention is used for explaining the present invention, does not form the present inventionImproper restriction, wherein:
The discarded mobile phone wiring board of Fig. 1 reclaims the process chart of gold and copper;
Fig. 2 supercritical water oxidation pretreatment time, temperature are decomposed debrominate effect to brominated flame-retardantThe impact of rate;
Fig. 3 dilute sulfuric acid soaks the XRD diffraction analysis collection of illustrative plates of reaction front and back solid phase product, on the wayIn: A: through the pretreated sample of supercritical water oxidation; B: through supercritical water oxidationSample after pretreatment and dilute sulfuric acid soak;
Different KI-iodine the leaching conditions of Fig. 4 return the leaching of gold in discarded mobile phone wiring board(supercritical water oxidation pretreatment condition is: temperature=400 DEG C, time=60 in the impact of the rate of producing effectsMinute, solid-to-liquid ratio=1:10g/mL).
Detailed description of the invention
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, belowThe present invention is further detailed explanation with detailed description of the invention by reference to the accompanying drawings.
Embodiment 1:
As shown in Figure 1, the mainboard of discarded mobile phone wiring board is separated to components and parts with components and partsOtherwise processed after classification, wiring board mainboard is processed into the fragment that is less than 1cm with shear pulverizer.The discarded mobile phone wiring board fragment of having sheared is added in supercritical water oxidation device, addThe hydrogen peroxide that enters 50 ml deionized water and 40 milliliter 30%, sealed reactor (also immediatelyCan before sealing, pass into oxygen 1-5 minute to substitute hydrogen peroxide), heating, temperature rises toAfter 400 degree, start timing, now container inner pressure is controlled at 23MPa by manual pressure device,React after 60 minutes and stop heating. Temperature is opened reaction unit after being down to room temperature, by reactantBe transferred to centrifugation in centrifuge tube. Get after centrifugation constant volume after 1 milliliter of dilution of water,Then with ion chromatography inorganic Br content wherein. Fig. 2 shows, above-mentioned overcriticalUnder water oxidation pre-treatment condition, the decomposition debrominate effect of brominated flame-retardant in discarded mobile phone wiring boardRate reaches 99.8%. In addition, get rare sulphur that solid product after centrifugation adds 1mol/LIn acid solution (solid-to-liquid ratio is controlled at 1:10g/mL), stirring reaction 20 minutes, centrifugation,After filtrate evaporating, concentrating and crystallizing, centrifugation again, separates the solid product obtaining dryAfter weigh, and carry out XRD powder diffraction analysis, result proves copper sulfate crystal, purityReach 98.5%, the rate of recovery of copper reaches 99%. Soak before and after reaction carrying out dilute sulfuric acidSolid phase adopts XRD powder diffraction analysis, as shown in Figure 3, shows that the immersion of dilute sulfuric acid canEffectively leach the metallic copper reclaiming wherein. Dried KI-iodine solution for solid product(KI concentration=320mM, elemental iodine concentration=40mM) soaks 120 minutes, solid-liquidThan being controlled at 1:10g/mL, as shown in Figure 4, the leaching rate of recovery of gold reaches 98%.
Embodiment 2:
As shown in Figure 1, the mainboard of discarded mobile phone wiring board is separated to components and parts with components and partsOtherwise processed after classification, wiring board mainboard is processed into the fragment that is less than 1cm with shear pulverizer.The discarded mobile phone wiring board fragment of having sheared is added in supercritical water oxidation device, addThe hydrogen peroxide that enters 90 ml deionized water and 60 milliliter 30%, sealed reactor (also immediatelyCan before sealing, pass into oxygen 1-5 minute to substitute hydrogen peroxide), heating, temperature rises toAfter 250 degree, start timing, now container inner pressure is controlled at by manual pressure device12MPa, reacts after 30 minutes and stops heating. Temperature is opened reaction unit after being down to room temperature,By reactant transfer to centrifugation in centrifuge tube. Get 1 milliliter of dilution of water after centrifugationRear constant volume, then with ion chromatography inorganic Br content wherein. Fig. 2 shows, upperState under supercritical water oxidation pretreatment condition, in discarded mobile phone wiring board, brominated flame-retardant dividesSeparate debrominate efficiency and reach 95%. In addition, the solid product of getting after centrifugation adds 0.5mol/LDilution heat of sulfuric acid in (solid-to-liquid ratio is controlled at 1:5g/mL), stirring reaction 5 minutes, centrifugalSeparate, after filtrate evaporating, concentrating and crystallizing, centrifugation again, separates the solid product obtainingAfter dry, weigh, and carry out XRD powder diffraction analysis, result proves copper sulfate crystal,Purity reaches 98.5%, and the rate of recovery of copper reaches 51%. Dried solid product iodatePotassium-iodine solution (KI concentration=320mM, elemental iodine concentration=40mM) soaks 30 pointsClock, solid-to-liquid ratio is controlled at 1:5g/mL, and the leaching rate of recovery of gold reaches 45%.
Embodiment 3:
As shown in Figure 1, the mainboard of discarded mobile phone wiring board is separated to components and parts with components and partsOtherwise processed after classification, wiring board mainboard is processed into the fragment that is less than 1cm with shear pulverizer.The discarded mobile phone wiring board fragment of having sheared is added in supercritical water oxidation device, addThe hydrogen peroxide that enters 50 ml deionized water and 40 milliliter 30%, sealed reactor (also immediatelyCan before sealing, pass into oxygen 1-5 minute to substitute hydrogen peroxide), heating, temperature rises toAfter 400 degree, start timing, now container inner pressure is controlled at by manual pressure device30MPa, reacts after 180 minutes and stops heating. Temperature is opened reaction unit after being down to room temperature,By reactant transfer to centrifugation in centrifuge tube. Get 1 milliliter of dilution of water after centrifugationRear constant volume, then with ion chromatography inorganic Br content wherein. Fig. 2 shows, upperState under supercritical water oxidation pretreatment condition, in discarded mobile phone wiring board, brominated flame-retardant dividesSeparate debrominate efficiency and reach 99.8%. In addition, the solid product of getting after centrifugation adds 3mol/LDilution heat of sulfuric acid in (solid-to-liquid ratio is controlled at 1:30g/mL), stirring reaction 40 minutes, fromThe heart separates, and after filtrate evaporating, concentrating and crystallizing, centrifugation again, separates the solid phase obtaining and produceThing is weighed after dry, and carries out XRD powder diffraction analysis, and result proves copper sulphate crystalline substanceBody, purity reaches 98.5%, and the rate of recovery of copper reaches 99.5%. Dried solid product is usedKI-iodine solution (KI concentration=320mM, elemental iodine concentration=40mM) soaks180 minutes, solid-to-liquid ratio was controlled at 1:30g/mL, as shown in Figure 4, and the leaching rate of recovery of goldReach 98%.
The explanation of above example is just for helping to understand core concept of the present invention; Meanwhile,For one of ordinary skill in the art, according to thought of the present invention, in detailed description of the inventionAnd all will change in range of application, in sum, this description should not be understoodFor limitation of the present invention.
Claims (1)
1. a method that reclaims gold and copper from discarded mobile phone, is characterized in that, comprises following stepRapid:
1) mainboard of discarded mobile phone is separated with components and parts, otherwise processed after components and parts classification, mainPlate is processed into the fragment that is less than 1cm with shear pulverizer;
2) fragment is added in supercritical water oxidation device, add deionized water, sealing,Controlling reactant solid-to-liquid ratio is 1:10 grams per milliliter; Before sealing, pass into oxygen 1-5 minute;3) heating reactor, temperature starts timing after rising to 400 DEG C, supercritical water oxidationDevice internal pressure is controlled at 23MPa by manual pressure device, reacts and stops after 60 minutesOnly heating;
4) reaction is opened reactor after finishing to be cooled to room temperature, after Separation of Solid and Liquid, solid phase is placed inStirring reaction 20 minutes in 1mol/L sulfuric acid solution, solid-to-liquid ratio is controlled at 1:10g/mL,Filter, filtrate evaporating, concentrating and crystallizing, reclaims CuSO4Crystal product;
5) dry being placed in KI-iodine solution of remaining solid residue thing soaked 120 minutes,Solid-to-liquid ratio is controlled at 1:10g/mL, filters, and obtains golden concentrated solution and reclaims wherein iodineChange potassium concn 320mM, elemental iodine concentration=40mM.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105420500B (en) * | 2015-11-10 | 2017-04-19 | 森蓝环保(上海)有限公司 | Method for separating and extracting all metal components from waste printed circuit boards through wet metallurgy |
| CN105256147A (en) * | 2015-11-30 | 2016-01-20 | 中国科学院生态环境研究中心 | Technique for recovering palladium in waste circuit board by means of supercritical fluid |
| CN105400958B (en) * | 2015-12-03 | 2018-02-02 | 福建工程学院 | Golden method and device in a kind of Rapid Leaching waste printed circuit board |
| CN105861852B (en) * | 2016-03-04 | 2018-09-28 | 北京科技大学 | A method of without cyanidation gold-extracted |
| CN113234926B (en) * | 2021-03-01 | 2022-06-14 | 广东省科学院稀有金属研究所 | Method for efficiently leaching copper and selenium from copper anode slime |
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| CN1426485A (en) * | 2000-04-28 | 2003-06-25 | 约翰逊马西有限公司 | Precious metal recovery from organics-precious metal compositions with supercritical water reactant |
| CN101608263A (en) * | 2009-07-13 | 2009-12-23 | 中国科学院生态环境研究中心 | The synthetic simultaneously Cu of enriching precious metal on abandoned printed circuit board 2O/TiO 2The technology of nano-photocatalyst |
| 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 |
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Patent Citations (3)
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| CN1426485A (en) * | 2000-04-28 | 2003-06-25 | 约翰逊马西有限公司 | Precious metal recovery from organics-precious metal compositions with supercritical water reactant |
| CN101608263A (en) * | 2009-07-13 | 2009-12-23 | 中国科学院生态环境研究中心 | The synthetic simultaneously Cu of enriching precious metal on abandoned printed circuit board 2O/TiO 2The technology of nano-photocatalyst |
| 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 |
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