CN1283817C - Method for recycling copper - Google Patents

Method for recycling copper Download PDF

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CN1283817C
CN1283817C CNB021467005A CN02146700A CN1283817C CN 1283817 C CN1283817 C CN 1283817C CN B021467005 A CNB021467005 A CN B021467005A CN 02146700 A CN02146700 A CN 02146700A CN 1283817 C CN1283817 C CN 1283817C
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liquid
copper
oxidizing gas
solid
oxyradical
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CN1498977A (en
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王志成
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The present invention discloses a method for recycling copper. In the method, copper-containing gel (copper sludge) is processed by addition treating agents and/or treatment auxiliary agents, so macromolecule agglomerant in the copper-containing gel is separated, and a copper-containing water solution and an oxidizing gas are obtained. After a converting agent and a converting auxiliary agent are added in and react with the copper-containing water solution and solid liquid are separated, copper oxide with high utility value and another oxidizing gas are obtained, wherein the liquid obtained in the solid-liquid separation can be saturated by the two oxidizing gases, and the liquid is converted into a strong oxidant and is recovered for reuse. The copper recycling method of the present invention can obtain copper oxide with high copper content, other products obtained when waste liquid is processed can be completely recovered and reused without other contaminant, such as residue, sludge, etc.

Description

The method that copper reclaims
Technical field
The present invention relates to a kind of recovery method of metal, refer to the method that a kind of copper reclaims especially.
Background technology
Press, the method for making of printed circuit board (PCB) (PCB) roughly comprises following several steps at present:
(a) copper panel is removed: comprise degrease, alkali (electrolysis or embathe), washing, pickling and drying;
(b) go up rete and be coated with sensitizer;
(c) exposure imaging: used photographic developer is a kind of alkaline aqueous solution that can be washed out by flowing water (abandons need not), is dipped in after the washing in 10% hydrochloric acid solution, washes out with deionized water then;
(d) wet etching: with chromic acid and sulfuric acid mixture liquid, iron(ic) chloride, ammonium persulfate, cupric chloride and other common acid mixed solution carry out wet etching;
(e) electroplate: form metal level with plating mode, use alkali lye in process;
(f) rete divests: use organic solution, and ketone such as acetone for example, ethyl acetate, the celo element, or use the acid solution that heated;
(g) washing and dry
Wherein, the solvent that divests photographic developer comprises trieline and chlorination methylene.The used medicament of wet etching comprises sulfuric acid, sulfuric acid/hydrofluoric acid, chromic acid, sulfuric acid/weight ammonium fluoride, fluosulfonic acid and chloroform/alcohol.On pcb board is made, be usually used in electroplated metal and comprise scolding tin, copper, nickel, tinsel, tin-nickel alloy and noble metal etc.
In addition, after forming several layers of line layer, can in the PCB substrate, form one and run through electroplating hole, in order to electrically connect line layer up and down.Wherein, running through electroplating hole is to form via cleaning, lose copper (alligatoring), activation and electroless copper mode.At wash phase, scavenging solution commonly used comprises acidity and basic solution.In the alligatoring stage, stripping copper etching liquor commonly used roughly is divided into three classes: persulfuric acid salt (persulfates) comprises ammonium persulphate, Sodium Persulfate (sodium sulfate) etc.; Cuprous chloride (copper (I) chloride) and hydrogen peroxide add sulfuric acid.Before substrate carries out electroless copper, must make the substrate activation with the initial oxidation reduction reaction earlier, generally be to use to comprise noble metal (for example saline solutions such as gold and silver, platinum, palladium, titanium) isoreactivity catalytic specie.When utilizing redox reaction to carry out electroless copper, need to use formaldehyde and highly basic.Wherein employed electroless copper plating liquid of electroless copper stage mainly comprises the cupric ion from copper sulfate or cupric nitrate, from the reductive agent of formaldehyde: sodium hydroxide and misfit agent etc.Carry out electro-coppering after the electroless copper immediately, with the electroless copper layer in the protection through hole.The method of electro-coppering comprises acid electroplating and basic plating, and the electroplate liquid that acid electroplating uses comprises copper sulfate, copper borate, boron fluoric acid copper, cupric pyrophosphate, burnt cupric nitrate etc.The general cupric cyanide that uses in the basic plating.
From the above, PCB factory finishes the waste water that is produced behind the PCB product and comprises each metal ion species and cupric ion.Copper is in great demand in the making of PCB, but in manufacturing processed, line layer time institute depleted amount was also very big during especially etching formed, and caused the wasting of resources, and manufacturing cost can't reduce.In addition, in whole PCB processing procedure, use a lot of acid solution and alkali lye, or even noble metal, directly be discharged among the environment meeting severe contamination living environment, threat to life health if these are unprocessed, therefore, the utmost point needs the method for the good recovery copper of a kind of efficient.
The research that has had many people to be devoted to reclaim so far, great majority only bias toward acid base equilibrium or remove the poisonous metal material by replacement(metathesis)reaction, but fail to improve the benefit that reclaims copper.In addition, the method for some recyclable copper is arranged also, yet produced other residue or mud, equally also pollute the environment.
For example, Taiwan patent announcement number the 363905th discloses a kind of resource recovery and treatment method of cupric waste, it is that the copper-contained sludge the like waste is added water furnishing pulpous state (paste), add sulfuric acid and oxygenant again and carry out acidification reaction, obtain copper sulfate mother liquor (filtrate) and insoluble material slag (filtered residue) through after the filtering separation, wherein the copper sulfate mother liquor obtains cupric sulfate pentahydrate (CuSO behind condensing crystal 45H 2O), insoluble material slag then in alkali lye and after bury (landfill).It is pending that this method stays residue etc. equally.
US6,274,045 disclose the method for a kind of Separation and Recovery noble metal and non-precious metal, comprise the pH-value of adjusting waste liquid; Add metal misfit agent, make the metal of desire recovery form metal ion; Add agglutinant (aggregating agent), ionic group is assembled; Dehydrate then.It is pending that this method stays another kind of waste etc. too.
Summary of the invention
The object of the invention is to provide a kind of method that reclaims copper, and the copper metal that is particularly useful for circuit card production and plating industry contained waste liquid reclaims again.
For reaching above-mentioned purpose, the present invention provides the method that a kind of copper reclaims, and is specially adapted to from aqueous copper solution feed recovery high-purity copper, and method comprises transforming agent and the charging of converting additive adding aqueous copper solution, carry out conversion reaction, produce first oxidizing gas and a suspension.Suspension is carried out obtaining cupric oxide solid and a liquid after the solid-liquid separation, and wherein liquid is saturated by first oxidizing gas, becomes the recovery liquid with oxidation capacity, gets back to the aqueous copper solution charging.
The method that the present invention also provides a kind of copper to reclaim is specially adapted to reclaim high-purity copper from a cupric gelinite that contains polymer coagulant, comprising:
(a) handle A agent and/or treatments B agent with one, or the acidic etching waste liquid that will directly take from PCB factory adds this cupric gelinite, and stir, produce one second oxidizing gas, and first suspension that contains polymer coagulant;
(b) make first suspension carry out solid-liquid separation, take out polymer coagulant, obtain one and have blue solution;
(c) transforming agent and converting additive are added the solution that has blueness, carry out conversion reaction, produce first oxic gas and second suspension;
(d) second suspension is carried out solid-liquid separation, obtain cupric oxide solid and a liquid, wherein this liquid is saturated by first and second oxidizing gas, becomes the recovery liquid with oxidation capacity, gets back to step (a).
Main points of view according to the present invention, the method that copper reclaims comprises the processing of aqueous copper solution and the processing of cupric gelinite.
Cupric gelinite (being commonly called as copper mud) is by treatment agent and/or handle the effect of auxiliary agent, or by the effect of acidic etching waste liquid, polymer coagulant contained in the cupric gelinite can be isolated, and obtains aqueous copper solution.Aqueous copper solution at this indication comprises that treated cupric gelinite is resulting, and original un-grated waste liquid.
The composition of aqueous copper solution mainly contains Cu 2+, Fe 3+, Fe 2+Sulfuric acid, nitric acid or aqueous chloride solution, adding transforming agent and converting additive reacts with it, after via solid-liquid separation, the solid that is produced obtains the high cupric oxide of utility value through after dehydrating processing, and a liquid part returns former processing program, and another part then can be used as the strong oxidizer that is used for water treatment.
Contain polymer coagulant and metallic salt in the cupric gelinite, can its macromolecular structure be changed,, polymer coagulant is separated taking-up to re-use then via solid-liquid separation by adding treatment agent and/or processing auxiliary agent generation misfit reaction.
Description of drawings
Fig. 1 is one of the present invention preferred embodiment, a kind of schema that reclaims the method for copper.
The figure number explanation:
A is a steel basin, and B is an equipment for separating liquid from solid, and C is the cupric liquid bath, D is a crystallizer tank, and E is an equipment for separating liquid from solid, and F is a misfit liquid accumulator tank, G is the oxidizing gas recovery system, the 1st, and upper clear liquid, the 2nd, resistates, the 100th, the cupric gelinite, the 200th, treatment agent, 200 ' is to handle auxiliary agent, the 3rd, polymer coagulant/aggegation auxiliary agent, the 300th, the not aqueous copper solution charging of pbz polymer agglutinant, the 4th, aqueous copper solution, the 400th, transforming agent, 400 ' is converting additive, the 5th, mixed solution, the 6th, cupric oxide, 7 is first oxidizing gases, the 8th, misfit liquid, the 9th, reclaim misfit liquid, the 10th, strong oxidizer, 11 is second oxidizing gases.
Embodiment
Usually; PCB manufactory and Electroplate Factory be common its pH-value of meeting balance before the discharging waste liquid; and add polymer coagulant with in and the electric charge of charge species in the waste liquid; make the micropartical aggegation form bigger particle by this; and the harmful metal ion in the displacement waste liquid forms metallic salt, makes can reach emission standard through the gained liquid after the solid-liquid separation.Excess sludge after the solid-liquid separation is called cupric gelinite 100, mainly contains polymer coagulant and metallic salt.Above-mentioned polymer coagulant is just comprising/the general water treatment agglutinant of using of negative ion type, for example Tai-Ace S 150 (Al 2(SO 4) 218H 2O), ferric sulfate (Fe 2(SO 4) 3), ferrous sulfate (FeSO 47H 2O), iron(ic) chloride (FeCl 36H 2O), tschermigite (Al 2(SO 4) 3(NH 4) 2SO 424H 2O), potassium alum (Al 2(SO 4) 3, K 2SO 424H 2O), slaked lime (Ca (OH) 2), unslaked lime (CaO), crystallization carbonated soda (Na 2CO 310H 2O), sodium aluminate (Na 2OAl 2O 3), magnesium oxide (MgO) and aggegation auxiliary agent, for example SODA ASH LIGHT 99.2 (Na 2CO 3), sodium bicarbonate (NaHCO 3), sodium hydroxide, active silicic acid and polymer electrolyte etc.
After above-mentioned cupric gelinite 100 weighed, insert steel basin A, add treatment agent 200 and/or handle auxiliary agent 200 '.The purpose that adds treatment agent 200 and/or processing auxiliary agent 200 ' is to change the structure of the polymer coagulant in the cupric gelinite 100, and it reacts as shown in the formula shown in (I):
Figure C0214670000061
Wherein ,-C-C-C-is a short chain molecule.
Employed treatment agent 200 and/or processing auxiliary agent 200 ' for example comprise sulfuric acid, nitric acid, hydrogenchloride, oxygenant and combination thereof respectively.The person all can use oxygenant as long as can produce the oxyradical after adding the cupric gelinite, for example comprises potassium permanganate, sodium permanganate, potassium manganate, sodium manganate, S-WAT, potassium sulfite, Potcrate, sodium chlorate and resemblance thereof.Its consumption be treatment agent and/or handle auxiliary agent after stir for some time and promptly produce a suspension and get final product, preferred number is the 20-80% of cupric gelinite weight.
Add treatment agent 200 and/or handle auxiliary agent 200 ' after steel basin A for some time, can produce second oxidizing gas 11 and a suspension that has oxidation capacity in a large number, wherein the oxidation capacity of second oxidizing gas 11 is from the molecule of its free radical that has, particularly oxyradical.Wherein oxyradical comprises hydroxyl free radical, sulphur oxyradical and chlorine oxyradical.These second oxidizing gases 11 are recyclable as the oxygenant in the subsequent processing steps.
In another specific embodiment, can utilize acidic etching waste liquid to replace treatment agent and/or processing auxiliary agent.Acidic etching waste liquid can be from the acid waste liquid of PCB factory, comprise solution such as copper sulfate, copper borate, boron fluoric acid copper, cupric pyrophosphate, burnt cupric nitrate or cupric chloride, the consumption of acidic etching waste liquid is as long as adding treatment agent and/or producing a suspension after processing auxiliary agent stirring for some time, and preferable quantity is the 50-1000% of cupric gelinite weight.
Afterwards, the suspension process solid-liquid separation with gained obtains upper clear liquid 1 and resistates 2.Wherein upper clear liquid 1 is for having blue cupric liquid.After the resistates 2 process equipment for separating liquid from solid B press filtrations, obtain khaki color solid part and liquid portion, wherein the solid part of gained is polymer coagulant/aggegation auxiliary agent 3 contained in the former cupric gelinite, recyclable as mentioned above utilization again, and the liquid portion of gained then is an aqueous copper solution 4.Above-mentioned equipment for separating liquid from solid B can be any device that carries out solid-liquid separation, for example strainer formula tripping device, centrifugal device and filter-pressing device.
Aqueous copper solution 4 and upper clear liquid 1 inserted among the cupric liquid bath C mix, obtain mixed solution 5.The mixed solution 5 of this moment mainly comprises Cu 2+, Fe 2+, Fe 3-Sulfuric acid, nitric acid or aqueous chloride solution.
Mixed solution 5 is inserted crystallizer tank D, and add transforming agent 400 and/or converting additive 400 '.By precipitin reaction, make metal in the mixed solution 5 form crystallization and precipitate.Precipitin reaction is as shown in the formula shown in (II):
The used transforming agent 400 of precipitin reaction for example comprises such as subsalt classes such as potassium hydroxide, sodium hydroxide, calcium hydroxides, and water.Used converting additive 400 ' is mainly burning agent and water.The burning agent for example comprises lime carbonate, yellow soda ash, salt of wormwood and composition thereof.
In addition, precipitin reaction also can produce the molecule of the oxidation capacity of some first oxidizing gas, 7, the first oxidizing gases 7 with oxidation capacity from its free radical that has, particularly oxyradical.Wherein oxyradical comprises hydroxyl free radical, sulphur oxyradical and chlorine oxyradical.Then, first oxidizing gas 7 is imported misfit liquid accumulator tank F.
If the not aqueous copper solution charging 300 of pbz polymer agglutinant is arranged, can directly raise into cupric liquid bath C, be mixed together with aqueous copper solution 4 and upper clear liquid 1, and then carry out follow-up treatment step together.
Can be required according to circumstances, can before entering crystallizer tank D, mixed solution 5 will be concentrated into desired concentration earlier, in order to follow-up crystallisation step.As long as reach the purpose of the cupric oxide crystallization yields that improves follow-up knot day step gained in this mixed solution 5 concentration, its scope of specific limited not is because the contained material of each waste liquid charging is to originate with waste liquid to decide.But in the situation of handling the PCB contained waste liquid, mixed solution 5 contains 15-25% copper (weight percent, down together) usually.
Liquid process equipment for separating liquid from solid E press filtration with the above-mentioned steps gained makes its solid-liquid separation, obtains a solids and a liquid.Wherein solids obtains a solid oxide copper 6 through the dehydration back, and liquid then is misfit liquid 8.This moment, the cupric oxide copper content that obtains was up to about more than 40%.The misfit liquid 8 of this moment is for containing NaCl, KCl, CaCl 2, Na 2SO 4, K 2SO 4And CaSO 4Deng saturated aqueous solution.Above-mentioned equipment for separating liquid from solid E can be any device that carries out solid-liquid separation, for example strainer formula tripping device, centrifugal device and filter-pressing device.
The misfit liquid 8 of gained is imported misfit liquid accumulator tank F, recovery misfit liquid 9 recyclable utilizations again from the discharge of misfit liquid accumulator tank, be poured into oxidizing gas recovery system G, first oxidizing gas 7 that second oxidizing gas 11 that is produced with steel basin A and crystallizer tank D are produced makes it saturated, and then gets back to steel basin A or become oxygenant product 10.Have very strong oxidation capacity through the saturated misfit liquid of oxidizing gas this moment, helps to change the molecular structure of polymer coagulant, and strengthen the effect of treatment agent 200 and/or processing auxiliary agent 200 '.In oxidizing gas recovery system G, be liquid for clear, colorless through second, first oxidizing gas 11 and 7 saturated recovery misfit liquid 9.Second oxidizing gas 11 that steel basin A is produced is 8.5 with respect to the productive rate of first oxidizing gas 7 that crystallizer tank D is produced: 1.5-9.5: 0.5.
The present invention is applied in and handles PCB factory waste liquid, can reach the effect of quite high copper recovery.Yet the present invention not only can be applied in and handle PCB factory waste liquid, and all contained waste liquids all can utilize the present invention's copper recovery method to reclaim highly purified copper.
Example I
As shown in Figure 1, the scale cupric gelinite 100 that gets 20T/d is inserted steel basin A.Sulfuric acid (H with 3.5T/d 2SO 4)/hydrochloric acid (HCl)/potassium permanganate (KMnO 4, potassium permanganate) and add steel basin A, continue to stir, have blue upper clear liquid 1, resistates 2 and second oxidizing gas 11 up to generation.Upper clear liquid 1 is inserted cupric liquid bath C.At this, use filter-pressing device as equipment for separating liquid from solid B, make resistates 2 press filtrations after, obtain khaki color solid product and aqueous copper solution 4.Second oxidizing gas 11 imports oxidizing gas recovery system G.Wherein the khaki color solid product is to be polymer coagulant 3 contained in the former cupric gelinite, and productive rate is 15T/d.
The aqueous copper solution 4 of gained is inserted cupric liquid bath C.In cupric liquid bath C, mix upper clear liquid 1 and aqueous copper solution 4, obtain mixed solution 5.Mixed solution 5 is inserted crystallizer tank D, and the transforming agent 400 of adding 15T/d and the converting additive 400 ' of 0.5T/d, make mixed solution 5 precipitations, also produce simultaneously first oxidizing gas 7, use filter-pressing device as equipment for separating liquid from solid E, carry out after the press filtration at this, obtain a misfit liquid 8 and a product, wherein product through dehydration after, obtain copper content greater than about 40% cupric oxide 6, productive rate is 30T/d.
Misfit liquid 8 enters misfit liquid accumulator tank F and reclaims misfit liquid 9, discharges from misfit liquid accumulator tank F, enters oxidizing gas recovery system G then, makes it further saturated by second oxidizing gas 11 and first oxidizing gas 7.The solution that presents clear, colorless through the recovery misfit liquid of second, first oxidizing gas 11 and 7 after saturated.Wherein, the recovery misfit liquid of about 20T/d is got back to steel basin A, and the recovery misfit liquid of rest part then can be made strong oxidizer 10.Wherein the productive rate of strong oxidizer 10 is 74T/d.The productivity ratio of 11 pairs first oxidizing gases 7 of second oxidizing gas is about 9: 1.
Example II
Scale gets the cupric gelinite 100 of 20T/d, inserts steel basin A.The main contained waste liquid of 100T/d is added steel basin A, continue to stir, have blue upper clear liquid 1, resistates 2 and second oxidizing gas 11 up to generation.Upper clear liquid 1 is inserted cupric liquid bath C.At this, use filter-pressing device as equipment for separating liquid from solid B, make resistates 2 press filtrations after, obtain khaki color solid product and aqueous copper solution 4.Second oxidizing gas 11 imports oxidizing gas recovery system G.Wherein the khaki color solid product is to be polymer coagulant 3 contained in the former cupric gelinite, and productive rate is 16.5T/d.
The aqueous copper solution 4 of gained is inserted cupric liquid bath C.In cupric liquid bath C, mix upper clear liquid 1 and aqueous copper solution 4, obtain mixed solution 5.Mixed solution 5 is inserted crystallizer tank D, and the transforming agent 400 of adding 35T/d and the converting additive 400 of 1T/d, make the cupric composition in the mixed solution 5 change into cupric oxide, also produce simultaneously first oxidizing gas 7, use filter-pressing device as equipment for separating liquid from solid E, carry out after the press filtration at this, obtain a filtrate 8 and a product, wherein product through dehydration after, obtain copper content greater than about 42% cupric oxide 6, productive rate is 40T/d.
Filtrate 8 enters treatment agent accumulator tank F and obtains a recovery liquid 9.Discharge from treatment agent accumulator tank F, enter oxidizing gas recovery system G then, make it further saturated by second oxidizing gas 11 and first oxidizing gas 7.Recovery liquid after second oxidizing gas 11 and first oxidizing gas 7 are saturated presents the solution of clear, colorless.Wherein the recovery liquid of about 21T/d is got back to steel basin A, and the recovery liquid of rest part then can be made strong oxidizer 10.Wherein the productive rate of strong oxidizer 10 is 7.5T/d.The productivity ratio of 11 pairs first oxidizing gases 7 of second oxidizing gas is about 9: 1.
It seems that from the viewpoint of the utilization of resources copper content weight percent of general copper mine only is 5%, however from the copper content of the makers' waste gas cupric of printed circuit board (PCB) gelinite up to 8-12%.Valuable material like this obtains copper content and is higher than 40% cupric oxide purity through the present invention's copper recovery method, significantly promotes the benefit of utilizing of copper.
Moreover, in copper recovery method of the present invention, not staying residue mud, the whole products that produced in the handling procedure (comprising polymer coagulant and oxygenant) are all recyclable to be utilized again, for the environment protection contribution greatly.
Therefore, the method that the present invention's copper reclaims can be a kind of very perfect and very high contained waste liquid treatment process of enforcement usefulness, after the present invention's method is handled, there is not resistates discarded fully, not only the rate of recovery of precious metals one bronze medal is very high, and the whole recovery process does not have secondary pollution, and can be replaced by direct acidic etching waste liquid from PCB factory in order to the reagent that takes out polymer coagulant, bring into play resource reutilization fully, have industry applications.

Claims (1)

1, a kind of method of copper recovery, it is characterized in that: this method may further comprise the steps:
(a) sulfuric acid or nitric acid or hydrogenchloride or potassium permanganate or sodium permanganate or potassium manganate or sodium manganate or S-WAT or potassium sulfite or Potcrate or sodium chlorate are joined in the cupric gelinite, after stirring for some time, second oxidizing gas that produces a suspension and have oxidation capacity in a large number, wherein, the oxidation capacity of second oxidizing gas is from its oxyradical that has, and wherein oxyradical comprises hydroxyl free radical, sulphur oxyradical and chlorine oxyradical;
(b) with gained suspension in (a) step through solid-liquid separation, obtain upper clear liquid and resistates, wherein upper clear liquid is to have blue cupric liquid, resistates through the equipment for separating liquid from solid press filtration after, obtain khaki color solid part and liquid portion;
(c) gained upper clear liquid in (b) step is mixed with the liquid portion of press filtration gained, add potassium hydroxide or sodium hydroxide or calcium hydroxide or lime carbonate or yellow soda ash or salt of wormwood, produce first oxidizing gas and a liquid, wherein, the oxidation capacity of first oxidizing gas is from its oxyradical that has, and wherein oxyradical comprises hydroxyl free radical, sulphur oxyradical and chlorine oxyradical;
(d) with gained liquid in (c) step through the equipment for separating liquid from solid press filtration, make its solid-liquid separation, obtain a solids and a liquid, wherein solids obtains a solid oxide copper through the dehydration back, liquid is misfit liquid, wherein misfit liquid makes its full closing by first oxidizing gas and second oxidizing gas, becomes the oxygenant product.
CNB021467005A 2002-11-07 2002-11-07 Method for recycling copper Expired - Fee Related CN1283817C (en)

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CN104120485A (en) * 2014-08-13 2014-10-29 湖北三江航天红林探控有限公司 Treatment process for copper plating bath solution
CN104744974B (en) * 2015-03-10 2017-10-17 广州市天承化工有限公司 A kind of PCB generates the production technology of macromolecule conductive film with modified activating solution and in PCB through hole and blind hole
CN107248436B (en) * 2016-04-28 2018-12-18 杭州富通电线电缆有限公司 A kind of coaxial cable production technology
CN112479429A (en) * 2020-11-27 2021-03-12 九江德福科技股份有限公司 Method for treating copper pyrophosphate wastewater

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