CN102730742A - Technique for producing soluble copper oxide from acidic etching waste liquor - Google Patents
Technique for producing soluble copper oxide from acidic etching waste liquor Download PDFInfo
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- CN102730742A CN102730742A CN2012102356026A CN201210235602A CN102730742A CN 102730742 A CN102730742 A CN 102730742A CN 2012102356026 A CN2012102356026 A CN 2012102356026A CN 201210235602 A CN201210235602 A CN 201210235602A CN 102730742 A CN102730742 A CN 102730742A
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Abstract
The invention discloses a technique for producing soluble copper oxide from acidic etching waste liquor, which comprises the following steps: electrolyzing acidic etching waste liquor to generate copper; dissolving electrolyzed cathode copper in an ammonia water-CO2 system to form a copper-ammonia solution; carrying out negative pressure ammonia evaporation on the copper-ammonia solution to form basic copper carbonate; and calcining the generated basic copper carbonate to generate copper oxide. The technique disclosed by the invention has the advantages of low production cost, simple technique and low environmental pollution in the production process; and the produced copper oxide has the advantages of low impurity content and high activity and is soluble in a plating solution.
Description
Technical field
The present invention relates to electroplate the production technique of grade active copper oxide, particularly relate to and utilize the wiring board acidic etching waste liquid directly to prepare the production technique of electroplating the level active copper oxide.
Background technology
Cupric oxide powder is a kind of important multifunctional inorganic fine materials; Be mainly used in the tinting material of glass, enamel, pottery etc. and the raw material of magneticsubstance; Be used to make pyrotechnics, dyestuff, catalyzer and other mantoquitas etc.; Also be used for Zantrel industry, the anti-creasing agent that also can be used for painting and electron trade etc.Electroplate the level active copper oxide and be mainly used in the PC board electroplating industry.Along with the developing rapidly of electronic industry, the turnout of circuit card constantly increased in recent years, and especially China surpassed Japan in 2006 has become the maximum PCB production base of the global output value.Along with the sustainable growth of printed circuit board industry, the cupric oxide powder particularly market demand of high-activity plating-grade copper oxide also constantly enlarges.The miniaturized of electronic product, high speed and digitized progress are promoting printed substrate to " fine wire; high-density; multi-level, big area, apertureization " development; Brought bigger change and challenge to circuit-board industry, the purity of electroplating the level active copper oxide and particle diameter etc. have been had higher requirement.
In the PCB ME, traditional copper-plating technique adopts soluble anode technology, and one type is the pure copper anode of in alkalescence and cyanide electroplating, using, and another kind is the phosphor-copper anode that in acid copper-plating, uses.In galvanized process; Impurity in the copper anode can be electroplated out or stay in the solution of plating tank with copper; They sink to bottom land easily and form the anode sludge and can carry out enrichment; Impurity is deposited on the plating piece surface can cause coarse and stress, and pollutent increases and can cause aqueduct to be difficult to control and produce defective production part, increases production cost because of scrapping or doing over again.Therefore, traditional soluble anode copper facing has shortcomings such as technology stability is poor, efficient is low.
Along with the manufacturing development of PCB, the vertical plating favored.Develop at present,, gradually adopt the level plating more more advanced than vertical plating for adapting to the needs of high-density, high precision, multi-functional, high aspect ratio multilayer printed circuit board product specific function.No matter be vertical the plating or the plating of more advanced level, all adopt insoluble anode and with cupric oxide as copper source supplementation with copper ion, insoluble anode can provide constant annode area and stable homogeneity, avoids the generation of anode slime; Cupric oxide can be simultaneously in electroplating process in the H that produces
+, keep the stable of electroplate liquid pH value.This processing requirement cupric oxide has higher activity, promptly in electroplate liquid, can dissolve (in 30 seconds) fast, and requires to have lower foreign matter content.
The method of manufacture of traditional high-purity copper oxide powder be with the copper of molten state with spray method in high temperature (about 1300 ℃) ejection down, warp combines with the oxygen of air and generates cupric oxide powder, the equipment and the technology of this kind method needs are very big.Or elemental copper changed into mantoquita with oxygenant or leaching agent with the elemental copper dissolving, make cupric oxide through technologies such as deposition, calcinings again.Be oxidized to cupric oxide by copper, it is insufficient that this method exists oxidation, easy remaining copper and the shortcoming that generates Red copper oxide in the product cupric oxide.
Adopt etching waste liquor to make raw material and directly prepare cupric oxide, can reduce the preparation cost of cupric oxide powder so greatly, can reduce pollution simultaneously, realize turning waste into wealth.But this type of waste liquid not only contains a large amount of sodium ions and cl ions, but also contains more impurity metal ion, and like iron, nickel, lead, zinc etc., these ions are easy to generate enrichment in the process of preparation cupric oxide, the quality of the cupric oxide that influence finally obtains.Therefore, adopt etching waste liquor to prepare the purity of the higher cupric oxide of the purity intermediate treatment technology that particularly the plating-grade copper oxide needs of high reactivity processable are suitable with the cupric oxide that guarantees to obtain at last.Related about using etching waste liquor in some disclosed patents, to have as the technology of feedstock production cupric oxide, introduce slightly in the face of the method in the patent that relates to down:
(1) application number is to disclose a kind of wet low-temperature oxidation in 01127175.2 the Chinese patent to decompose the process method of producing active copper oxide; With copper sulfate and copper material is raw material; LTO through 80-85 ℃; Obtain copper sulfate through crystallization, with the sodium hydroxide reaction, make active copper oxide through ball milling, press filtration, washing, oven dry, pulverizing more then.
(2) application number is the preparation method who discloses a kind of nano cupric oxide in 200710071896.2 the Chinese patent, makes cupric oxide with cupric nitrate and sodium hydroxide reaction through press filtration, drying, roasting.
(3) application number is to disclose a kind of method that adopts acidic etching waste liquid to prepare high-purity copper oxide in 201010269573.6 the Chinese patent; Acidic copper chloride waste etching solution is injected 30-35% (weight percent), temperature 40-60 ℃ sodium hydroxide solution, generate cupric oxide.Cupric oxide generates the brilliant cupric oxide of needle-like through the washing drying and sintering.
(4) application number is the production technique that 201010207485.3 Chinese patent discloses a kind of high-activity plating-grade copper oxide; With wiring board acidic copper chloride, cupric nitrate or copper sulfate etching waste liquor and liquid sodium hydroxide or Pottasium Hydroxide pH9-13, temperature 50-100 ℃ down reaction generate the bullion cupric oxide, make through microwave drying, pulverizing, washing, ultrasonic washing, microwave after drying and disintegrating process etc. afterwards and electroplate a level active copper oxide.
(5) application number is that disclosing a kind of in 201110231641.4 the Chinese patent is the method for feedstock production cupric oxide with the acidic etching liquid; Using sodium hydroxide or Pottasium Hydroxide to transfer to pH acidic etching liquid is 10～13; Add pure water then reaction soln is forwarded in the stainless steel cauldron that liner is a tetrafluoroethylene, 120～200 ℃ of hydro-thermal reactions are produced cupric oxide.
(6) having mentioned among the Japanese Patent JP8012327 with the acidic etching waste liquid is raw material, through chemical precipitation prepared cupric oxide, is employed in the middle deposition of hot water (40-80 ℃) and controls the effect that sedimentary composition improves filtration and washing.Cl ion content in the cupric oxide powder that this method obtains has 100ppm.
(7) application number is to disclose a kind of method of making copper plated material in 01132459.7 the patent; The carbonate solution of copper salt solution (cupric chloride, copper sulfate or cupric nitrate) and selection from basic metal, earth alkali metal and amine (NH4) is mixed; React the generation verdigris down for 75～90 ℃ in pH8.0～9.0 and temperature, verdigris is calcined in irreducibility atmosphere and is generated cupric oxide then.
(8) application number is in 200410101371.5 the patent, also mentions the method in 01132459.7 a kind of copper salt solution and alkaline solution reaction being obtained cupric oxide powder, heats the synthesis technique that this cupric oxide powder generates highly purified cupric oxide powder then.
(9) application number is the preparation method who discloses a kind of cupric oxide in 200610119045.6 the Chinese patent; Utilize acid copper-containing solution (cupric nitrate, cupric chloride, copper sulfate) for raw material and alkaline cupric chloride ammonium ion or the synthetic alkali type nantokite (basic copper nitrate, Basic Chrome Sulphate, basic copper chloride) of sodium hydroxide, again alkali type nantokite product and sodium hydroxide reaction are generated verditer or cupric oxide.
(10) application number is the preparation method who discloses a kind of oblique system cupric oxide in 200810067243.1 the Chinese patent, is presoma with the synthetic basic copper chloride, passes through and sodium hydroxide reacted oblique system cupric oxide again.The preparation of its presoma basic copper chloride is to be disclosed method in 200610060144.1 the Chinese patent according to application number, in will passing through in advance with to pH＞1.5 and remove PC board acidic copper chloride waste etching solution or the technical grade Cupric Chloride Solution and the scope internal reaction generation basic copper chloride of ammoniacal liquor of beavy metal impurities such as arsenic, lead in pH4～7.
(11) application number is also to disclose a kind of method for preparing high-purity cupric oxide powder through acid contained waste liquid in 200810035631.1 the Chinese patent.It is through with acid contained waste liquid and precipitation agent (like supercarbonate, carbonate, ammoniacal liquor, sodium hydroxide or Pottasium Hydroxide etc.) mixed precipitation; And the deposition that obtains with the solution washing that contains a certain amount of ionogen (in carbonate, supercarbonate, nitrate salt, ammonium salt or the ammoniacal liquor one or more), the oven dry calcining obtains cupric oxide then.
(12) application number is that 200710076208.1 Chinese patent discloses a kind of method of producing cupric oxide with alkaline etching waste liquid for producing through ammonia distillation process.
Above-mentioned 12 pieces of patents, method is each has something to recommend him, although the preparation technology of each patent is not quite similar, the advantage of oneself is arranged respectively.But also exist significant disadvantages separately simultaneously.The thickness state can appear in solution in the process of method (1) oxygenerating copper, need therefore can produce a large amount of washess through washing procedure repeatedly; Method (2) needs to adopt ethanol to make solvent, has improved production cost, and can produce nitrogen peroxide or nitrogen protoxide waste gas in the process of preparation cupric oxide, and environment is caused certain pollution; Method (3) though in realized the zero release of waste water, acidic copper chloride waste etching solution does not pass through any removal of impurities process, under the condition of pH value 8.0, various metallic impurity are precipitated and enrichment easily; Method (4), (5), (7)～(9) exist and the identical shortcoming of method (3), all do not relate to and how to remove metallic impurity; Method (10) preparation oblique system cupric oxide, but its activity is not verified; Method (11) is although adopted washing process to reduce metallic impurity and Cl ionic content such as the sodium in the cupric oxide, iron, nickel to a certain extent; But still contain more sodium ion (hundreds of is to several thousand ppm) and cl ions (content is greater than 45ppm), and also the activity of cupric oxide is not verified.Method (12) makes with alkaline etching waste liquid for producing long-time ammonia still process under high temperature, highly basic state, so the cupric oxide activity is also lower.
Summary of the invention
Purpose: the present invention is directed to the problem that exists in the prior art; The production technique of a kind of foreign matter content plating-grade copper oxide very low, can be rapidly-soluble in electroplate liquid is provided; It is raw material that route of the present invention directly adopts acidic etching waste liquid, adopts online reclaiming acidic etching liquid of ion-exchange membrane electrolysis and reduction to generate cathode copper, ammonia and soaks the high-activity plating-grade copper oxide that novel process that copper and negative pressure ammonia still process combines is produced processable; And advantages such as it is low to have production cost, and technology is simple.
Technical scheme: for solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of technology of producing the processable cupric oxide with acidic etching waste liquid is characterized in that this technology may further comprise the steps:
(1) online collection acidic etching waste liquid is removed trickle insoluble particle in the acidic etching waste liquid etc. with the acidic etching waste liquid of collecting with micron filter;
(2) acidic etching waste liquid after will filtering feeds in the membrane electrolyser and carries out electrolysis with ion-exchange film;
(3) the electrolytic reduction copper of membrane electrolyser cathodic area generation and the mixture of solution are carried out solid-liquid separation; Part liquid gets into electrolyzer again; Be used for the density of auxiliary adjustment acid etching regenerated liquid, thereby chemical constitution, redox potential and the density of acidic etching waste liquid are recovered as before;
(4) cathode copper after the solid-liquid separation soaks with ammoniacal liquor, feeds pressurized air and CO in the immersion process
2
(5) copper ammon solution that ammonia is soaked generation filters;
(6) will filter copper ammon solution afterwards and carry out ammonia still process, water absorbs the ammonia that evaporates in the ammonia still process process and regenerates ammoniacal liquor;
(7) ventilation breather that ammonia still process is obtained carries out centrifugal back and uses the pure water washed twice;
(8) ventilation breather that obtains after centrifugal is dried at 80～150 ℃;
(9) ventilation breather after the oven dry is calcined;
(10) cupric oxide that generates is carried out fragmentation, screening, the specification product after the screening carry out vacuum packaging.
So far, technology is accomplished.
As of the present invention preferred, in the present invention, the copper concentration of the acidic etching waste liquid in the said step (1) is 10～1200mg/L, and the aperture of micron filter is between 5～15 μ m.
As of the present invention preferred, in the present invention, the middle cationic exchange membrane of placing copper of membrane electrolyser in the said step (2); The oxidizing reaction that cuprous chlorine coordination ion takes place in the positive column of membrane electrolyser generates copper chlorine coordination ion, realizes the regeneration of acidic etching waste liquid:
2(CuCl
3)
2-+Cl
-→2(CuCl
4)
2-+2e
The reduction reaction that copper chlorine coordination ion takes place in the cathodic area generates copper
2(CuCl
4)
2-+Cu+2Cl
-→2(CuCl
3)
2-
2(CuCl
3)
2-→2(CuCl
2)
-+2Cl
-
2(CuCl
2)
2-+2e→2Cu↓+4Cl
In the present invention; Said step (3) acidic etching waste liquid is through can directly realizing the regeneration of acidic etching liquid after the electrolysis with ion-exchange film; Acidic etching liquid after the regeneration need not add any additives and just can directly return production line, can realize that the online recycling of acidic etching waste liquid and reduction generate cathode copper.
As of the present invention preferred, in the present invention, the ammoniacal liquor soaking temperature of copper is 30～70 ℃ in the said step (4), NH
3Be not less than 4:1 with the ratio of the amount of substance of Cu; Feed CO in the ammoniacal liquor immersion process of said step (4)
2And pressurized air, adopt CO
2Replace traditional volatile salt/bicarbonate of ammonia, soak in the process at ammonia and can not introduce new impurity, the quality of the cupric oxide that has guaranteed finally to obtain.
As of the present invention preferred, in the present invention, the concentration of the copper ammon solution that obtains after filtering in the said step (5) is 75～100g/L.
As of the present invention preferred, in the present invention, the ammonia still process process in the said step (6) adopts negative pressure ammonia still process, and the vacuum degree control in the ammonia still process process is at 0.04～0.09MPa, and the ammonia still process temperature is controlled at 55～90 ℃, and the ammonia still process time is no more than 12 hours; Described ammonia absorbs and adopts pure water, and the absorbing pure water ammonia generates ammoniacal liquor, can not introduce other impurity, has both realized the recycle of ammonia, has ensured the quality of the cupric oxide of final formation again.
As of the present invention preferred, in the present invention, the calcining temperature in the said step (9) is 250～800 ℃.
As of the present invention preferred, in the present invention, the cupric oxide powder in the said step (10) is broken to the 800-1000 order, crosses 800-1000 purpose sieve then, and coarse particles returns broken process and pulverizes again.
Beneficial effect: technology of producing the processable cupric oxide with acidic etching waste liquid of the present invention; Has following advantage with respect to prior art the present invention: can dissolve fast in the cupric oxide electroplate liquid that this explained hereafter is come out; Promptly realize dissolving fully in time of 30 seconds being less than; The content of various metallic impurity is very low, and the content of cl ions can drop to below the 10ppm; And can reach the online recycling that realizes acidic etching waste liquid simultaneously, both can eliminate the risk in the acidic etching waste liquid transfer process, the secondary pollution of avoiding acidic etching waste liquid to produce in handling realizes the efficient recycling of resource simultaneously; And adopt ion-exchange membrane electrolysis can make the amount of separating out of chlorine in the process lower, more friendly to environment; It is little to have in the production process pollution to environment, low, the active advantages of higher of the cupric oxide foreign matter content of producing.
Description of drawings
Fig. 1 is production process flow process figure of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Instance 1:
Produce the technology of processable cupric oxide with acidic etching waste liquid; Comprise the steps: (1) online collection acidic etching waste liquid, it is that the micron filter of 5 μ m is removed the trickle insoluble particle in the acidic etching waste liquid etc. that the acidic etching waste liquid collected is used the aperture;
(2) acidic etching waste liquid after will filtering feeds in the membrane electrolyser and carries out electrolysis with ion-exchange film, places the cationic exchange membrane of copper in the middle of the membrane electrolyser;
The oxidizing reaction that cuprous chlorine coordination ion takes place in the positive column of membrane electrolyser generates copper chlorine coordination ion, realizes the regeneration of acidic etching waste liquid:
2(CuCl
3)
2-+Cl
-→2(CuCl
4)
2-+2e
The reduction reaction that copper chlorine coordination ion takes place in the cathodic area generates copper;
2(CuCl
4)
2-+Cu+2Cl
-→2(CuCl
3)
2-
2(CuCl
3)
2-→2(CuCl
2)
-+2Cl
-
2(CuCl
2)
2-+2e→2Cu↓+4Cl
(3) the electrolytic reduction copper of membrane electrolyser cathodic area generation and the mixture of solution are carried out solid-liquid separation; Part liquid gets into electrolyzer again; Be used for the density of auxiliary adjustment acid etching regenerated liquid, thereby chemical constitution, redox potential and the density of acidic etching waste liquid are recovered as before;
(4) use of the cathode copper after solid-liquid separation temperature is that 30～70 ℃ of ammoniacal liquor soak NH
3With the ratio of the amount of substance of Cu be 5:1; Feed pressurized air and CO in the immersion process
2
(5) copper ammon solution that ammoniacal liquor is soaked filters;
(6) will filter copper ammon solution afterwards adopts negative pressure ammonia still process to carry out ammonia still process; Vacuum degree control in the ammonia still process process is at 0.04～0.09MPa; The ammonia still process temperature is controlled at 55～90 ℃, and the ammonia still process time is 12h, and water absorbs the ammonia that evaporates in the ammonia still process process and regenerates ammoniacal liquor;
(7) ventilation breather that ammonia still process is obtained carries out centrifugal back and uses the pure water washed twice;
(8) ventilation breather that obtains after centrifugal is dried at 80～150 ℃;
(9) ventilation breather after the oven dry is calcined at 250～800 ℃;
(10) cupric oxide that generates is crushed to the 800-1000 order, crosses 800-1000 purpose sieve then, the specification product after the screening carry out vacuum packaging.
The cupric oxide foreign matter content that makes with this method is low, active high, in electroplate liquid, can dissolve fully about 18 seconds.
Instance 2-embodiment 9:
Use the prepared processable cupric oxide identical, and carry out testing experiment with embodiment 1.Difference is respectively listed different micron filters aperture, NH in the use table 1
3With the ratio of the amount of substance of Cu, ammoniacal liquor soaking temperature, ammonia still process vacuum tightness, ammonia still process temperature, ammonia still process time, bake out temperature, calcining temperature, cross grit number.The test experiments result of prepared cupric oxide also is shown in Table 1.
Table 1
Can find out that from the test result shown in the table 1 the cupric oxide foreign matter content of explained hereafter of the present invention is low, active high, in electroplate liquid, being no more than 20 seconds can dissolve fully.
Below disclose the present invention with preferred embodiment, so it is not in order to restriction the present invention, and all employings are equal to replacement or the technical scheme that obtained of equivalent transformation mode, all drop within protection scope of the present invention.
Claims (8)
1. technology of producing the processable cupric oxide with acidic etching waste liquid is characterized in that this technology may further comprise the steps:
(1) online collection acidic etching waste liquid is removed trickle insoluble particle in the acidic etching waste liquid etc. with the acidic etching waste liquid of collecting with micron filter;
(2) acidic etching waste liquid after will filtering feeds in the membrane electrolyser and carries out electrolysis with ion-exchange film;
(3) the electrolytic reduction copper of membrane electrolyser cathodic area generation and the mixture of solution are carried out solid-liquid separation; Part liquid gets into electrolyzer again; Be used for the density of auxiliary adjustment acid etching regenerated liquid, thereby chemical constitution, redox potential and the density of acidic etching waste liquid are recovered as before;
(4) cathode copper after the solid-liquid separation soaks with ammoniacal liquor, feeds pressurized air and CO in the immersion process
2
(5) copper ammon solution that ammonia is soaked generation filters;
(6) will filter copper ammon solution afterwards and carry out ammonia still process, water absorbs the ammonia that evaporates in the ammonia still process process and regenerates ammoniacal liquor;
(7) ventilation breather that ammonia still process is obtained carries out centrifugal back and uses the pure water washed twice;
(8) ventilation breather that obtains after centrifugal is dried at 80～150 ℃;
(9) ventilation breather after the oven dry is calcined;
(10) cupric oxide that generates is carried out fragmentation, screening, the specification product after the screening carry out vacuum packaging.
2. technology of producing the processable cupric oxide according to claim 1 with acidic etching waste liquid, it is characterized in that: the copper concentration of the acidic etching waste liquid in the said step (1) is 10～1200mg/L, the aperture of micron filter is between 5～15 μ m.
3. technology of producing the processable cupric oxide with acidic etching waste liquid according to claim 1 is characterized in that: the middle cationic exchange membrane of placing copper of membrane electrolyser in the said step (2).
4. technology of producing the processable cupric oxide with acidic etching waste liquid according to claim 1 is characterized in that: the ammoniacal liquor soaking temperature of copper is 30～70 ℃ in the said step (4), NH
3Be not less than 4:1 with the ratio of the amount of substance of Cu.
5. technology of producing the processable cupric oxide with acidic etching waste liquid according to claim 1 is characterized in that: the concentration of the copper ammon solution that obtains after filtering in the said step (5) is 75～100 g/L.
6. technology of producing the processable cupric oxide with acidic etching waste liquid according to claim 1; It is characterized in that: the ammonia still process process in the said step (6) adopts negative pressure ammonia still process; Vacuum degree control in the ammonia still process process is at 0.04～0.09MPa; The ammonia still process temperature is controlled at 55～90 ℃, and the ammonia still process time is no more than 12 hours.
7. technology of producing the processable cupric oxide with acidic etching waste liquid according to claim 1, it is characterized in that: the calcining temperature in the said step (9) is 250～800 ℃.
8. technology of producing the processable cupric oxide according to claim 1 with acidic etching waste liquid, it is characterized in that: the cupric oxide powder in the said step (10) is broken to the 800-1000 order, crosses 800-1000 purpose sieve, and coarse particles returns broken process and pulverizes again.
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| CN106661738A (en) * | 2014-04-01 | 2017-05-10 | 西格玛工程集团 | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
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