CN111635994A - A kind of method for recovering copper from acid copper-containing etching solution and preparing cuprous oxide - Google Patents
A kind of method for recovering copper from acid copper-containing etching solution and preparing cuprous oxide Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 151
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 143
- 238000005530 etching Methods 0.000 title claims abstract description 78
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 50
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 title claims description 39
- 239000012074 organic phase Substances 0.000 claims abstract description 80
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- 239000002699 waste material Substances 0.000 claims abstract description 51
- 239000012071 phase Substances 0.000 claims abstract description 42
- 239000008346 aqueous phase Substances 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000013517 stratification Methods 0.000 claims abstract description 9
- 238000009388 chemical precipitation Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 238000000605 extraction Methods 0.000 claims description 68
- 239000007788 liquid Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003638 chemical reducing agent Substances 0.000 claims description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 19
- 229910001431 copper ion Inorganic materials 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
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- 239000008103 glucose Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 15
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 17
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 17
- 238000005191 phase separation Methods 0.000 description 16
- 238000011084 recovery Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 241000530268 Lycaena heteronea Species 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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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
- 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
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- Mechanical Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
本发明公开了一种从酸性含铜蚀刻液中回收铜并制备氧化亚铜的方法，包括以下步骤：S1、将酸性含铜蚀刻废液进行过滤处理，得到粗含铜溶液；S2、将粗含铜溶液调节pH至2～4，加入萃取剂并混合搅拌，静置分层后，上层为初次含铜有机相，下层为初次水相；将初次水相进行回收用于蚀刻生产线；S3、将含铜有机相用去离子水水洗，分离得到二次含铜有机相与一次洗涤水相；S4、在二次含铜有机相中加入硫酸并充分搅拌，静置分层后，上层为含萃取剂有机相，下层为含CuSO4水相；S5、将一次洗涤水相加入到含萃取剂有机相中进行水洗，静置分层后，得到纯净萃取剂有机相，以备步骤S2使用；S6、采用水热法或者化学沉淀法由含CuSO4水相制备得到氧化亚铜。
The invention discloses a method for recovering copper from an acidic copper-containing etching solution and preparing cuprous oxide, which comprises the following steps: S1, filtering the acidic copper-containing etching waste solution to obtain a crude copper-containing solution; S2, filtering the crude copper-containing solution The copper-containing solution is adjusted to pH 2 to 4, an extractant is added, mixed and stirred, and after standing for stratification, the upper layer is the primary copper-containing organic phase, and the lower layer is the primary aqueous phase; the primary aqueous phase is recovered for the etching production line; S3, The copper-containing organic phase is washed with deionized water, and the secondary copper-containing organic phase and the primary washing water phase are obtained by separation; S4, sulfuric acid is added to the secondary copper-containing organic phase and fully stirred, and after standing for stratification, the upper layer is composed of copper-containing organic phases. Extracting agent organic phase, the lower layer is an aqueous phase containing CuSO 4 ; S5, adding a washing aqueous phase to the extracting agent-containing organic phase for washing, and after standing for stratification, a pure extracting agent organic phase is obtained for use in step S2; S6, using a hydrothermal method or a chemical precipitation method to prepare cuprous oxide from an aqueous phase containing CuSO 4 .
Description
技术领域technical field
本发明涉及铜资源回收利用领域，尤其涉及一种从酸性含铜蚀刻液中回收铜并制备氧化亚铜的方法。The invention relates to the field of copper resource recovery and utilization, in particular to a method for recovering copper from an acidic copper-containing etching solution and preparing cuprous oxide.
背景技术Background technique
印刷电路板经蚀刻后会产生大量含铜废蚀刻液，且随着电子工业的发展，含铜废蚀刻液排放量日益增大。蚀刻废液可分为酸性和碱性两大类，在中国主要为酸性蚀刻液。酸性废液主要含氯化铜及盐酸等，铜离子含量一般为10～250g/L、游离盐酸浓度一般为0.5～6mol/L。酸性蚀刻废液若直接排放，会严重污染环境，并导致重金属铜资源的巨大浪费。因此，酸性蚀刻废液的有效处理及铜的回收利用对于环境保护和铜资源的高效利用具有重要的经济和环保意义。目前，从酸性蚀刻废液中回收铜的方法主要有化学沉淀法、吸附法、电解沉积法和溶剂萃取法等。回收产品主要有氧化铜、硫酸铜等，其产品品质低、市场价值较低，相比较而言，氧化亚铜具有更好的市场前景。一方面，氧化亚铜可以作为船舶防污涂料，具有污染少、毒性低、有效期长、成本低等诸多优点，其需求量随着中国船舶工业和航海业的发展壮大而逐年增长；另一方面，氧化亚铜还具有理想的光电压和光记忆性质，在光电子领域应用前景广阔。此外，氧化亚铜在有机催化、农业、光催化、玻璃和陶瓷等方面的应用也得到了一定的发展。After the printed circuit board is etched, a large amount of copper-containing waste etching solution will be produced, and with the development of the electronics industry, the discharge of copper-containing waste etching solution is increasing. Etching waste liquid can be divided into two categories: acidic and alkaline, mainly acidic etching liquid in China. The acidic waste liquid mainly contains copper chloride and hydrochloric acid. If the acid etching waste liquid is directly discharged, it will seriously pollute the environment and lead to a huge waste of heavy metal copper resources. Therefore, the effective treatment of acid etching waste liquid and the recycling of copper have important economic and environmental significance for environmental protection and efficient utilization of copper resources. At present, the methods for recovering copper from acid etching waste liquid mainly include chemical precipitation method, adsorption method, electrolytic deposition method and solvent extraction method. The main recycled products are copper oxide, copper sulfate, etc., which have low product quality and low market value. In comparison, cuprous oxide has better market prospects. On the one hand, cuprous oxide can be used as antifouling paint for ships, which has many advantages such as less pollution, low toxicity, long validity period and low cost. , Cuprous oxide also has ideal photovoltage and photomemory properties, and has broad application prospects in the field of optoelectronics. In addition, the application of cuprous oxide in organic catalysis, agriculture, photocatalysis, glass and ceramics has also been developed to some extent.
但是，目前从酸性含铜蚀刻废液中萃取分离铜离子并制备氧化亚铜的方法还存在以下问题：However, the method for extracting and separating copper ions from the acidic copper-containing etching waste liquid and preparing cuprous oxide still has the following problems:
1、其制备工艺仅仅适合于实验室研究，无法实现大规模工业化应用；1. Its preparation process is only suitable for laboratory research and cannot achieve large-scale industrial application;
2、对于酸性含铜蚀刻废液的处理设备结构复杂，操作维护工作困难；2. The structure of the treatment equipment for acid copper-containing etching waste liquid is complex, and the operation and maintenance work is difficult;
3、制备工艺大多采用电沉积方法进行制备且制备产品以纯铜为主，电沉积设备结构复杂、能耗高、经济价值较低。3. Most of the preparation processes are prepared by electrodeposition methods, and the prepared products are mainly pure copper. The electrodeposition equipment has complex structure, high energy consumption and low economic value.
发明内容SUMMARY OF THE INVENTION
本发明目的是针对上述问题，提供一种反应速率快、回收效率高的从酸性含铜蚀刻液中回收铜并制备氧化亚铜的方法。The purpose of the present invention is to solve the above problems, and provide a method for recovering copper from an acidic copper-containing etching solution and preparing cuprous oxide with fast reaction rate and high recovery efficiency.
为了实现上述目的，本发明的技术方案是：In order to achieve the above object, the technical scheme of the present invention is:
一种从酸性含铜蚀刻液中回收铜并制备氧化亚铜的方法，包括以下步骤：A method for recovering copper and preparing cuprous oxide from an acidic copper-containing etching solution, comprising the following steps:
S1、将酸性含铜蚀刻废液进行过滤处理，去除酸性含铜蚀刻废液中的不溶性颗粒，然后加入NaOH将酸性含铜蚀刻废液的pH值调至2～4，并依次加入Na2SO4和BaCO3，静置60分钟，去除沉淀后得到粗含铜溶液；S1. Filter the acidic copper-containing etching waste liquid to remove the insoluble particles in the acidic copper-containing etching waste liquid, then add NaOH to adjust the pH value of the acidic copper-containing etching waste liquid to 2-4, and sequentially add Na 2 SO 4 and BaCO 3 , let stand for 60 minutes, remove the precipitate to obtain a crude copper-containing solution;
S2、将步骤S1中得到的粗含铜溶液用氨水调节pH至2～4，然后将其转入到萃取缸中，加入萃取剂并混合搅拌，静置分层后，上层为初次含铜有机相，下层为初次水相；将初次水相进行回收用于蚀刻生产线；S2, adjust the pH of the crude copper-containing solution obtained in step S1 to 2～4 with ammonia water, then transfer it into the extraction cylinder, add an extractant and mix and stir, after standing for stratification, the upper layer is the primary copper-containing organic phase, the lower layer is the primary water phase; the primary water phase is recycled for the etching production line;
S3、将步骤S2中得到的含铜有机相用去离子水水洗，分离得到二次含铜有机相与一次洗涤水相；S3, the copper-containing organic phase obtained in step S2 is washed with deionized water, and the secondary copper-containing organic phase and the primary washing water phase are obtained by separation;
S4、将步骤S3中得到的二次含铜有机相转入反萃取缸中，同时加入硫酸并充分搅拌，静置分层后，上层为含萃取剂有机相，下层为含CuSO4水相；S4, the secondary copper-containing organic phase obtained in step S3 is transferred into the stripping cylinder, simultaneously adding sulfuric acid and fully stirring, after standing for stratification, the upper layer is the organic phase containing the extraction agent, and the lower layer is the aqueous phase containing CuSO ;
S5、将步骤S3中得到的一次洗涤水相加入到含萃取剂有机相中进行水洗，静置分层后，得到纯净萃取剂有机相，以备步骤S2使用；S5, the primary washing water phase obtained in step S3 is added to the organic phase containing the extractant for washing, and after standing for stratification, a pure extractant organic phase is obtained for use in step S2;
S6、向步骤S4中得到的含CuSO4水相中加入NaOH或KOH调节pH至碱性，加入还原剂，采用水热法或者化学沉淀法制备得到氧化亚铜。S6. Add NaOH or KOH to the CuSO 4 -containing aqueous phase obtained in step S4 to adjust pH to alkaline, add a reducing agent, and prepare cuprous oxide by hydrothermal method or chemical precipitation method.
进一步的，所述萃取剂为Mextral984H，浓度为10～50％，用于萃取剂的稀释剂为MextralDT100，萃取剂与酸性含铜蚀刻废液的体积比为5～15：1，萃取级数为1～5。Further, the extractant is Mextral984H, the concentration is 10-50%, the diluent used for the extractant is MextralDT100, the volume ratio of the extractant to the acid copper-containing etching waste liquid is 5-15:1, and the extraction stage is 1 to 5.
进一步的，所述步骤S4中的硫酸浓度为100～220g/L，硫酸与二次含铜有机相的体积比为1：1～5。Further, the sulfuric acid concentration in the step S4 is 100-220 g/L, and the volume ratio of the sulfuric acid to the secondary copper-containing organic phase is 1:1-5.
进一步的，所述步骤S6中采用水热法制备氧化亚铜包括以下步骤:Further, in described step S6, adopting hydrothermal method to prepare cuprous oxide comprises the following steps:
S61、将含CuSO4水相加入到水热反应釜中，用1mol/L的NaOH溶液或KOH溶液调节pH至碱性，然后加入还原剂并进行密封，水热反应温度为150～200℃，水热反应时间1～24h，得到氧化亚铜溶液；S61, adding the aqueous phase containing CuSO 4 to the hydrothermal reaction kettle, adjusting the pH to alkaline with 1 mol/L NaOH solution or KOH solution, then adding a reducing agent and sealing, the hydrothermal reaction temperature is 150～200 ℃, The hydrothermal reaction time is 1～24h to obtain cuprous oxide solution;
S62、将步骤S61得到的氧化亚铜溶液进行离心分离，并用水和乙醇交替清洗、过滤，滤液至中性后将过滤后的氧化亚铜固体放入真空干燥箱内，干燥6～12h，即得到高纯度的氧化亚铜。S62, centrifuge the cuprous oxide solution obtained in step S61, wash and filter alternately with water and ethanol, put the filtered cuprous oxide solid into a vacuum drying box after the filtrate is neutral, and dry for 6 to 12 hours, that is, Obtain high-purity cuprous oxide.
进一步的，所述步骤S6中采用化学沉淀法制备氧化亚铜包括以下步骤:Further, in described step S6, adopting chemical precipitation method to prepare cuprous oxide comprises the following steps:
S63、将含CuSO4水相加入到搅拌反应器中，用1mol/L的NaOH溶液或KOH溶液调节pH至碱性，然后加入还原剂，反应1～6h；S63, adding the aqueous phase containing CuSO 4 into the stirring reactor, adjusting the pH to alkaline with 1 mol/L NaOH solution or KOH solution, then adding a reducing agent, and reacting for 1-6 hours;
S64、将步骤S63得到的氧化亚铜溶液进行离心分离，并用水和乙醇交替清洗、过滤，滤液至中性后将过滤后的氧化亚铜固体放入真空干燥箱内，干燥6～12h，即得到高纯度的氧化亚铜。S64, centrifuge the cuprous oxide solution obtained in step S63, and alternately wash and filter with water and ethanol, after the filtrate becomes neutral, put the filtered cuprous oxide solid in a vacuum drying box, and dry for 6 to 12 hours, that is, Obtain high-purity cuprous oxide.
进一步的，所述步骤S6中的还原剂为亚硫酸盐、葡萄糖、酒石酸、水合肼、硼氢化钠、抗坏血酸、次亚磷酸钠中的一种或多种组合；所述还原剂与含CuSO4水相中铜离子的摩尔比为1～5：1。Further, the reducing agent in the step S6 is one or more combinations of sulfite, glucose, tartaric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, and sodium hypophosphite ; The molar ratio of copper ions in the water phase is 1-5:1.
与现有技术相比，本发明具有的优点和积极效果是：Compared with the prior art, the present invention has the following advantages and positive effects:
1、本发明中的制备工艺能有效处理酸性含铜蚀刻液，避免了含铜蚀刻液的排放造成环境污染，同时铜的回收率可以达到99.5％，具有极好的金属铜回收利用率；1. The preparation process in the present invention can effectively treat the acid copper-containing etching solution, avoids environmental pollution caused by the discharge of the copper-containing etching solution, and at the same time, the recovery rate of copper can reach 99.5%, with excellent metal copper recovery rate;
2、本发明中的工艺制备得到的氧化亚铜产品纯度可以达到99.9％，具有极高的附加价值；2. The purity of the cuprous oxide product prepared by the process of the present invention can reach 99.9%, and has extremely high added value;
3、本发明工艺中的萃取剂回收方便，并可重复利用，减少了萃取剂的排放污染并节约了工艺成本；3. The extraction agent in the process of the present invention is easy to recover and can be reused, which reduces the discharge pollution of the extraction agent and saves the process cost;
4、本发明工艺过程产生的水经回收后可满足蚀刻生产线的用水要求，具有显著的节水及环保性。4. The water produced in the process of the present invention can meet the water requirements of the etching production line after being recycled, and has remarkable water saving and environmental protection.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.
图1为本发明的工艺流程框架图；Fig. 1 is the process flow frame diagram of the present invention;
图2为本发明所制备氧化亚铜的SEM图；Fig. 2 is the SEM image of cuprous oxide prepared by the present invention;
图3为本发明所制备氧化亚铜的XRD谱图。Fig. 3 is the XRD spectrum of cuprous oxide prepared by the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work, any modifications, equivalent replacements, improvements, etc., should be included in the protection scope of the present invention. Inside.
实施例1Example 1
某酸性蚀刻废液，Cu2+浓度为200g/L、H+浓度为2.5mol/L，含有大量氯离子。如图1工艺流程示意图所示，将酸性含铜蚀刻废液进行过滤预处理，去除工业酸性含铜蚀刻废液中的细微不溶性颗粒，然后加入适量NaOH将溶液的pH值调至2～4，并依次加入适量Na2SO4和BaCO3，静置60分钟，采用精密过滤器去除沉淀后加入适量氨水，再次将pH值调至2～4，得到粗含铜溶液。采用MextralDT100稀释的萃取剂Mextral984H萃取粗铜溶液中的铜离子，其中萃取剂浓度为50％，萃取剂与含铜蚀刻废液体积比为(O/A)15:1，萃取级数为5级，萃取后得到蓝色含铜萃取相(有机相)和萃余相(水相)。萃余相(水相)进行组分调节，作为再生蚀刻液。含铜萃取相(有机相)进行第一次水洗，得到蓝色透明含铜有机相和一次洗涤水。将蓝色透明含铜有机相与浓度为220g/L的硫酸溶液按体积比2:1充分混合进行反萃取，静置分相后，上层为有机相，下层为含硫酸铜水相。采用一次洗涤水对上层有机相进行二次洗涤，静置分相后，分离有机相作为萃取剂重复使用。往反萃取后的含硫酸铜水相中加入适量KOH调节pH至碱性，然后按铜离子与还原剂酒石酸摩尔比1:2加入酒石酸，强力搅拌后转入反应釜中进行水热反应，水热温度为180℃，水热时间为24h。待反应结束后，离心分离，分别用去离子水和乙醇循环洗涤2次，然后放入真空干燥箱中，干燥12h，得到纳米氧化亚铜粉末，其纯度为99.9％，铜回收率为99.5％。A certain acid etching waste liquid, the Cu 2+ concentration is 200g/L, the H + concentration is 2.5mol/L, and contains a large amount of chloride ions. As shown in the schematic diagram of the process flow in Figure 1, the acid copper-containing etching waste liquid is filtered and pretreated to remove fine insoluble particles in the industrial acid copper-containing etching waste liquid, and then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4. Then add appropriate amount of Na 2 SO 4 and BaCO 3 in turn, let stand for 60 minutes, use a precision filter to remove the precipitate, add appropriate amount of ammonia water, and adjust the pH value to 2-4 again to obtain a crude copper-containing solution. The extraction agent Mextral984H diluted with MextralDT100 is used to extract copper ions in the crude copper solution. The concentration of the extraction agent is 50%, the volume ratio of the extraction agent to the copper-containing etching waste liquid is (O/A) 15:1, and the extraction stage is 5 grades. , after extraction, a blue copper-containing extract phase (organic phase) and raffinate phase (aqueous phase) were obtained. The raffinate phase (aqueous phase) is adjusted in composition and used as a regeneration etching solution. The copper-containing extraction phase (organic phase) is washed with water for the first time to obtain a blue transparent copper-containing organic phase and a washing water. The blue transparent copper-containing organic phase and the sulfuric acid solution with a concentration of 220 g/L were fully mixed in a volume ratio of 2:1 for back extraction, and after standing for phase separation, the upper layer was the organic phase, and the lower layer was the copper sulfate-containing aqueous phase. The upper organic phase is washed twice with primary washing water, and after standing for phase separation, the separated organic phase is reused as an extractant. Add an appropriate amount of KOH to the back-extracted copper sulfate-containing aqueous phase to adjust the pH to alkaline, then add tartaric acid according to the molar ratio of copper ions to reducing agent tartaric acid 1:2, and then transfer to the reactor for hydrothermal reaction after vigorous stirring. The thermal temperature is 180°C, and the hydrothermal time is 24h. After the reaction is over, centrifuged, washed twice with deionized water and ethanol, and then put into a vacuum drying box and dried for 12 hours to obtain nano-cuprous oxide powder with a purity of 99.9% and a copper recovery rate of 99.5%. .
实施例2Example 2
某酸性蚀刻废液，Cu2+浓度为150g/L、H+浓度为2mol/L，含有大量氯离子。如图1工艺流程示意图所示，将酸性含铜蚀刻废液进行过滤预处理，去除工业酸性含铜蚀刻废液中的细微不溶性颗粒，然后加入适量NaOH将溶液的pH值调至2～4，并依次加入适量Na2SO4和BaCO3，静置60分钟，采用精密过滤器去除沉淀后加入适量氨水，再次将pH值调至2～4，得到粗含铜溶液。采用MextralDT100稀释的萃取剂Mextral984H萃取粗铜溶液中的铜离子，其中萃取剂浓度为40％，萃取剂与含铜蚀刻废液体积比为(O/A)10:1，萃取级数为3级，萃取后得到蓝色含铜萃取相(有机相)和萃余相(水相)。萃余相(水相)进行组分调节，作为再生蚀刻液。含铜萃取相(有机相)进行第一次水洗，得到蓝色透明含铜有机相和一次洗涤水。将蓝色透明含铜有机相与浓度为180g/L的硫酸溶液按体积比2:1充分混合进行反萃取，静置分相后，上层为有机相，下层为含硫酸铜水相。采用一次洗涤水对上层有机相进行二次洗涤，静置分相后，分离有机相作为萃取剂重复使用。往反萃取后的硫酸铜溶液中加入适量NaOH调节pH至碱性，然后按铜离子与还原剂葡萄糖摩尔比1:1加入葡萄糖，磁力搅拌后转入反应釜中进行水热反应，水热温度为150℃，水热时间为12h，待反应结束后，离心分离，分别用去离子水和乙醇洗涤2次，然后放入真空干燥箱中，干燥6h，得到纳米氧化亚铜粉末，其纯度为99.5％，铜回收率为99％。A certain acid etching waste liquid, Cu 2+ concentration is 150g/L, H + concentration is 2mol/L, and contains a lot of chloride ions. As shown in the schematic diagram of the process flow in Figure 1, the acid copper-containing etching waste liquid is filtered and pretreated to remove fine insoluble particles in the industrial acid copper-containing etching waste liquid, and then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4. Then add appropriate amount of Na 2 SO 4 and BaCO 3 in turn, let stand for 60 minutes, use a precision filter to remove the precipitate, add appropriate amount of ammonia water, and adjust the pH value to 2-4 again to obtain a crude copper-containing solution. The extraction agent Mextral984H diluted with MextralDT100 is used to extract copper ions in the crude copper solution. The concentration of the extraction agent is 40%, the volume ratio of the extraction agent to the copper-containing etching waste liquid is (O/A) 10:1, and the extraction stage is 3 levels. , after extraction, a blue copper-containing extract phase (organic phase) and raffinate phase (aqueous phase) were obtained. The raffinate phase (aqueous phase) is adjusted in composition and used as a regeneration etching solution. The copper-containing extraction phase (organic phase) is washed with water for the first time to obtain a blue transparent copper-containing organic phase and a washing water. The blue transparent copper-containing organic phase and the sulfuric acid solution with a concentration of 180 g/L were fully mixed in a volume ratio of 2:1 to carry out back extraction. After standing for phase separation, the upper layer was the organic phase, and the lower layer was the copper sulfate-containing aqueous phase. The upper organic phase is washed twice with primary washing water, and after standing for phase separation, the separated organic phase is reused as an extractant. Add an appropriate amount of NaOH to the back-extracted copper sulfate solution to adjust the pH to alkaline, then add glucose according to the mol ratio of copper ions to reducing agent glucose 1:1, and transfer to the reactor after magnetic stirring for hydrothermal reaction. The hydrothermal temperature The temperature is 150°C, the hydrothermal time is 12h, after the reaction is over, centrifuged, washed twice with deionized water and ethanol respectively, and then put into a vacuum drying box and dried for 6h to obtain nano-cuprous oxide powder, whose purity is 99.5% copper recovery rate of 99%.
实施例3Example 3
某酸性蚀刻废液，Cu2+浓度为50g/L、H+浓度为0.7mol/L，含有大量氯离子。如图1工艺流程示意图所示，将酸性含铜蚀刻废液进行过滤预处理，去除工业酸性含铜蚀刻废液中的细微不溶性颗粒，然后加入适量NaOH将溶液的pH值调至2～4，并依次加入适量Na2SO4和BaCO3，静置60分钟，采用精密过滤器去除沉淀后加入适量氨水，再次将pH值调至2～4，得到粗含铜溶液。采用MextralDT100稀释的萃取剂Mextral984H萃取粗铜溶液中的铜离子，其中萃取剂浓度为20％，萃取剂与含铜蚀刻废液体积比为(O/A)5:1，萃取级数为1级，萃取后得到蓝色含铜萃取相(有机相)和萃余相(水相)。萃余相(水相)进行组分调节，作为再生蚀刻液。含铜萃取相(有机相)进行第一次水洗，得到蓝色透明含铜有机相和一次洗涤水。将蓝色透明含铜有机相与浓度为100g/L的硫酸溶液按体积比2:1充分混合进行反萃取，静置分相后，上层为有机相，下层为含硫酸铜水相。采用一次洗涤水对上层有机相进行二次洗涤，静置分相后，分离有机相作为萃取剂重复使用。往反萃取后的硫酸铜溶液中加入适量NaOH调节pH至碱性，然后按铜离子与还原剂亚硫酸钠摩尔比为1:1.2加入亚硫酸钠，在烧杯中反应6h，待反应结束后，离心分离，分别用去离子水和乙醇洗涤2次，然后放入真空干燥箱中，干燥8h，得到纳米氧化亚铜粉末，其纯度为99.5％，铜回收率为98％。A certain acid etching waste liquid, Cu 2+ concentration is 50g/L, H + concentration is 0.7mol/L, and contains a lot of chloride ions. As shown in the schematic diagram of the process flow in Figure 1, the acid copper-containing etching waste liquid is filtered and pretreated to remove fine insoluble particles in the industrial acid copper-containing etching waste liquid, and then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4. Then add appropriate amount of Na 2 SO 4 and BaCO 3 in turn, let stand for 60 minutes, use a precision filter to remove the precipitate, add appropriate amount of ammonia water, and adjust the pH value to 2-4 again to obtain a crude copper-containing solution. The extraction agent Mextral984H diluted with MextralDT100 is used to extract copper ions in the crude copper solution. The concentration of the extraction agent is 20%, the volume ratio of the extraction agent to the copper-containing etching waste liquid is (O/A) 5:1, and the extraction stage is 1 level. , after extraction, a blue copper-containing extract phase (organic phase) and raffinate phase (aqueous phase) were obtained. The raffinate phase (aqueous phase) is adjusted in composition and used as a regeneration etching solution. The copper-containing extraction phase (organic phase) is washed with water for the first time to obtain a blue transparent copper-containing organic phase and a washing water. The blue transparent copper-containing organic phase and the sulfuric acid solution with a concentration of 100g/L are fully mixed in a volume ratio of 2:1 for back extraction, and after standing for phase separation, the upper layer is the organic phase, and the lower layer is the copper sulfate-containing aqueous phase. The upper organic phase is washed twice with primary washing water, and after standing for phase separation, the separated organic phase is reused as an extractant. Add an appropriate amount of NaOH to the back-extracted copper sulfate solution to adjust the pH to alkaline, then add sodium sulfite according to the molar ratio of copper ions and reducing agent sodium sulfite to 1:1.2, and react in a beaker for 6 hours. Washed twice with deionized water and ethanol, then placed in a vacuum drying box and dried for 8 hours to obtain nano-cuprous oxide powder with a purity of 99.5% and a copper recovery rate of 98%.
实施例4Example 4
某酸性蚀刻废液，Cu2+浓度为180g/L、H+浓度为3mol/L，含有大量氯离子。如图1工艺流程示意图所示，将酸性含铜蚀刻废液进行过滤预处理，去除工业酸性含铜蚀刻废液中的细微不溶性颗粒，然后加入适量NaOH将溶液的pH值调至2～4，并依次加入适量Na2SO4和BaCO3，静置60分钟，采用精密过滤器去除沉淀后加入适量氨水，再次将pH值调至2～4，得到粗含铜溶液。采用MextralDT100稀释的萃取剂Mextral984H萃取粗铜溶液中的铜离子，其中萃取剂浓度为20％，萃取剂与含铜蚀刻废液体积比为(O/A)8:1，萃取级数为3级，萃取后得到蓝色含铜萃取相(有机相)和萃余相(水相)。萃余相(水相)进行组分调节，作为再生蚀刻液。含铜萃取相(有机相)进行第一次水洗，得到蓝色透明含铜有机相和一次洗涤水。将蓝色透明含铜有机相与浓度为150g/L的硫酸溶液按体积比2:1充分混合进行反萃取，静置分相后，上层为有机相，下层为含硫酸铜水相。采用一次洗涤水对上层有机相进行二次洗涤，静置分相后，分离有机相作为萃取剂重复使用。往反萃取后的硫酸铜溶液中加入适量NaOH调节pH至碱性，然后按铜离子与还原剂水合肼摩尔比为1:3加入水合肼，在烧杯中反应2h，待反应结束后，离心分离，分别用去离子水和乙醇洗涤2次，然后放入真空干燥箱中，干燥3h，得到纳米氧化亚铜粉末，其纯度为99％，铜回收率为90％。A certain acid etching waste liquid, the Cu 2+ concentration is 180g/L, the H + concentration is 3mol/L, and contains a large amount of chloride ions. As shown in the schematic diagram of the process flow in Figure 1, the acid copper-containing etching waste liquid is filtered and pretreated to remove fine insoluble particles in the industrial acid copper-containing etching waste liquid, and then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4. Then add appropriate amount of Na 2 SO 4 and BaCO 3 in turn, let stand for 60 minutes, use a precision filter to remove the precipitate, add appropriate amount of ammonia water, and adjust the pH value to 2-4 again to obtain a crude copper-containing solution. The extraction agent Mextral984H diluted with MextralDT100 is used to extract copper ions in the crude copper solution, wherein the concentration of the extraction agent is 20%, the volume ratio of the extraction agent to the copper-containing etching waste liquid is (O/A) 8:1, and the extraction stage is 3 , after extraction, a blue copper-containing extract phase (organic phase) and raffinate phase (aqueous phase) were obtained. The raffinate phase (aqueous phase) is adjusted in composition and used as a regeneration etching solution. The copper-containing extraction phase (organic phase) is washed with water for the first time to obtain a blue transparent copper-containing organic phase and a washing water. The blue transparent copper-containing organic phase and the sulfuric acid solution with a concentration of 150 g/L were fully mixed in a volume ratio of 2:1 for back extraction, and after standing for phase separation, the upper layer was the organic phase, and the lower layer was the copper sulfate-containing aqueous phase. The upper organic phase is washed twice with primary washing water, and after standing for phase separation, the separated organic phase is reused as an extractant. Add an appropriate amount of NaOH to the back-extracted copper sulfate solution to adjust the pH to alkaline, and then add hydrazine hydrate according to the molar ratio of copper ions to reducing agent hydrazine hydrate as 1:3, and react in a beaker for 2 hours. After the reaction is completed, centrifuge separation , washed twice with deionized water and ethanol respectively, then put it into a vacuum drying box and dried for 3 hours to obtain nano cuprous oxide powder with a purity of 99% and a copper recovery rate of 90%.
实施例5Example 5
某酸性蚀刻废液，Cu2+浓度为80g/L、H+浓度为1mol/L，含有大量氯离子。如图1工艺流程示意图所示，将酸性含铜蚀刻废液进行过滤预处理，去除工业酸性含铜蚀刻废液中的细微不溶性颗粒，然后加入适量NaOH将溶液的pH值调至2～4，并依次加入适量Na2SO4和BaCO3，静置60分钟，采用精密过滤器去除沉淀后加入适量氨水，再次将pH值调至2～4，得到粗含铜溶液。采用MextralDT100稀释的萃取剂Mextral984H萃取粗铜溶液中的铜离子，其中萃取剂浓度为10％，萃取剂与含铜蚀刻废液体积比为(O/A)12:1，萃取级数为3级，萃取后得到蓝色含铜萃取相(有机相)和萃余相(水相)。萃余相(水相)进行组分调节，作为再生蚀刻液。含铜萃取相(有机相)进行第一次水洗，得到蓝色透明含铜有机相和一次洗涤水。将蓝色透明含铜有机相与浓度为150g/L的硫酸溶液按体积比2:1充分混合进行反萃取，静置分相后，上层为有机相，下层为含硫酸铜水相。采用一次洗涤水对上层有机相进行二次洗涤，静置分相后，分离有机相作为萃取剂重复使用。往反萃取后的硫酸铜溶液中加入适量NaOH调节pH至碱性，然后按铜离子与还原剂硼氢化钠摩尔比为1:2加入硼氢化钠，在烧杯中反应1h，待反应结束后，离心分离，分别用去离子水和乙醇洗涤2次，然后放入真空干燥箱中，干燥12h，得到纳米氧化亚铜粉末，其纯度为99.5％，铜回收率为96％。A certain acid etching waste liquid, Cu 2+ concentration is 80g/L, H + concentration is 1mol/L, and contains a lot of chloride ions. As shown in the schematic diagram of the process flow in Figure 1, the acid copper-containing etching waste liquid is filtered and pretreated to remove fine insoluble particles in the industrial acid copper-containing etching waste liquid, and then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4. Then add appropriate amount of Na 2 SO 4 and BaCO 3 in turn, let stand for 60 minutes, use a precision filter to remove the precipitate, add appropriate amount of ammonia water, and adjust the pH value to 2-4 again to obtain a crude copper-containing solution. The extraction agent Mextral984H diluted with MextralDT100 is used to extract copper ions in the crude copper solution. The concentration of the extraction agent is 10%, the volume ratio of the extraction agent to the copper-containing etching waste liquid is (O/A) 12:1, and the extraction stage is 3. , after extraction, a blue copper-containing extract phase (organic phase) and raffinate phase (aqueous phase) were obtained. The raffinate phase (aqueous phase) is adjusted in composition and used as a regeneration etching solution. The copper-containing extraction phase (organic phase) is washed with water for the first time to obtain a blue transparent copper-containing organic phase and a washing water. The blue transparent copper-containing organic phase and the sulfuric acid solution with a concentration of 150 g/L were fully mixed in a volume ratio of 2:1 for back extraction, and after standing for phase separation, the upper layer was the organic phase, and the lower layer was the copper sulfate-containing aqueous phase. The upper organic phase is washed twice with primary washing water, and after standing for phase separation, the separated organic phase is reused as an extractant. Add an appropriate amount of NaOH to the back-extracted copper sulfate solution to adjust the pH to alkaline, and then add sodium borohydride according to the molar ratio of copper ions to reducing agent sodium borohydride as 1:2, and react in a beaker for 1 hour. Centrifugal separation, washed twice with deionized water and ethanol respectively, then placed in a vacuum drying box and dried for 12 hours to obtain nano-cuprous oxide powder with a purity of 99.5% and a copper recovery rate of 96%.
实施例6Example 6
某酸性蚀刻废液，Cu2+浓度为120g/L、H+浓度为2mol/L，含有大量氯离子。如图1工艺流程示意图所示，将酸性含铜蚀刻废液进行过滤预处理，去除工业酸性含铜蚀刻废液中的细微不溶性颗粒，然后加入适量NaOH将溶液的pH值调至2～4，并依次加入适量Na2SO4和BaCO3，静置60分钟，采用精密过滤器去除沉淀后加入适量氨水，再次将pH值调至2～4，得到粗含铜溶液。采用MextralDT100稀释的萃取剂Mextral984H萃取粗铜溶液中的铜离子，其中萃取剂浓度为30％，萃取剂与含铜蚀刻废液体积比为(O/A)8:1，萃取级数为4级，萃取后得到蓝色含铜萃取相(有机相)和萃余相(水相)。萃余相(水相)进行组分调节，作为再生蚀刻液。含铜萃取相(有机相)进行第一次水洗，得到蓝色透明含铜有机相和一次洗涤水。将蓝色透明含铜有机相与浓度为220g/L的硫酸溶液按体积比2:1充分混合进行反萃取，静置分相后，上层为有机相，下层为含硫酸铜水相。采用一次洗涤水对上层有机相进行二次洗涤，静置分相后，分离有机相作为萃取剂重复使用。往反萃取后的硫酸铜溶液中加入适量NaOH调节pH至碱性，然后按铜离子与混合还原剂(抗坏血酸和葡萄糖)摩尔比为1:5加入混合还原剂，磁力搅拌后转入反应釜中进行水热反应，水热温度为200℃，水热时间为2h，待反应结束后，离心分离，分别用去离子水和乙醇洗涤2次，然后放入真空干燥箱中，干燥6h，得到纳米氧化亚铜粉末，其纯度为99.8％，铜回收率为99％。A certain acid etching waste liquid, Cu 2+ concentration is 120g/L, H + concentration is 2mol/L, and contains a lot of chloride ions. As shown in the schematic diagram of the process flow in Figure 1, the acid copper-containing etching waste liquid is filtered and pretreated to remove fine insoluble particles in the industrial acid copper-containing etching waste liquid, and then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4. Then add appropriate amount of Na 2 SO 4 and BaCO 3 in turn, let stand for 60 minutes, use a precision filter to remove the precipitate, add appropriate amount of ammonia water, and adjust the pH value to 2-4 again to obtain a crude copper-containing solution. The extraction agent Mextral984H diluted with MextralDT100 is used to extract copper ions in the crude copper solution. The concentration of the extraction agent is 30%, the volume ratio of the extraction agent to the copper-containing etching waste liquid is (O/A) 8:1, and the number of extraction stages is 4. , after extraction, a blue copper-containing extract phase (organic phase) and raffinate phase (aqueous phase) were obtained. The raffinate phase (aqueous phase) is adjusted in composition and used as a regeneration etching solution. The copper-containing extraction phase (organic phase) is washed with water for the first time to obtain a blue transparent copper-containing organic phase and a washing water. The blue transparent copper-containing organic phase and the sulfuric acid solution with a concentration of 220 g/L were fully mixed in a volume ratio of 2:1 for back extraction, and after standing for phase separation, the upper layer was the organic phase, and the lower layer was the copper sulfate-containing aqueous phase. The upper organic phase is washed twice with primary washing water, and after standing for phase separation, the separated organic phase is reused as an extractant. Add an appropriate amount of NaOH to the copper sulfate solution after back-extraction to adjust the pH to alkaline, then add the mixed reducing agent according to the molar ratio of copper ion and mixed reducing agent (ascorbic acid and glucose) as 1:5, and transfer to the reaction kettle after magnetic stirring. The hydrothermal reaction was carried out, the hydrothermal temperature was 200 °C, and the hydrothermal time was 2 h. After the reaction was over, centrifuged, washed twice with deionized water and ethanol respectively, and then put it into a vacuum drying box and dried for 6 h to obtain nanometers. Cuprous oxide powder with a purity of 99.8% and a copper recovery of 99%.
实施例7Example 7
某酸性蚀刻废液，Cu2+浓度为100g/L、H+浓度为1.5mol/L，含有大量氯离子。如图1工艺流程示意图所示，将酸性含铜蚀刻废液进行过滤预处理，去除工业酸性含铜蚀刻废液中的细微不溶性颗粒，然后加入适量NaOH将溶液的pH值调至2～4，并依次加入适量Na2SO4和BaCO3，静置60分钟，采用精密过滤器去除沉淀后加入适量氨水，再次将pH值调至2～4，得到粗含铜溶液。采用MextralDT100稀释的萃取剂Mextral984H萃取粗铜溶液中的铜离子，其中萃取剂浓度为25％，萃取剂与含铜蚀刻废液体积比为(O/A)10:1，萃取级数为3级，萃取后得到蓝色含铜萃取相(有机相)和萃余相(水相)。萃余相(水相)进行组分调节，作为再生蚀刻液。含铜萃取相(有机相)进行第一次水洗，得到蓝色透明含铜有机相和一次洗涤水。将蓝色透明含铜有机相与浓度为220g/L的硫酸溶液按体积比2:1充分混合进行反萃取，静置分相后，上层为有机相，下层为含硫酸铜水相。采用一次洗涤水对上层有机相进行二次洗涤，静置分相后，分离有机相作为萃取剂重复使用。往反萃取后的硫酸铜溶液中加入适量NaOH调节pH为碱性，然后按铜离子与混合还原剂(葡萄糖和次亚磷酸钠)摩尔比为1:4加入混合还原剂，磁力搅拌后转入反应釜中进行水热反应，水热温度为200℃，水热时间为2h，待反应结束后，离心分离，分别用去离子水和乙醇洗涤2次，然后放入真空干燥箱中，干燥6h，得到纳米氧化亚铜粉末，其纯度为99.5％，铜回收率为99.5％。A certain acid etching waste liquid, with Cu 2+ concentration of 100g/L and H + concentration of 1.5mol/L, contains a large amount of chloride ions. As shown in the schematic diagram of the process flow in Figure 1, the acid copper-containing etching waste liquid is filtered and pretreated to remove fine insoluble particles in the industrial acid copper-containing etching waste liquid, and then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4. Then add appropriate amount of Na 2 SO 4 and BaCO 3 in turn, let stand for 60 minutes, use a precision filter to remove the precipitate, add appropriate amount of ammonia water, and adjust the pH value to 2-4 again to obtain a crude copper-containing solution. The extraction agent Mextral984H diluted with MextralDT100 is used to extract copper ions in the crude copper solution, wherein the concentration of the extraction agent is 25%, the volume ratio of the extraction agent to the copper-containing etching waste liquid is (O/A) 10:1, and the number of extraction stages is 3 , after extraction, a blue copper-containing extract phase (organic phase) and raffinate phase (aqueous phase) were obtained. The raffinate phase (aqueous phase) is adjusted in composition and used as a regeneration etching solution. The copper-containing extraction phase (organic phase) is washed with water for the first time to obtain a blue transparent copper-containing organic phase and a washing water. The blue transparent copper-containing organic phase and the sulfuric acid solution with a concentration of 220 g/L were fully mixed in a volume ratio of 2:1 for back extraction, and after standing for phase separation, the upper layer was the organic phase, and the lower layer was the copper sulfate-containing aqueous phase. The upper organic phase is washed twice with primary washing water, and after standing for phase separation, the separated organic phase is reused as an extractant. Add an appropriate amount of NaOH to the back-extracted copper sulfate solution to adjust the pH to be alkaline, and then add the mixed reducing agent according to the molar ratio of copper ions to the mixed reducing agent (glucose and sodium hypophosphite) as 1:4, and then transfer to the solution after magnetic stirring. The hydrothermal reaction was carried out in the reaction kettle, the hydrothermal temperature was 200 °C, and the hydrothermal time was 2 h. After the reaction was completed, centrifuged, washed twice with deionized water and ethanol respectively, and then put it in a vacuum drying box and dried for 6 h. , to obtain nano-cuprous oxide powder with a purity of 99.5% and a copper recovery rate of 99.5%.
实施例8Example 8
某酸性蚀刻废液，Cu2+浓度为160g/L、H+浓度为3mol/L，含有大量氯离子。如图1工艺流程示意图所示，将酸性含铜蚀刻废液进行过滤预处理，去除工业酸性含铜蚀刻废液中的细微不溶性颗粒，然后加入适量NaOH将溶液的pH值调至2～4，并依次加入适量Na2SO4和BaCO3，静置60分钟，采用精密过滤器去除沉淀后加入适量氨水，再次将pH值调至2～4，得到粗含铜溶液。采用MextralDT100稀释的萃取剂Mextral984H萃取粗铜溶液中的铜离子，其中萃取剂浓度为25％，萃取剂与含铜蚀刻废液体积比为(O/A)10:1，萃取级数为2级，萃取后得到蓝色含铜萃取相(有机相)和萃余相(水相)。萃余相(水相)进行组分调节，作为再生蚀刻液。含铜萃取相(有机相)进行第一次水洗，得到蓝色透明含铜有机相和一次洗涤水。将蓝色透明含铜有机相与浓度为220g/L的硫酸溶液按体积比2:1充分混合进行反萃取，静置分相后，上层为有机相，下层为含硫酸铜水相。采用一次洗涤水对上层有机相进行二次洗涤，静置分相后，分离有机相作为萃取剂重复使用。往反萃取后的硫酸铜溶液中加入适量NaOH调节pH至碱性，然后按铜离子与混合还原剂(葡萄糖和酒石酸)摩尔比为1:4加入混合还原剂，磁力搅拌后转入反应釜中进行水热反应，水热温度为200℃，水热时间为1h，待反应结束后，离心分离，分别用去离子水和乙醇洗涤2次，然后放入真空干燥箱中，干燥6h，得到纳米氧化亚铜粉末，其纯度为99.5％，铜回收率为95％。A certain acid etching waste liquid, Cu 2+ concentration is 160g/L, H + concentration is 3mol/L, and contains a lot of chloride ions. As shown in the schematic diagram of the process flow in Figure 1, the acid copper-containing etching waste liquid is filtered and pretreated to remove fine insoluble particles in the industrial acid copper-containing etching waste liquid, and then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4. Then add appropriate amount of Na 2 SO 4 and BaCO 3 in turn, let stand for 60 minutes, use a precision filter to remove the precipitate, add appropriate amount of ammonia water, and adjust the pH value to 2-4 again to obtain a crude copper-containing solution. The extraction agent Mextral984H diluted with MextralDT100 is used to extract copper ions in the crude copper solution. The concentration of the extraction agent is 25%, the volume ratio of the extraction agent to the copper-containing etching waste liquid is (O/A) 10:1, and the extraction stage is 2. , after extraction, a blue copper-containing extract phase (organic phase) and raffinate phase (aqueous phase) were obtained. The raffinate phase (aqueous phase) is adjusted in composition and used as a regeneration etching solution. The copper-containing extraction phase (organic phase) is washed with water for the first time to obtain a blue transparent copper-containing organic phase and a washing water. The blue transparent copper-containing organic phase and the sulfuric acid solution with a concentration of 220 g/L were fully mixed in a volume ratio of 2:1 for back extraction, and after standing for phase separation, the upper layer was the organic phase, and the lower layer was the copper sulfate-containing aqueous phase. The upper organic phase is washed twice with primary washing water, and after standing for phase separation, the separated organic phase is reused as an extractant. Add an appropriate amount of NaOH to the back-extracted copper sulfate solution to adjust the pH to alkaline, then add the mixed reducing agent according to the molar ratio of copper ions to the mixed reducing agent (glucose and tartaric acid) as 1:4, and then transfer to the reaction kettle after magnetic stirring. The hydrothermal reaction was carried out with a hydrothermal temperature of 200 °C and a hydrothermal time of 1 h. After the reaction was completed, centrifuged, washed twice with deionized water and ethanol respectively, and then put it into a vacuum drying box and dried for 6 h to obtain nanometers. Cuprous oxide powder with 99.5% purity and 95% copper recovery.
图2、图3分别为上述实施例制得的氧化亚铜的SEM图、XRD谱图；通过上述实施例可以看出本发明具有以下有益效果：Fig. 2, Fig. 3 are respectively the SEM image and the XRD spectrogram of the cuprous oxide obtained by the above-mentioned embodiment; It can be seen from the above-mentioned embodiment that the present invention has the following beneficial effects:
1、本发明中的制备工艺能有效处理酸性含铜蚀刻液，避免了含铜蚀刻液的排放造成环境污染，同时铜的回收率可以达到99.5％，具有极好的金属铜回收利用率；1. The preparation process in the present invention can effectively treat the acid copper-containing etching solution, avoids environmental pollution caused by the discharge of the copper-containing etching solution, and at the same time, the recovery rate of copper can reach 99.5%, with excellent metal copper recovery rate;
2、本发明中的工艺制备得到的氧化亚铜产品纯度可以达到99.9％，具有极高的附加价值；2. The purity of the cuprous oxide product prepared by the process of the present invention can reach 99.9%, and has extremely high added value;
3、本发明工艺中的萃取剂回收方便，并可重复利用，减少了萃取剂的排放污染并节约了工艺成本；3. The extraction agent in the process of the present invention is easy to recover and can be reused, which reduces the discharge pollution of the extraction agent and saves the process cost;
4、本发明工艺过程产生的水经回收后可满足蚀刻生产线的用水要求，具有显著的节水及环保性。4. The water produced in the process of the present invention can meet the water requirements of the etching production line after being recycled, and has remarkable water saving and environmental protection.
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| CN112376049A (en) * | 2020-11-09 | 2021-02-19 | 江苏净拓环保科技有限公司 | Method for recovering acidic etching solution |
| CN112813271A (en) * | 2020-12-31 | 2021-05-18 | 深圳市星河环境技术有限公司 | Method for recovering brownification waste liquid |
| CN113403134A (en) * | 2021-06-23 | 2021-09-17 | 江西省科学院能源研究所 | Copper wire drawing oil waste liquid treatment method |
| CN114836631A (en) * | 2022-06-15 | 2022-08-02 | 蜂巢能源科技股份有限公司 | Recycling method of copper-manganese solution generated by extracting and recycling battery material |
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| CN117303431A (en) * | 2023-11-29 | 2023-12-29 | 泰兴冶炼厂有限公司 | Special copper oxide powder for photovoltaic and preparation process thereof |
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| CN112376049A (en) * | 2020-11-09 | 2021-02-19 | 江苏净拓环保科技有限公司 | Method for recovering acidic etching solution |
| CN112813271A (en) * | 2020-12-31 | 2021-05-18 | 深圳市星河环境技术有限公司 | Method for recovering brownification waste liquid |
| CN113403134A (en) * | 2021-06-23 | 2021-09-17 | 江西省科学院能源研究所 | Copper wire drawing oil waste liquid treatment method |
| CN114836631A (en) * | 2022-06-15 | 2022-08-02 | 蜂巢能源科技股份有限公司 | Recycling method of copper-manganese solution generated by extracting and recycling battery material |
| CN114836631B (en) * | 2022-06-15 | 2023-12-01 | 蜂巢能源科技股份有限公司 | Recycling method of copper-manganese liquid generated by extraction and recovery of battery materials |
| CN116463506A (en) * | 2023-04-07 | 2023-07-21 | 浙江泰能新材料有限公司 | Method for extracting and preparing 3D printing spherical copper powder from copper waste |
| CN117303431A (en) * | 2023-11-29 | 2023-12-29 | 泰兴冶炼厂有限公司 | Special copper oxide powder for photovoltaic and preparation process thereof |
| CN117303431B (en) * | 2023-11-29 | 2024-02-09 | 泰兴冶炼厂有限公司 | Special copper oxide powder for photovoltaic and preparation process thereof |
| CN117945451A (en) * | 2024-03-26 | 2024-04-30 | 江苏泰禾金属工业有限公司 | Method for preparing cuprous oxide from copper-containing acidic etching solution |
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