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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- CN104692446B CN104692446B CN201510119702.6A CN201510119702A CN104692446B CN 104692446 B CN104692446 B CN 104692446B CN 201510119702 A CN201510119702 A CN 201510119702A CN 104692446 B CN104692446 B CN 104692446B
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Abstract
The invention discloses the preparation method of a kind of high-purity low chlorine oxide of high activity copper, comprise the following steps: copper-containing raw material, chelating agent, auxiliary agent and deionized water are added mix homogeneously in reactor and obtains mixed liquor, it is slowly added to precipitant solution in described mixed liquor, filter after reacting 2 3h at 40 80 DEG C, wash with water to pH be 7.0～7.5, in 100～120 DEG C be dried 1～3 hour, then at 300～600 DEG C calcining 0.5～2 hour after obtain high-purity low chlorine oxide of high activity copper.Product quality and performance that the present invention produces are the most excellent, and product purity >=99.0%, the chloride ion content that prepare are less than 15 seconds less than 20ppm, dissolution time.
Description
One, technical field
The present invention relates to the production method of a kind of high-purity low chlorine oxide of high activity copper, belong to electronic application Material Field.
Two, background technology
Along with developing rapidly of electronics industry, printed circuit board (PCB) manufactures to multiple stratification, functionalization and the direction such as integrated
Develop rapidly.Printed circuit design uses micro hole, thin space, thin wire etc. in a large number so that PCB manufacturing technology difficulty is more come
The highest, conventional vertical copper plating process can not meet the technology requirement of high-quality, high reliability, interconnected pores etc., then produces
Horizontal copper plating technology.Horizontal electro-coppering production technology requires supplementation with copper ion to maintain the copper ion concentration in plating solution, and
The active copper oxide to be relied on (or claiming plating-grade copper oxide) that supplements of this copper ion completes.Because active copper oxide has relatively
High chemism, it is ensured that its energy rapid solution is in electroplate liquid, thus meets the use requirement of horizontal copper facing novel technique.
In recent years, active copper oxide preparation method research of great interest, its development trend be research and develop chlorine high-purity, low and
Highly active copper oxide technology of preparing, the active copper oxide product purity i.e. developed should be not less than 99%, chlorinity should be not more than
30ppm, dissolution time should be not more than 30 seconds.The method preparing high-purity low chlorine oxide of high activity copper of the openest report is main
Have two kinds, a kind of be with company limited of Taixing smeltery as representative with cathode copper, liquefied ammonia, high-purity carbon dioxide etc. as raw material,
Using and first prepare strong aqua ammonia, be then passed through high-purity carbon dioxide in strong aqua ammonia and prepare carbonated aqueous ammonia, this carbonated aqueous ammonia is at certain bar
React with copper under part and obtain copper ammonia complexation solution, then by heating, ammonia still process, separate, wash, be dried, the operation such as calcining prepared
The method of high-purity low chlorine active copper oxide.The Chinese invention that the applicants such as company limited of Taixing smeltery have been disclosed more than one piece similar is special
Profit, their application number respectively: 201210559034.5,201210559066.5,201210559070.1,201210559104.7,
201210559223.2,201210559225.1 etc..These documents give active copper oxide product purity be 99.5%, dissolve
Time is the data such as 26 seconds, but does not provides the numerical value of product chlorinity.Another kind is with Byen Kunshan Rense Avfall Qiandeng Co., Ltd.
For represent with copper-containing etching waste solution, liquid sodium hydroxide etc. as primary raw material, use first copper-containing etching waste solution is purified,
Remove impurity, is subsequently adding sodium hydroxide solution, blended reaction, is filtrated to get crude product copper oxide；Again by crude product copper oxide drying,
Pulverizing, washing, ultrasonic washing, microwave after drying and disintegrating process, the method preparing oxide of high activity copper.The most
Disclosed Chinese invention patent has: 201010207485.3,201210235602.6 etc..These documents give active oxidation
The data that copper products purity is more than 99%, dissolution time was more than 17 seconds, but do not provide the numerical value of chlorinity in product yet.
Be not difficult to find out from above-mentioned document, at present the preparation method of the high-purity low chlorine oxide of high activity copper of report remains many not
Foot；And up to the present, and have no the open report being provided simultaneously with chlorine high-purity, low and highly active copper oxide technology of preparing.As
Above-mentioned first method mainly uses cathode copper as raw material, causes production cost higher；Although it addition, document title say be
Low chlorine products, but document is not given the numerical value of product chlorinity.Second method mainly employs copper-containing etching waste solution conduct
Raw material, makes production cost obtain certain reduction, but in order to remove ferrum present in raw material, nickel, lead, zinc and chloride ion etc.,
The production technology used is complex, makes wash water consumption have bigger increase etc., and does not also provide the chlorinity etc. of product in document
Numerical value.
Three, summary of the invention
The present invention be directed to the weak point that existing technology of preparing exists, it is desirable to provide the system of a kind of high-purity low chlorine oxide of high activity copper
Preparation Method, makes product purity >=99.0% prepared, chloride ion content less than 20ppm, dissolution time less than 15 seconds.
The technical scheme that the present invention solves technical problem employing is as follows:
The preparation method of the high-purity low chlorine oxide of high activity copper of the present invention, according to the following steps operation:
Copper-containing raw material, chelating agent, auxiliary agent and deionized water are added mix homogeneously in reactor and obtains mixed liquor, mixed liquor contains
The mass concentration (in terms of copper)≤18% of copper raw material, chelating agent is (0.8～1.1) with the mol ratio of copper: 1, auxiliary agent and the matter of copper
Amount ratio is (0.005～0.01): 1；Being slowly added to precipitant solution in described mixed liquor, precipitant with the mol ratio of copper is
(2.4～3): 1, filter after reacting 2-3h at 40-80 DEG C, and washing with water to pH is 7.0～7.5, is dried 1～3 in 100～120 DEG C
Hour, and in 300～600 DEG C calcining 0.5～2 hour after obtain high-purity low chlorine oxide of high activity copper.
Described copper-containing raw material is copper sulfate, copper nitrate or copper acetate.
Described chelating agent is acetic acid, sodium acetate, potassium acetate, ammonium acetate, lactic acid, sodium lactate, potassium lactate, DL-Lactic acid ammonium salt., Fructus Citri Limoniae
Acid, sodium citrate, potassium citrate, ammonium citrate or potassium 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, the present invention has the beneficial effect that:
1, production technology used by the present invention is the simplest, and equipment is more easy to select, and operates the easiest, and production cost is the cheapest.
2, the present invention produces product quality and performance are the most excellent, and product purity >=99.0%, the chloride ion content that prepare are little
In 20ppm, dissolution time less than 15 seconds.
Four, detailed description of the invention
Embodiment 1:
1, copper sulfate, sodium lactate, PEG20000 and deionized water are added in reactor, be uniformly mixed and obtain mixed liquor.
In mixed liquor, the mass concentration of copper is 10%, sodium lactate and the mass ratio that mol ratio is 1.1:1, PEG20000 and copper of copper sulfate
For 0.006:1.
2, being slowly added to the sodium hydroxide solution that mass concentration is 10% in described mixed liquor, sodium hydroxide with the mol ratio of copper is
2.5:1, filters after reacting 3h at 45 DEG C, and washing with water to pH is 7.1, is dried 2.5 hours in 105 DEG C, and forges in 350 DEG C
Obtain high-purity low chlorine oxide of high activity copper after burning 2 hours, record its purity be 99.1%, chloride ion content be 15ppm, dissolving
Time is 12.0 seconds.
The method of testing of dissolution time is: the sulfuric acid solution that 16mL mass concentration is 98% is diluted with water to 1000mL, then
Add 10g copper oxide, under normal temperature condition, the time that record cupric oxide powder is completely dissolved.The method of testing of following example is identical.
Embodiment 2:
1, copper acetate, acetic acid, OP-10 and deionized water are added in reactor, be uniformly mixed and obtain mixed liquor.Mixing
In liquid, the mass concentration of copper is 5%, and acetic acid is 0.008:1 with the mass ratio that mol ratio is 0.9:1, OP-10 and copper of copper acetate.
2, being slowly added to the sodium hydroxide solution that mass concentration is 20% in described mixed liquor, sodium hydroxide with the mol ratio of copper is
3.0:1.Filtering after reacting 2.5h at 60 DEG C, washing with water to pH is 7.2, is dried 2 hours in 110 DEG C, and forges in 550 DEG C
Obtain high-purity low chlorine oxide of high activity copper after burning 1 hour, record its purity be 99.7%, chloride ion content be 16ppm, dissolving
Time is 14.6 seconds.
Embodiment 3:
1, copper nitrate, potassium citrate, PVP and deionized water are added in reactor, be uniformly mixed and obtain mixed liquor.Mixed
Closing the mass concentration of copper in liquid is 15%, and the mol ratio of potassium citrate and copper sulfate is 1.0:1, PVP and the mass ratio of copper is
0.01:1。
2, being slowly added to the potassium hydroxide solution that mass concentration is 35% in described mixed liquor, potassium hydroxide with the mol ratio of copper is
2.8:1.Filtering after reacting 1h at 80 DEG C, washing with water to pH is 7.3, is dried 1 hour in 120 DEG C, and in 450 DEG C of calcinings
Obtain high-purity low chlorine oxide of high activity copper after 1.5 hours, record its purity be 99.5%, chloride ion content be 18ppm, dissolve time
Between be 13.2 seconds.
Claims (4)
1. the preparation method of high-purity low chlorine oxide of high activity copper, it is characterised in that comprise the following steps:
Copper-containing raw material, chelating agent, auxiliary agent and deionized water are added mix homogeneously in reactor and obtains mixed liquor, it is slowly added to precipitant solution in described mixed liquor, filter after reacting 2-3h at 40-80 DEG C, wash with water to pH be 7.0 ~ 7.5, in 100 ~ 120 DEG C be dried 1 ~ 3 hour, then at 350 ~ 550 DEG C calcining 1 ~ 2 hour after obtain high-purity low chlorine oxide of high activity copper；
Described copper-containing raw material is copper sulfate, copper nitrate or copper acetate；
Described chelating agent is acetic acid, sodium acetate, potassium acetate, ammonium acetate, lactic acid, sodium lactate, potassium lactate, DL-Lactic acid ammonium salt., citric acid, sodium citrate, potassium citrate, ammonium citrate or potassium citrate sodium；Described chelating agent is (0.8 ~ 1.1) with the mol ratio of copper in copper-containing raw material: 1；
Described auxiliary agent is PVP, OP-10 or PEG20000；Described auxiliary agent is (0.005 ~ 0.01) with the mass ratio of copper in copper-containing raw material: 1.
Preparation method the most according to claim 1, it is characterised in that:
Mass concentration≤18% of copper-containing raw material in described mixed liquor.
Preparation method the most according to claim 1, it is characterised in that:
Described precipitant solution is sodium hydroxide solution or potassium hydroxide solution；The mass concentration of described precipitant solution is 1 ~ 45%.
4. according to the preparation method described in claim 1 or 3, it is characterised in that:
Described precipitant is (2.4 ~ 3) with the mol ratio of copper in copper-containing raw material: 1.
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| CN105347382B (en) * | 2015-12-10 | 2017-06-23 | 济南大学 | A kind of preparation method of garland shape copper oxide nano 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 |
| 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 |
| 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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| CN102491403B (en) * | 2011-12-19 | 2014-01-29 | 聊城大学 | Method for preparing copper oxide powder by using complexed-precipitation method |
| CN103030169B (en) * | 2012-12-26 | 2015-07-15 | 中北大学 | Shape-controlled preparation method of nanometer copper oxide |
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