CN104692446B - A kind of preparation method of high-purity low chlorine oxide of high activity copper - Google Patents
A kind of preparation method of high-purity low chlorine oxide of high activity copper Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000010949 copper Substances 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 38
- 230000000694 effects Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910001902 chlorine oxide Inorganic materials 0.000 title claims 3
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 title claims 3
- 239000002994 raw material Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 4
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 239000001508 potassium citrate Substances 0.000 claims description 4
- 229960002635 potassium citrate Drugs 0.000 claims description 4
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 4
- 235000011082 potassium citrates Nutrition 0.000 claims description 4
- 239000001540 sodium lactate Substances 0.000 claims description 4
- 235000011088 sodium lactate Nutrition 0.000 claims description 4
- 229940005581 sodium lactate Drugs 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229960000448 lactic acid Drugs 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229960004109 potassium acetate Drugs 0.000 claims description 2
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 claims description 2
- 239000001521 potassium lactate Substances 0.000 claims description 2
- 235000011085 potassium lactate Nutrition 0.000 claims description 2
- 229960001304 potassium lactate Drugs 0.000 claims description 2
- YPSNMKHPDJVGEX-UHFFFAOYSA-L potassium;sodium;3-carboxy-3-hydroxypentanedioate Chemical compound [Na+].[K+].OC(=O)CC(O)(C([O-])=O)CC([O-])=O YPSNMKHPDJVGEX-UHFFFAOYSA-L 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims 3
- RZOBLYBZQXQGFY-UHFFFAOYSA-N ammonium lactate Chemical compound [NH4+].CC(O)C([O-])=O RZOBLYBZQXQGFY-UHFFFAOYSA-N 0.000 claims 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 25
- 239000005751 Copper oxide Substances 0.000 abstract description 22
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 22
- 239000000460 chlorine Substances 0.000 abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 abstract description 20
- 239000011259 mixed solution Substances 0.000 abstract description 13
- 239000000243 solution Substances 0.000 abstract description 13
- 238000004090 dissolution Methods 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000008139 complexing agent Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004251 Ammonium lactate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种高纯低氯高活性氧化铜的制备方法，包括以下步骤：将含铜原料、络合剂、助剂及去离子水加入反应釜中混合均匀得到混合液，向所述混合液中缓慢加入沉淀剂溶液，在40‑80℃下反应2‑3h后过滤，用水洗至pH为7.0～7.5，于100～120℃干燥1～3小时，再于300～600℃煅烧0.5～2小时后得到高纯低氯高活性氧化铜。本发明生产出的产品质量及性能更为优异，制得的产品纯度≥99.0％、氯离子含量小于20ppm、溶解时间小于15秒。The invention discloses a preparation method of high-purity, low-chlorine and high-activity copper oxide, which comprises the following steps: adding copper-containing raw materials, complexing agents, auxiliary agents and deionized water into a reaction kettle and mixing uniformly to obtain a mixed solution, and adding the Slowly add precipitant solution into the mixture, react at 40-80°C for 2-3h, filter, wash with water until pH is 7.0-7.5, dry at 100-120°C for 1-3 hours, and then calcinate at 300-600°C for 0.5 After ~2 hours, high-purity, low-chlorine and high-activity copper oxide was obtained. The quality and performance of the product produced by the invention are more excellent, the purity of the prepared product is more than 99.0%, the chloride ion content is less than 20ppm, and the dissolution time is less than 15 seconds.
Description
一、技术领域1. Technical field
本发明涉及一种高纯低氯高活性氧化铜的生产方法，属于电子应用材料领域。The invention relates to a production method of high-purity, low-chlorine and high-activity copper oxide, which belongs to the field of electronic application materials.
二、背景技术2. Background technology
随着电子工业的飞速发展，印制电路板(PCB)制造向多层化、功能化和集成化等方向迅速发展。印制电路设计大量采用微小孔、窄间距、细导线等，使得PCB制造技术难度越来越高，常规的垂直电镀铜工艺不能满足高质量、高可靠性、互连孔等的技术要求，于是产生了水平电镀铜技术。水平电镀铜生产工艺中需要补充铜离子来维持镀液中的铜离子浓度，而该铜离子的补充则要依靠活性氧化铜(或称电镀级氧化铜)来完成。因为活性氧化铜具有较高的化学活性，可保证其能快速溶解于电镀液中，从而满足水平镀铜新工艺技术的使用要求。With the rapid development of the electronics industry, the manufacturing of printed circuit boards (PCBs) is rapidly developing in the direction of multi-layer, functional and integrated. Printed circuit design uses a large number of tiny holes, narrow spacing, thin wires, etc., which makes PCB manufacturing technology more and more difficult. The conventional vertical copper plating process cannot meet the technical requirements of high quality, high reliability, and interconnection holes. Therefore, The horizontal electroplating copper technology has been produced. In the horizontal electroplating copper production process, it is necessary to supplement copper ions to maintain the concentration of copper ions in the plating solution, and the supplement of copper ions depends on active copper oxide (or electroplating grade copper oxide) to complete. Because the active copper oxide has high chemical activity, it can be guaranteed to be quickly dissolved in the electroplating solution, so as to meet the requirements of the new technology of horizontal copper plating.
近年来，活性氧化铜制取方法研究受到了广泛的关注，其发展趋势是研发高纯、低氯及高活性的氧化铜制备技术，即研制的活性氧化铜产品纯度应不低于99％、氯含量应不大于30ppm、溶解时间应不大于30秒等。目前公开报道的制备高纯低氯高活性氧化铜的方法主要有两种，一种是以泰兴冶炼厂有限公司为代表的以电解铜、液氨、高纯二氧化碳等为原料，采用先制备浓氨水，然后向浓氨水中通入高纯二氧化碳制得碳化氨水，此碳化氨水在一定条件下与铜反应得到铜氨络合溶液，再通过加热、蒸氨、分离、洗涤、干燥、煅烧等工序制得高纯低氯活性氧化铜的方法。泰兴冶炼厂有限公司等申请人已公开了多件类似的中国发明专利，它们的申请号分别是：201210559034.5、201210559066.5、201210559070.1、201210559104.7、201210559223.2、201210559225.1等。这些文献中给出了活性氧化铜产品纯度为99.5％、溶解时间为26秒等数据，但未给出产品氯含量的数值。另一种是以昆山市千灯三废净化有限公司为代表的以含铜蚀刻废液、液体氢氧化钠等为主要原料，采用先对含铜蚀刻废液进行净化、除杂，然后加入氢氧化钠溶液，经混合反应、过滤得到粗品氧化铜；再将粗品氧化铜经干燥、粉碎、水洗、超声波洗涤、微波再次干燥及粉碎工艺，制得高活性氧化铜的方法。此方面已公开的中国发明专利有：201010207485.3、201210235602.6等。这些文献中给出了活性氧化铜产品纯度在99％以上、溶解时间大于17秒的数据，但也未给出产品中氯含量的数值。In recent years, the research on the preparation method of activated copper oxide has received extensive attention. Its development trend is to develop high-purity, low-chlorine and high-activity copper oxide preparation technology, that is, the purity of the developed activated copper oxide product should not be lower than 99%. Chlorine content should not exceed 30ppm, dissolution time should not exceed 30 seconds, etc. At present, there are mainly two methods for preparing high-purity, low-chlorine and high-activity copper oxide publicly reported. One is represented by Taixing Smelter Co., Ltd., using electrolytic copper, liquid ammonia, and high-purity carbon dioxide as raw materials. Ammonia water, and then pass high-purity carbon dioxide into the concentrated ammonia water to obtain carbonized ammonia water. The carbonized ammonia water reacts with copper under certain conditions to obtain a copper-ammonia complex solution, and then undergoes processes such as heating, ammonia distillation, separation, washing, drying, and calcination. A method for preparing high-purity low-chlorine active copper oxide. Applicants such as Taixing Smelter Co., Ltd. have disclosed several similar Chinese invention patents, and their application numbers are: 201210559034.5, 201210559066.5, 201210559070.1, 201210559104.7, 201210559223.2, 201210559225.1, etc. In these documents, the purity of the active copper oxide product is 99.5%, and the dissolution time is 26 seconds, etc., but the value of the chlorine content of the product is not given. The other is represented by Kunshan Qiandeng Sanwaste Purification Co., Ltd., which uses copper-containing etching waste liquid and liquid sodium hydroxide as the main raw materials. The sodium solution is mixed and reacted and filtered to obtain crude copper oxide; then the crude copper oxide is dried, pulverized, washed with water, ultrasonically washed, microwave dried again and pulverized to obtain highly active copper oxide. The published Chinese invention patents in this respect include: 201010207485.3, 201210235602.6, etc. These documents give the data that the purity of the active copper oxide product is above 99%, and the dissolution time is greater than 17 seconds, but the numerical value of the chlorine content in the product is not given.
从上述文献中不难看出，目前报道的高纯低氯高活性氧化铜的制备方法中尚存在诸多不足；且到目前为止，并未见同时具备高纯、低氯及高活性的氧化铜制备技术的公开报道。如上述的第一种方法主要用电解铜作为原料，导致生产成本偏高；另外，尽管文献标题说的是低氯产品，但文献中并未给出产品氯含量的数值。第二种方法主要使用了含铜蚀刻废液作为原料，使生产成本得到了一定的降低，但为了除去原料中存在的铁、镍、铅、锌及氯离子等，采用的生产工艺较为复杂，使洗水用量有较大的增加等，且文献中也未给出产品的氯含量等数值。It is not difficult to see from the above-mentioned documents that there are still many deficiencies in the preparation methods of high-purity, low-chlorine and high-activity copper oxide reported at present; Public reporting of technology. For example, the first method above mainly uses electrolytic copper as a raw material, resulting in high production costs; in addition, although the title of the document says that it is a low-chlorine product, the value of the chlorine content of the product is not given in the document. The second method mainly uses copper-containing etching waste liquid as a raw material, which reduces the production cost to a certain extent, but in order to remove iron, nickel, lead, zinc and chloride ions in the raw material, the production process adopted is relatively complicated. The amount of washing water has been greatly increased, etc., and the values such as the chlorine content of the product have not been given in the literature.
三、发明内容3. Contents of the invention
本发明是针对现有制备技术存在的不足之处，旨在提供一种高纯低氯高活性氧化铜的制备方法，使制得的产品纯度≥99.0％、氯离子含量小于20ppm、溶解时间小于15秒。The present invention aims at the deficiencies of the existing preparation technology, and aims to provide a preparation method of high-purity, low-chlorine and high-activity copper oxide, so that the prepared product has a purity of ≥99.0%, a chloride ion content of less than 20ppm, and a dissolution time of less than 15 seconds.
本发明解决技术问题采用的技术方案如下：The technical solution adopted by the present invention to solve technical problems is as follows:
本发明高纯低氯高活性氧化铜的制备方法，按以下步骤操作：The preparation method of high-purity low-chlorine high-activity copper oxide of the present invention, operates according to the following steps:
将含铜原料、络合剂、助剂及去离子水加入反应釜中混合均匀得到混合液，混合液中含铜原料的质量浓度(以铜计)≤18％，络合剂与铜的摩尔比为(0.8～1.1):1，助剂与铜的质量比为(0.005～0.01):1；向所述混合液中缓慢加入沉淀剂溶液，沉淀剂与铜的摩尔比为(2.4～3):1，在40-80℃下反应2-3h后过滤，用水洗至pH为7.0～7.5，于100～120℃干燥1～3小时，并于300～600℃煅烧0.5～2小时后得到高纯低氯高活性氧化铜。Add the copper-containing raw material, complexing agent, auxiliary agent and deionized water into the reactor and mix evenly to obtain a mixed solution. The mass concentration of the copper-containing raw material (calculated as copper) in the mixed solution is ≤18%, and the molar amount of the complexing agent and copper is Ratio is (0.8～1.1):1, the mass ratio of auxiliary agent and copper is (0.005～0.01):1; Slowly add precipitant solution in the mixed solution, the molar ratio of precipitant and copper is (2.4～3 ): 1, filter after reacting at 40-80°C for 2-3h, wash with water until the pH is 7.0-7.5, dry at 100-120°C for 1-3 hours, and calcined at 300-600°C for 0.5-2 hours to obtain High purity low chlorine high activity copper oxide.
所述含铜原料为硫酸铜、硝酸铜或乙酸铜。The copper-containing raw material is copper sulfate, copper nitrate or copper acetate.
所述络合剂为乙酸、乙酸钠、乙酸钾、乙酸铵、乳酸、乳酸钠、乳酸钾、乳酸铵、柠檬酸、柠檬酸钠、柠檬酸钾、柠檬酸铵或柠檬酸钾钠。The complexing agent is acetic acid, sodium acetate, potassium acetate, ammonium acetate, lactic acid, sodium lactate, potassium lactate, ammonium lactate, citric acid, sodium citrate, potassium citrate, ammonium citrate or potassium sodium citrate.
所述助剂为聚乙烯吡咯烷酮(PVP)、十六烷基三甲基溴化铵(CTAB)、OP-10、PEG800或PEG20000。The auxiliary agent is polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide (CTAB), OP-10, PEG800 or PEG20000.
所述沉淀剂溶液为氢氧化钠溶液或氢氧化钾溶液；所述沉淀剂溶液的质量浓度为1～45％。The precipitant solution is sodium hydroxide solution or potassium hydroxide solution; the mass concentration of the precipitant solution is 1-45%.
与已有技术相比，本发明有益效果体现在：Compared with the prior art, the beneficial effects of the present invention are reflected in:
1、本发明所用生产工艺更为简单，设备更易选择，操作更为简便，生产成本更为低廉。1. The production process used in the present invention is simpler, the equipment is easier to select, the operation is simpler, and the production cost is lower.
2、本发明生产出的产品质量及性能更为优异，制得的产品纯度≥99.0％、氯离子含量小于20ppm、溶解时间小于15秒。2. The quality and performance of the product produced by the present invention are more excellent, the purity of the produced product is ≥99.0%, the chloride ion content is less than 20ppm, and the dissolution time is less than 15 seconds.
四、具体实施方式4. Specific implementation
实施例1：Example 1:
1、将硫酸铜、乳酸钠、PEG20000和去离子水加入反应釜中，搅拌混合均匀得到混合液。混合液中铜的质量浓度为10％，乳酸钠与硫酸铜的摩尔比为1.1:1，PEG20000与铜的质量比为0.006:1。1. Add copper sulfate, sodium lactate, PEG20000 and deionized water into the reaction kettle, stir and mix evenly to obtain a mixed solution. The mass concentration of copper in the mixed solution is 10%, the molar ratio of sodium lactate to copper sulfate is 1.1:1, and the mass ratio of PEG20000 to copper is 0.006:1.
2、向所述混合液中缓慢加入质量浓度为10％的氢氧化钠溶液，氢氧化钠与铜的摩尔比为2.5:1，在45℃下反应3h后过滤，用水洗至pH为7.1，于105℃干燥2.5小时，并于350℃煅烧2小时后得到高纯低氯高活性氧化铜，测得其纯度为99.1％、氯离子含量为15ppm、溶解时间为12.0秒。2. Slowly add a sodium hydroxide solution with a mass concentration of 10% to the mixed solution, the molar ratio of sodium hydroxide to copper is 2.5:1, react at 45°C for 3 hours, filter, wash with water until the pH is 7.1, Dry at 105°C for 2.5 hours, and calcined at 350°C for 2 hours to obtain high-purity, low-chlorine, high-activity copper oxide with a purity of 99.1%, a chloride ion content of 15ppm, and a dissolution time of 12.0 seconds.
溶解时间的测试方法为：将16mL质量浓度为98％的硫酸溶液加水稀释至1000mL，然后加入10g氧化铜，常温条件下，记录氧化铜粉完全溶解的时间。以下实施例的测试方法相同。实施例2：The test method of dissolution time is: dilute 16mL of sulfuric acid solution with a mass concentration of 98% to 1000mL with water, then add 10g of copper oxide, and record the time for the copper oxide powder to completely dissolve under normal temperature conditions. The test methods of the following examples are the same. Example 2:
1、将乙酸铜、乙酸、OP-10和去离子水加入反应釜中，搅拌混合均匀得到混合液。混合液中铜的质量浓度为5％，乙酸与乙酸铜的摩尔比为0.9:1，OP-10与铜的质量比为0.008:1。1. Add copper acetate, acetic acid, OP-10 and deionized water into the reaction kettle, stir and mix evenly to obtain a mixed solution. The mass concentration of copper in the mixed solution is 5%, the molar ratio of acetic acid to copper acetate is 0.9:1, and the mass ratio of OP-10 to copper is 0.008:1.
2、向所述混合液中缓慢加入质量浓度为20％的氢氧化钠溶液，氢氧化钠与铜的摩尔比为3.0:1。在60℃下反应2.5h后过滤，用水洗至pH为7.2，于110℃干燥2小时，并于550℃煅烧1小时后得到高纯低氯高活性氧化铜，测得其纯度为99.7％、氯离子含量为16ppm、溶解时间为14.6秒。2. Slowly add sodium hydroxide solution with a mass concentration of 20% into the mixed solution, and the molar ratio of sodium hydroxide to copper is 3.0:1. After reacting at 60°C for 2.5h, filter, wash with water until the pH is 7.2, dry at 110°C for 2 hours, and calcined at 550°C for 1 hour to obtain high-purity, low-chlorine and high-activity copper oxide. The measured purity is 99.7%, The chloride ion content was 16 ppm, and the dissolution time was 14.6 seconds.
实施例3：Example 3:
1、将硝酸铜、柠檬酸钾、PVP和去离子水加入反应釜中，搅拌混合均匀得到混合液。混合液中铜的质量浓度为15％，柠檬酸钾与硫酸铜的摩尔比为1.0:1，PVP与铜的质量比为0.01:1。1. Add copper nitrate, potassium citrate, PVP and deionized water into the reaction kettle, stir and mix evenly to obtain a mixed solution. The mass concentration of copper in the mixed solution is 15%, the molar ratio of potassium citrate to copper sulfate is 1.0:1, and the mass ratio of PVP to copper is 0.01:1.
2、向所述混合液中缓慢加入质量浓度为35％的氢氧化钾溶液，氢氧化钾与铜的摩尔比为2.8:1。在80℃下反应1h后过滤，用水洗至pH为7.3，于120℃干燥1小时，并于450℃煅烧1.5小时后得到高纯低氯高活性氧化铜，测得其纯度为99.5％、氯离子含量为18ppm、溶解时间为13.2秒。2. Slowly add potassium hydroxide solution with a mass concentration of 35% into the mixed solution, and the molar ratio of potassium hydroxide to copper is 2.8:1. After reacting at 80°C for 1 hour, filter, wash with water until the pH is 7.3, dry at 120°C for 1 hour, and calcined at 450°C for 1.5 hours to obtain high-purity, low-chlorine and high-activity copper oxide. The measured purity is 99.5%, chlorine The ion content was 18 ppm, and the dissolution time was 13.2 seconds.
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