CN104058445A - Preparation method of high-purity electroplating-grading copper oxide - Google Patents
Preparation method of high-purity electroplating-grading copper oxide Download PDFInfo
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- CN104058445A CN104058445A CN201310095033.4A CN201310095033A CN104058445A CN 104058445 A CN104058445 A CN 104058445A CN 201310095033 A CN201310095033 A CN 201310095033A CN 104058445 A CN104058445 A CN 104058445A
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Abstract
The invention relates to a preparation method of high-purity electroplating-grading copper oxide, which adopts acidic etching waste liquid as a raw material, and prepares the high-purity electroplating-grading copper oxide by adding an oxidizing agent into a prepared copper oxide crude product to process organic matter, and performing purification twice to obtain the product. The prepared copper oxide has purity of up to more than 99.0 wt%, is low in contents of various metal and nonmetal impurities, and has a high dissolving rate of less than 30 s. When pore filling is carried out by an electroplating pore-filling liquid, the high-purity electroplating-grading copper oxide has a denting amount of less than 5 microns, and is widely applicable to various electroplating occasions.
Description
Technical field
The present invention relates to cupric oxide production technique, a kind of particularly method of preparing high-purity plating-grade copper oxide with acidic etching waste liquid, utilizes PCB factory wiring board acidic etching waste liquid to prepare plating-grade copper oxide.
Background technology
Cupric oxide powder is a kind of important multifunctional inorganic fine materials, is widely used in electronics, catalysis, pottery, glass, medicine and other fields.Plating-grade copper oxide is mainly used in electroplating printed circuit board industry.Developing rapidly along with electronic industry in recent years, miniaturization, high speed and the digitized progress of electronic product promoting printed circuit board (PCB) to " fine wire; high-density; multi-level; big area; aperture " development, brought larger change and challenge to circuit-board industry, and the quality of plating-grade copper oxide is had higher requirement.
Along with the manufacturing development of PCB, using insoluble anode, to carry out electroplating technique application more and more extensive, and this technique is taking cupric oxide as copper source supplementation with copper ion, meanwhile, cupric oxide can also in electroplating process in the H that produces
+, keep the stable of electroplate liquid pH value.This processing requirement cupric oxide has high purity and high reactivity (dissolution rate is less than 30s).
In PCB factory wiring board acidic etching waste liquid, contain a large amount of cupric ions, not only avoided the wasting of resources if recycle, also alleviate the pollution to environment.Therefore explore the novel method of utilizing acidic etching waste liquid to prepare plating-grade copper oxide, and by reclaiming the insoluble anode electroplating technology of gained cupric oxide direct reuse to wiring board, in processing industrial effluent, can realize very high economic benefit.But in etching solution except Cu
2+outside, also contain a small amount of Cl
-, Cu
+, Zn
2+, Fe
3+, Ni
+deng and organism, if these impurity are present in cupric oxide the quality that can affect cupric oxide, therefore must be by purity and the activity of rational production technique guarantee cupric oxide.
About the production technique of preparing cupric oxide taking acidic etching waste liquid as raw material, in current discloseder patents of invention, also have and relate to, mainly contain following several conventional technique:
1) Chinese Patent Application No. 201010269573.6 discloses a kind of method that adopts acidic etching waste liquid to prepare high-purity copper oxide, the method adds acidic copper chloride waste etching solution in the sodium hydroxide solution of 40～60 DEG C of 30wt%～35wt%, temperature, generate cupric oxide, and cupric oxide washing, dry, sintering are finally made purity and be greater than the brilliant cupric oxide of 99.0% needle-like.
2) Chinese Patent Application No. 201010207485.3 discloses a kind of production technique of high-activity plating-grade copper oxide, taking wiring board acidic copper chloride or cupric nitrate or copper sulfate etching waste liquor and liquid sodium hydroxide or potassium hydroxide as main raw material, synthetic crude product cupric oxide is through microwave drying, pulverizing, washing, ultrasonic washing, microwave dry and disintegrating process again, make content and can reach more than 99% cupric oxide, and foreign matter content is low, dissolution rate is fast.
3) China's number of applying for a patent 200810035361.1 discloses a kind of method of preparing high-purity copper oxide by acid contained waste liquid, acid contained waste liquid is mixed and reacted with precipitation agent (as sodium hydroxide, potassium hydroxide, supercarbonate, carbonate, ammoniacal liquor etc.), until cupric ion precipitates completely; Precipitation slurry, after filtering, is used washing composition and water washing successively, then dries, calcines, pulverizes and make high pure and ultra-fine cupric oxide powder.
4) United States Patent (USP) 2001/0051103Al has mentioned taking acidic etching waste liquid as raw material and 60 DEG C of sodium hydroxide solutions reaction 2 hours, then through washing, dry, pulverize and finally obtain purity up to 99.0% cupric oxide powder.
Above patent mainly obtains cupric oxide precipitation by adding alkali and acidic etching waste liquid generation neutralization reaction, and removes foreign ion in cupric oxide as Zn by washing
2+, Fe
3+, Ni
+, K
+, Na
+, Cl
-deng, but seldom report, the organic matter removal in acidic etching waste liquid is inquired into, and organic impurities and Cu
+ion pair acid electroplating filling perforation disadvantageous effect highly significant.
In prior art, mainly obtain cupric oxide precipitation by adding alkali and acidic etching waste liquid generation neutralization reaction, and remove foreign ion in cupric oxide as Zn by washing
2+, Fe
3+, Ni
+, K
+, Na
+, Cl
-deng, but organism is not effectively removed.In fact, in acid copper-plating, the too high meeting of organic content directly affects plating porefilling capability, causes the recessed very large of filling perforation, and organic existence can cause electroplating filling perforation additive (particularly photo etching) and consume too fastly, and therefore organism must effectively be controlled.The present invention is making on the basis of cupric oxide crude product taking acidic etching waste liquid as raw material, is oxidized and combined filtering processing by oxygenant, removes up hill and dale organism, makes the cupric oxide of final preparation electroplate filling perforation excellent property.
The present invention and the existing Technology tool of comparing has the following advantages:
The present invention by adding oxygenant oxide treatment organism, carries out secondarily purified method and obtains high-purity plating-grade copper oxide powder on the basis that makes cupric oxide crude product.Prepared high-purity plating-grade copper oxide, its purity 99.0wt% is above, various metals and nonmetallic impurity content is extremely low, dissolution rate is fast, be less than 30s, use plating filling perforation liquid medicine to carry out filling perforation to this high-purity plating-grade copper oxide, recessedly all be less than 5 microns, can be widely used in various plating occasions.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of preparation method of high-purity plating-grade copper oxide, the purity 99.0wt% of the plating-grade copper oxide of acquisition is above, various metals and nonmetallic impurity content is extremely low, dissolution rate is fast, is less than 30s.Use and electroplate filling perforation liquid medicine it is carried out to filling perforation, be recessedly all less than 5 microns, can be widely used in various plating occasions.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for high-purity plating-grade copper oxide, taking acidic etching waste liquid as raw material, is making on the basis of cupric oxide crude product, by adding oxidizer treatment organism, carries out secondarily purified method and obtains high-purity plating-grade copper oxide powder.The high-purity plating-grade copper oxide obtaining, its purity is more than 99.0wt%, and its dissolution rate, below 30s, electroplates that filling perforation is recessed is less than 5 microns.
The preparation method of high-purity plating-grade copper oxide of the present invention, specifically comprises the steps:
1) neutralization: acidic etching waste liquid is filtered, remove insoluble solid impurities, mix with the aqueous sodium hydroxide solution of 30wt%～50wt%, react under whipped state 0.5～2 hour, obtain mud shape cupric oxide; Acid copper chloride etching liquid reacts release of heat and forms copper hydroxide with sodium hydroxide, copper hydroxide dewaters immediately and forms mud shape cupric oxide;
2) filter: the mud shape cupric oxide that step 1) is obtained filters, and makes its solid-liquid separation obtain cupric oxide filter cake;
3) washing: by step 2) the cupric oxide filter cake that obtains disperses, and adds washing composition and deionized water (DI water) washing to remove metallic impurity ions, obtains the cupric oxide after washing; Wherein, described washing
Agent is for containing the electrolytical aqueous solution of 0.001wt%～20wt%;
4) dry, pulverizing: the cupric oxide after the washing that step 3) is obtained is dried 1～10 hour at 40～250 DEG C; Then pulverize;
5) oxidation: the cupric oxide that step 4) is obtained and the aqueous sulfuric acid of 30wt%～50wt% are mixed to get copper-bath, then add oxygenant to be oxidized organism wherein, reacts under whipped state 0.5～2 hour, obtains the copper-bath after oxidation; The oxygenant adding decomposes oxidation operation, and simultaneously by the Cu that may contain in solution
+become Cu
2+if contain Cu in solution
+, in oxidation of organic compounds, its oxidation transformation is become to Cu
2+, filter;
6) neutralization: the filtering solution that step 5) is obtained mixes with the aqueous sodium hydroxide solution of 30wt%～50wt%, reacts 0.5～2 hour under whipped state, again obtains mud shape cupric oxide;
7) filter, wash: the mud shape cupric oxide of step 6) gained is filtered, then use deionized water wash;
8) be dried, pulverize, sieve: the washing that step 7) is obtained is dried 1～10 hour to neutral cupric oxide at 40～250 DEG C, then pulverizes, sieves, and obtains described high-purity plating-grade copper oxide.
So far the technique of, preparing high-purity plating-grade copper oxide with acidic etching waste liquid completes.
Preferably, step 2 in the present invention), 5), 7) described in filtration adopt the mode of press filtration, suction filtration or centrifugation.
Preferably, described in step 3), ionogen is one or more in carbonate, supercarbonate, vitriol, nitrate, ammonium salt and ammoniacal liquor.
Preferably, washing composition described in step 3) is for containing the electrolytical solution of 0.05wt%～5wt%.
Preferably, the oxygenant described in step 5) is hydrogen peroxide, peroxide salt, persulphate or their mixture and/or mixture.
The order number of the plating-grade copper oxide preferably, obtaining in step 8) is 100～500 orders; Being preferably order number is 100～300 orders.
The weight percentage of the above-mentioned each solution of the present invention is the weight percentage of solute wherein, and the solvent of solution is water, if the sodium hydroxide solution of 30wt%～50wt% is that the weight percentage of sodium hydroxide solute in this aqueous solution is 30wt%～50wt%; The electrolytical solution of 0.001wt%～20wt% is that the weight percentage of ionogen in this aqueous solution is 0.001wt%～20wt%; The sulphuric acid soln of 30wt%～50wt% is that the weight percentage of sulfuric acid solute in this aqueous solution is 30wt%～50wt%.
The present invention adopts the washing composition that contains the electrolytical aqueous solution of 0.001wt%～20wt% to wash the cupric oxide filter cake of acquisition, to remove metallic impurity ion, the purity and the activity that improve the finished product cupric oxide is also played a significant role.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
The acidic etching waste liquid using in following embodiment basic composition is Cu
2+: 120～140g/L, HCl:80～150g/L.In impure be the related impurities of acidic etching waste liquid.
Embodiment 1
The present embodiment provides a kind of preparation method of high-purity plating-grade copper oxide, and it comprises the steps:
1) acidic etching waste liquid is filtered with strainer, remove the insoluble particle in acidic etching waste liquid, then get 2L etching solution and mix with 30wt% aqueous sodium hydroxide solution, stirring reaction 1h;
2) mud shape cupric oxide step 1) reaction being generated is transferred in sand core funnel and carries out suction filtration, separates and obtains cupric oxide filter cake;
3) by step 2) the cupric oxide filter cake that obtains disperses, and first washes with water, then washs with the metabisulfite solution of 0.05wt%, finally wash with water again;
4) by step 2) washed filter cake first at 50 DEG C dry 10 hours, pulverize;
5) cupric oxide step 4) being obtained mixes with 50wt% sulphuric acid soln, is made into the copper-bath of 200g/L, then adds the superoxol stirring reaction 1 hour of 5ml/L, filters;
6) copper sulfate after step 5) filtration is mixed with 30wt% aqueous sodium hydroxide solution, stir 1h;
7) mud shape cupric oxide step 6) being obtained moves in sand core funnel and carries out suction filtration, then washes with water until neutral;
8) cupric oxide filter cake step 7) being obtained is dried 10 hours at 100 DEG C, is then crushed to 200 orders and can obtains high-purity plating-grade copper oxide.
After testing, the prepared plating-grade copper oxide of the present embodiment, its purity is 99.05wt%, dissolution rate is 21s.
The test that photo etching consumes: this plating-grade copper oxide adds sulfuric acid and is made into after copper-bath, to the consumption of photo etching little (adding photo etching concentration is 0.7ml/L, and after 24 hours, the photo etching concentration of test is 0.692ml/L), testing method is cyclic voltammetry; In the copper-bath being wherein made into: CuSO
45H
2o200g/L, H
2sO
445ml/L, chlorion 55ppm, photo etching concentration 0.7ml/L, inhibitor concentration 30ml/L, leveling agent concentration 13ml/L.And the plating-grade copper oxide that existing market is buied, it adds photo etching concentration is 0.7ml/L, and after 24 hours, the photo etching concentration of test is no more than 0.4ml/L, and the consumption of photo etching is very large, need to constantly dose photo etching just to be carried out, and cost is very high.
Electroplate the test of porefilling capability: this plating-grade copper oxide, it is electroplated filling perforation and (adopts EVF to electroplate filling perforation additive and carry out filling perforation, photo etching concentration 0.7ml/L, inhibitor concentration 30ml/L, leveling agent concentration 13ml/L) ability is strong, filling perforation effect: be recessedly less than 5 microns.
Embodiment 2
The present embodiment provides a kind of preparation method of high-purity plating-grade copper oxide, and it comprises the steps:
1) acidic etching waste liquid is removed to the insoluble particle in acidic etching waste liquid with strainer, then get 5L etching solution and mix with 40wt% aqueous sodium hydroxide solution, stir 2h;
2) mud shape cupric oxide step (1) reaction being generated is transferred in sand core funnel and carries out suction filtration, separates and obtains cupric oxide filter cake;
3) by step 2) the cupric oxide filter cake that obtains disperses, and first washes with water, then washs with the sodium hydrogen carbonate solution of 5wt%, finally wash with water again;
4) filter cake washed step 3) is first dried to 3 hours at 100 DEG C, pulverizes;
5) cupric oxide step 4) being obtained mixes with 50wt% sulphuric acid soln, is made into the copper-bath of 180g/L, then adds the superoxol stirring reaction 1 hour of 10ml/L, filters;
6) by the copper sulfate after step 5) filtration and 40wt% aqueous sodium hydroxide solution, stir 2h;
7) mud shape cupric oxide step 6) being obtained moves in sand core funnel and carries out suction filtration, then washes with water until neutral;
8) cupric oxide filter cake step 7) being obtained is dried 5 hours at 200 DEG C, is then crushed to 300 orders and can obtains high-purity plating-grade copper oxide.
After testing, the prepared plating-grade copper oxide of the present embodiment, its purity is up to 99.1wt%, and dissolution rate is 16s.
The test that photo etching consumes: this plating-grade copper oxide adds sulfuric acid and is made into after copper-bath, to the consumption of photo etching little (adding photo etching concentration is 0.7ml/L, and after 24 hours, the photo etching concentration of test is 0.694ml/L), testing method is cyclic voltammetry; In the copper-bath being wherein made into: CuSO
45H
2o200g/L, H
2sO
445ml/L, chlorion 55ppm, photo etching concentration 0.7ml/L, inhibitor concentration 30ml/L, leveling agent concentration 13ml/L.And the plating-grade copper oxide that existing market is buied, it adds photo etching concentration is 0.7ml/L, and after 24 hours, the photo etching concentration of test is no more than 0.4ml/L, and the consumption of photo etching is very large, need to constantly dose photo etching just to be carried out, and cost is very high.
Electroplate the test of porefilling capability: this plating-grade copper oxide, it is electroplated filling perforation and (adopts EVF to electroplate filling perforation additive and carry out filling perforation, photo etching concentration 0.7ml/L, inhibitor concentration 30ml/L, leveling agent concentration 13ml/L) ability is strong, filling perforation effect: be recessedly less than 3 microns.
Embodiment 3
The present embodiment provides a kind of preparation method of high-purity plating-grade copper oxide, and it comprises the steps:
1) acidic etching waste liquid is removed to the insoluble particle in acidic etching waste liquid with strainer, then get 3L etching solution and mix with 48wt% aqueous sodium hydroxide solution, stir 2h;
2) mud shape cupric oxide step 1) reaction being generated is transferred in sand core funnel and carries out suction filtration, separates and obtains cupric oxide filter cake;
3) by step 2) obtain cupric oxide filter cake disperse, first wash with water, then use the copper carbonate solution washing of 1wt%, finally wash with water again;
4) filter cake washed step 3) is first dried to 1 hour at 150 DEG C, then pulverizes;
5) cupric oxide step 4) being obtained mixes with 50wt% sulphuric acid soln, is made into the copper-bath of 190g/L, then adds the ammonium persulphate stirring reaction 1 hour of 1g/L, filters;
6) copper sulfate after step 5) filtration is mixed with 48wt% aqueous sodium hydroxide solution, stir 2h;
7) mud shape cupric oxide step 6) being obtained moves in sand core funnel and carries out suction filtration, then washes with water until neutral;
8) cupric oxide filter cake step 7) being obtained is dried 2 hours at 250 DEG C, is then crushed to 120 orders and can obtains high-purity plating-grade copper oxide.
After testing, the prepared plating-grade copper oxide of the present embodiment, its purity is up to 99.11wt%, and dissolution rate is 15s.
The test that photo etching consumes: this plating-grade copper oxide adds sulfuric acid and is made into after copper-bath, to the consumption of photo etching little (adding photo etching concentration is 0.7ml/L, and after 24 hours, the photo etching concentration of test is 0.698ml/L), testing method is cyclic voltammetry; In the copper-bath being wherein made into: CuSO
45H
2o200g/L, H
2sO
445ml/L, chlorion 55ppm, photo etching concentration 0.7ml/L, inhibitor concentration 30ml/L, leveling agent concentration 13ml/L.And the plating-grade copper oxide that existing market is buied, it adds photo etching concentration is 0.7ml/L, and after 24 hours, the photo etching concentration of test is no more than 0.4ml/L, and the consumption of photo etching is very large, need to constantly dose photo etching just to be carried out, and cost is very high.
Electroplate the test of porefilling capability: this plating-grade copper oxide, it is electroplated filling perforation and (adopts EVF to electroplate filling perforation additive and carry out filling perforation, photo etching concentration 0.7ml/L, inhibitor concentration 30ml/L, leveling agent concentration 13ml/L) ability is strong, filling perforation effect: be recessedly less than 5 microns.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (7)
1. a preparation method for high-purity plating-grade copper oxide, taking acidic etching waste liquid as raw material, is making on the basis of cupric oxide crude product, by adding oxidizer treatment organism, carries out secondarily purified method and obtains high-purity plating-grade copper oxide powder; The high-purity plating-grade copper oxide obtaining, its purity is more than 99.0wt%, and its dissolution rate is below 30s.
2. the preparation method of high-purity plating-grade copper oxide as claimed in claim 1, comprises the steps:
1) neutralization: acidic etching waste liquid is filtered, remove insoluble solid impurities, mix with the aqueous sodium hydroxide solution of 30wt%～50wt%, react under whipped state 0.5～2 hour, obtain mud shape cupric oxide;
2) filter: the mud shape cupric oxide that step 1) is obtained filters, and makes its solid-liquid separation obtain cupric oxide filter cake;
3) washing: by step 2) the cupric oxide filter cake that obtains disperses, and adds washing composition and deionized water wash to remove metallic impurity ion, obtains the cupric oxide after washing; Wherein, described washing composition is for containing the electrolytical aqueous solution of 0.001wt%～20wt%;
4) dry, pulverizing: the cupric oxide after the washing that step 3) is obtained is dried 1～10 hour at 40～250 DEG C, then pulverizes;
5) oxidation: the cupric oxide that step 4) is obtained mixes with the aqueous sulfuric acid of 30wt%～50wt%, obtain copper-bath, then add oxygenant to be oxidized organism wherein, under whipped state, react 0.5～2 hour, oxidation operation is decomposed or degraded, and simultaneously by the Cu that may contain in solution
+become Cu
2+, filter;
6) neutralization: the filtering solution that step 5) is obtained mixes with the aqueous sodium hydroxide solution of 30wt%～50wt%, reacts 0.5～2 hour under whipped state, again obtains mud shape cupric oxide;
7) filter, wash: the mud shape cupric oxide of step 6) gained is first filtered, then use deionized water wash;
8) be dried, pulverize, sieve: the washing that step 7) is obtained is dried 1～10 hour to neutral cupric oxide at 40～250 DEG C, then pulverizes, sieves, and obtains described high-purity plating-grade copper oxide.
3. the preparation method of high-purity plating-grade copper oxide as claimed in claim 2, is characterized in that, oxygenant described in step 5) is hydrogen peroxide, peroxide salt, persulphate or their mixture and/or mixture.
4. the preparation method of high-purity plating-grade copper oxide as claimed in claim 2, is characterized in that, washing composition described in step 3) is for containing the electrolytical solution of 0.05wt%～5wt%.
5. the preparation method of the high-purity plating-grade copper oxide as described in claim 2 or 4, is characterized in that, ionogen described in step 3) is one or more in carbonate, supercarbonate, vitriol, nitrate, ammonium salt and ammoniacal liquor.
6. the preparation method of high-purity plating-grade copper oxide as claimed in claim 2, is characterized in that, described step 2), 5), 7) filter the mode of press filtration, suction filtration or centrifugation of employing.
7. the preparation method of high-purity plating-grade copper oxide as claimed in claim 2, is characterized in that, the order number of the plating-grade copper oxide obtaining in step 8) is 100～500 orders.
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Cited By (1)
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