CN104692446A - Preparation method of high-purity low-chlorine high-activity copper oxide - Google Patents
Preparation method of high-purity low-chlorine high-activity copper oxide Download PDFInfo
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- CN104692446A CN104692446A CN201510119702.6A CN201510119702A CN104692446A CN 104692446 A CN104692446 A CN 104692446A CN 201510119702 A CN201510119702 A CN 201510119702A CN 104692446 A CN104692446 A CN 104692446A
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Abstract
The invention discloses a preparation method of high-purity low-chlorine high-activity copper oxide. The method comprises the following steps: adding a copper-containing raw material, a complexing agent, an assistant and de-ionized water into a reaction kettle and uniformly mixing to obtain mixed solution; slowly adding precipitant solution into the mixed solution, reacting for 2-3 hours at 40-80 DEG C and then filtering, washing with water until pH is 7.0-7.5, drying for 1-3 hours at 100-120 DEG C, and calcining for 0.5-2 hours at 300-600 DEG C to obtain the high-purity low-chlorine high-activity copper oxide. The produced product has more superior quality and performance; the purity of the prepared product is greater than or equal to 99.0 percent, the chlorine ion content is smaller than 20 ppm, and the dissolution time is smaller than 15 seconds.
Description
One, technical field
The present invention relates to a kind of production method of high-purity low chlorine oxide of high activity copper, belong to electronic application Material Field.
Two, background technology
Along with the develop rapidly of electronic industry, printed circuit board (PCB) manufactures and develops rapidly to multiple stratification, functionalization and the direction such as integrated.Printed electronic circuit design adopts micro-holes, thin space, thin wire etc. in a large number, make PCB manufacturing technology difficulty more and more higher, conventional vertical copper plating process can not meet the technical requirements of high quality, high reliability, interconnected pores etc., so create horizontal copper plating technology.Need supplementation with copper ion to maintain the copper ion concentration in plating solution in horizontal electro-coppering production technique, supplementing of this cupric ion then will rely on active copper oxide (or claiming plating-grade copper oxide).Because active copper oxide has higher chemically reactive, can ensure that its energy rapid solution is in electroplate liquid, thus meet the service requirements of horizontal copper facing novel technique.
In recent years, the research of active copper oxide preparation method receives to be paid close attention to widely, its development trend is research and development high-purity, low chlorine and highly active cupric oxide technology of preparing, and the active copper oxide product purity namely developed should be not less than 99%, cl content should be not more than 30ppm, dissolution time should be not more than 30 seconds.The method of the high-purity low chlorine oxide of high activity copper of preparation of open report mainly contains two kinds at present, a kind of is be representative with electrolytic copper, liquefied ammonia, high-purity carbon dioxide etc. for raw material with company limited of Taixing smeltery, adopt and first prepare strong aqua, then in strong aqua, pass into high-purity carbon dioxide and obtain carbonated aqueous ammonia, this carbonated aqueous ammonia is obtained by reacting copper ammonia complexation solution with copper under certain condition, then obtains the method for high-purity low chlorine active copper oxide by operations such as heating, ammonia still process, separation, washing, drying, calcinings.The applicants such as company limited of Taixing smeltery have disclosed the similar Chinese invention patent of more than one piece, their application number respectively: 201210559034.5,201210559066.5,201210559070.1,201210559104.7,201210559223.2,201210559225.1 etc.Give in these documents that active copper oxide product purity is 99.5%, dissolution time is the data such as 26 seconds, but do not provide the numerical value of product cl content.Another kind be with Byen Kunshan Rense Avfall Qiandeng Co., Ltd. be representative with copper-containing etching waste solution, liquid sodium hydroxide etc. for main raw material, employing first purifies copper-containing etching waste solution, removal of impurities, then add sodium hydroxide solution, obtain crude product cupric oxide through hybrid reaction, filtration; Again by crude product cupric oxide drying, pulverizing, washing, ultrasonic washing, microwave dry and disintegrating process again, the method for obtained oxide of high activity copper.Published Chinese invention patent has in this respect: 201010207485.3,201210235602.6 etc.Give in these documents active copper oxide product purity more than 99%, the dissolution time data that are greater than 17 seconds, but do not provide the numerical value of cl content in product yet.
Be not difficult to find out from above-mentioned document, remain in many deficiencies in the preparation method of the high-purity low chlorine oxide of high activity copper reported at present; And up to the present, and have no the open report simultaneously possessing high-purity, low chlorine and highly active cupric oxide technology of preparing.First method described above mainly uses electrolytic copper as raw material, causes production cost higher; In addition, although document title says is low chlorine products, the numerical value of product cl content in document, is not provided.Second method mainly employs copper-containing etching waste solution as raw material, production cost is made to obtain certain reduction, but in order to remove iron, nickel, lead, zinc and the chlorion etc. that exist in raw material, the production technique adopted is comparatively complicated, make wash water consumption have larger increase etc., and in document, also do not provide the numerical value such as the cl content of product.
Three, summary of the invention
The present invention be directed to the weak point that existing technology of preparing exists, aim to provide a kind of preparation method of high-purity low chlorine oxide of high activity copper, product purity >=99.0% making to obtain, chloride ion content are less than 20ppm, dissolution time is less than 15 seconds.
The technical scheme that technical solution problem of the present invention adopts is as follows:
The preparation method of the high-purity low chlorine oxide of high activity copper of the present invention, operates according to the following steps:
Copper-containing raw material, complexing agent, auxiliary agent and deionized water are added in reactor to mix and obtains mixed solution, the mass concentration (in copper)≤18% of copper-containing raw material in mixed solution, the mol ratio of complexing agent and copper is (0.8 ~ 1.1): 1, and the mass ratio of auxiliary agent and copper is (0.005 ~ 0.01): 1; Slowly precipitant solution is added in described mixed solution, the mol ratio of precipitation agent and copper is (2.4 ~ 3): 1, filter react 2-3h at 40-80 DEG C after, wash with water to pH be 7.0 ~ 7.5, in 100 ~ 120 DEG C of dryings 1 ~ 3 hour, and obtain high-purity low chlorine oxide of high activity copper in 300 ~ 600 DEG C of calcinings after 0.5 ~ 2 hour.
Described copper-containing raw material is copper sulfate, cupric nitrate or venus crystals.
Described complexing agent is acetic acid, sodium acetate, potassium acetate, ammonium acetate, lactic acid, Sodium.alpha.-hydroxypropionate, potassium lactate, DL-Lactic acid ammonium salt, citric acid, Trisodium Citrate, Tripotassium Citrate, ammonium citrate or Tripotassium Citrate sodium.
Described auxiliary agent is polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), OP-10, PEG800 or PEG20000.
Described precipitant solution is sodium hydroxide solution or potassium hydroxide solution; The mass concentration of described precipitant solution is 1 ~ 45%.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention's production technique used is more simple, and equipment is more easily selected, and operate more easy, production cost is more cheap.
2, the quality product produced of the present invention and performance more excellent, obtained product purity >=99.0%, chloride ion content are less than 20ppm, dissolution time is less than 15 seconds.
Four, embodiment
Embodiment 1:
1, copper sulfate, Sodium.alpha.-hydroxypropionate, PEG20000 and deionized water are added in reactor, be uniformly mixed and obtain mixed solution.In mixed solution, the mass concentration of copper is 10%, and the mol ratio of Sodium.alpha.-hydroxypropionate and copper sulfate is the mass ratio of 1.1:1, PEG20000 and copper is 0.006:1.
2, in described mixed solution, the sodium hydroxide solution that mass concentration is 10% is slowly added, the mol ratio of sodium hydroxide and copper is 2.5:1, filter react 3h at 45 DEG C after, wash with water to pH be 7.1, in 105 DEG C of dryings 2.5 hours, and obtain high-purity low chlorine oxide of high activity copper in 350 DEG C of calcinings after 2 hours, record that its purity is 99.1%, chloride ion content is 15ppm, dissolution time is 12.0 seconds.
The testing method of dissolution time is: by 16mL mass concentration be 98% sulphuric acid soln be diluted with water to 1000mL, then add 10g cupric oxide, under normal temperature condition, record the cupric oxide powder consoluet time.The testing method of following examples is identical.Embodiment 2:
1, venus crystals, acetic acid, OP-10 and deionized water are added in reactor, be uniformly mixed and obtain mixed solution.In mixed solution, the mass concentration of copper is 5%, and the mol ratio of acetic acid and venus crystals is the mass ratio of 0.9:1, OP-10 and copper is 0.008:1.
2, in described mixed solution, slowly add the sodium hydroxide solution that mass concentration is 20%, the mol ratio of sodium hydroxide and copper is 3.0:1.Filter react 2.5h at 60 DEG C after, washing with water to pH is 7.2, in 110 DEG C of dryings 2 hours, and obtains high-purity low chlorine oxide of high activity copper in 550 DEG C of calcinings after 1 hour, records that its purity is 99.7%, chloride ion content is 16ppm, dissolution time is 14.6 seconds.
Embodiment 3:
1, cupric nitrate, Tripotassium Citrate, PVP and deionized water are added in reactor, be uniformly mixed and obtain mixed solution.In mixed solution, the mass concentration of copper is 15%, and the mol ratio of Tripotassium Citrate and copper sulfate is the mass ratio of 1.0:1, PVP and copper is 0.01:1.
2, in described mixed solution, slowly add the potassium hydroxide solution that mass concentration is 35%, the mol ratio of potassium hydroxide and copper is 2.8:1.Filter react 1h at 80 DEG C after, washing with water to pH is 7.3, in 120 DEG C of dryings 1 hour, and obtains high-purity low chlorine oxide of high activity copper in 450 DEG C of calcinings after 1.5 hours, records that its purity is 99.5%, chloride ion content is 18ppm, dissolution time is 13.2 seconds.
Claims (7)
1. a preparation method for high-purity low chlorine oxide of high activity copper, is characterized in that comprising the following steps:
Copper-containing raw material, complexing agent, auxiliary agent and deionized water are added in reactor to mix and obtains mixed solution, slowly precipitant solution is added in described mixed solution, filter react 2-3h at 40-80 DEG C after, wash with water to pH be 7.0 ~ 7.5, in 100 ~ 120 DEG C of dryings 1 ~ 3 hour, then obtain high-purity low chlorine oxide of high activity copper in 300 ~ 600 DEG C of calcinings after 0.5 ~ 2 hour.
2. preparation method according to claim 1, is characterized in that:
Described copper-containing raw material is copper sulfate, cupric nitrate or venus crystals.
3. preparation method according to claim 1 and 2, is characterized in that:
Mass concentration≤18% of copper-containing raw material in described mixed solution.
4. preparation method according to claim 1, is characterized in that:
Described complexing agent is acetic acid, sodium acetate, potassium acetate, ammonium acetate, lactic acid, Sodium.alpha.-hydroxypropionate, potassium lactate, DL-Lactic acid ammonium salt, citric acid, Trisodium Citrate, Tripotassium Citrate, ammonium citrate or Tripotassium Citrate sodium; In described complexing agent and copper-containing raw material, the mol ratio of copper is (0.8 ~ 1.1): 1.
5. preparation method according to claim 1, is characterized in that:
Described auxiliary agent is PVP, CTAB, OP-10, PEG800 or PEG20000; In described auxiliary agent and copper-containing raw material, the mass ratio of copper is (0.005 ~ 0.01): 1.
6. preparation method according to claim 1, is characterized in that:
Described precipitant solution is sodium hydroxide solution or potassium hydroxide solution; The mass concentration of described precipitant solution is 1 ~ 45%.
7. preparation method according to claim 1 or 5, is characterized in that:
In described precipitation agent and copper-containing raw material, the mol ratio of copper is (2.4 ~ 3): 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347382A (en) * | 2015-12-10 | 2016-02-24 | 济南大学 | Method for preparing garland-shaped nanometer copper oxide material |
| CN105523578A (en) * | 2016-02-04 | 2016-04-27 | 新疆维吾尔自治区分析测试研究院 | Nanometer copper oxide with controllable morphology as well as preparation method and application of nanometer copper oxide |
| CN109110797A (en) * | 2018-09-20 | 2019-01-01 | 西安凯立新材料股份有限公司 | A kind of preparation method of sector multi-layer cupric oxide powder |
| CN114988492A (en) * | 2022-05-31 | 2022-09-02 | 西安合升汇力新材料有限公司 | Nickel-rich ternary cathode material and preparation method and application thereof |
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| CN102320644A (en) * | 2011-08-17 | 2012-01-18 | 金川集团有限公司 | Method for preparing copper-oxide powder |
| CN102491403A (en) * | 2011-12-19 | 2012-06-13 | 班朝磊 | Method for preparing copper oxide powder by using complexed-precipitation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347382A (en) * | 2015-12-10 | 2016-02-24 | 济南大学 | Method for preparing garland-shaped nanometer copper oxide material |
| CN105523578A (en) * | 2016-02-04 | 2016-04-27 | 新疆维吾尔自治区分析测试研究院 | Nanometer copper oxide with controllable morphology as well as preparation method and application of nanometer copper oxide |
| CN109110797A (en) * | 2018-09-20 | 2019-01-01 | 西安凯立新材料股份有限公司 | A kind of preparation method of sector multi-layer cupric oxide powder |
| CN109110797B (en) * | 2018-09-20 | 2020-09-01 | 西安凯立新材料股份有限公司 | Preparation method of sector multi-layer copper oxide powder |
| CN114988492A (en) * | 2022-05-31 | 2022-09-02 | 西安合升汇力新材料有限公司 | Nickel-rich ternary cathode material and preparation method and application thereof |
| CN114988492B (en) * | 2022-05-31 | 2024-05-10 | 西安合升汇力新材料有限公司 | Nickel-rich ternary positive electrode material and preparation method and application thereof |
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