CN102002729A - Copper-containing waste etching solution treatment method and etching solution regeneration method - Google Patents
Copper-containing waste etching solution treatment method and etching solution regeneration method Download PDFInfo
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- CN102002729A CN102002729A CN2009101681555A CN200910168155A CN102002729A CN 102002729 A CN102002729 A CN 102002729A CN 2009101681555 A CN2009101681555 A CN 2009101681555A CN 200910168155 A CN200910168155 A CN 200910168155A CN 102002729 A CN102002729 A CN 102002729A
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Abstract
The invention provides a copper-containing waste etching solution treatment method. In the electrodialysis step, copper ions and ammonium ions contained in the copper-containing waste etching solution are removed for obtaining treatment solution with low copper content. The concentration of the copper ions in the treatment solution with the low copper content is not more than 1ppm. In the reduction step, the removed copper ions are reduced for producing copper, copper oxide and/or cuprous oxide, and the removed ammonium ions are reduced for producing ammonia gas. The invention further relates to an etching solution regeneration method.
Description
Technical field
The invention relates to a kind of etching waste liquor facture and etching solution renovation process, and particularly relevant for a kind of facture of copper-containing etching waste solution and a kind of renovation process of cupric etching solution.
Background technology
In the processing procedure of preparation display panels and printed circuit board (PCB), often need to use various etching solutions to carry out the etching of metallic substance.The metal ion that produces in the etching process can constantly accumulate in the etching solution, after the concentration of metal ion in the etching solution is elevated to a certain degree, will makes that etching solution can't bear to use, and become etching waste liquor.Contain a large amount of metal ions, acidity or alkaline etching reagent and other chemical substance in these etching waste liquors, therefore can't arbitrarily throw aside, must could discharge through specific liquid waste disposal.
In the art, other are different along with manufacturer and industry, and used etching solution prescription and tolerable concentration of metal ions all are not quite similar.With domestic some Thin Film Transistor-LCD (thin filmtransistor liquid crystal display, TFT LCD) the employed etching solution of manufacturer is an example, when the concentration of cupric ion in the etching solution arrives about 1000ppm, etching solution has just lost etched ability, and the etching solution that must more renew.In addition, (print circuit board, PCB) in the etched etching solution of the copper that manufacturer utilized, tolerable copper ion concentration is about 130g/L at some printed circuit board (PCB).Though but in which kind of situation, still contain hydrogen peroxide and the etching additive of a large amount of acid, about 5-6wt% in these etching waste liquors, these compositions fail to utilize fully, equal to have increased manufacturing cost virtually.In addition, the manufacturer need pay extra one-tenth and clear and handled these waste liquids originally.
The processing mode of at present the most frequently used copper-containing etching waste solution is sulfuric acid conversion method of evaporation and electrolytic process.The sulfuric acid conversion method of evaporation is to add sulfuric acid and heating in etching waste liquor, so that the reaction of the cupric ion in the waste liquid produces copper sulfate, the acid (example hydrochloric acid, nitric acid) in the still recyclable in addition waste liquid.Yet the sulfuric acid conversion method of evaporation must be added a large amount of sulfuric acid, and can't reclaim hydrogen peroxide and chemical etchant in the waste liquid.Electrolytic process can be in order to reclaiming the copper metal, but the chemical etchant of this facture in also can't the efficient recovery etching waste liquor.
In view of this, association area is needed the facture that proposes a kind of more efficient copper-containing etching waste solution badly, not only can reduce the processing cost of waste liquid, can also promote the recycle value of waste liquid.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of treatment process of more efficient copper-containing etching waste solution and the renovation process of cupric etching solution, not only can reduce the processing cost of waste liquid, can also promote the recycle value of waste liquid.
One embodiment of the present invention has proposed the treatment process of the copper-containing etching waste solution that carries out in a reactive tank.Above-mentioned copper-containing etching waste solution comprises cupric ion, ammonium ion and hydrogen peroxide at least.This treatment process not only can obtain the copper of economically valuable, and the various products that produce in the reaction process also have the value of recycling respectively.
According to the specific embodiment of the invention, comprise at least in the above-mentioned reactive tank: a cathode compartment wherein is provided with a negative electrode; One liquid waste disposal chamber; One first positively charged ion dialysis membrane is located between cathode compartment and the liquid waste disposal chamber; One anolyte compartment wherein is provided with an anode; And one second positively charged ion dialysis membrane, be located between anolyte compartment and the liquid waste disposal chamber.
At first, sulphuric acid soln (concentration expressed in percentage by weight is 2-20%), aqueous electrolyte liquid and copper-containing etching waste solution are injected respectively among anolyte compartment, cathode compartment and the liquid waste disposal chamber.Thereafter, anticathode and anodal closure, so that:
(1) water molecules in the anolyte compartment carries out oxidizing reaction; And
(2) ammonium ion and cupric ion pass the first positively charged ion dialysis membrane and enter cathode compartment, and in cathode compartment, carry out reduction reaction, to produce ammonia and copper, cupric oxide and/or Red copper oxide respectively, wherein ammonia is partially soluble at least in the aqueous electrolyte liquid and contains the ammonium hydroxide aqueous solution so that it becomes.
In some optional specific embodiment of the present invention, used sulphuric acid soln concentration expressed in percentage by weight is 4-10%.
According to the specific embodiment of the invention, above-mentioned aqueous electrolyte liquid comprises an ionogen at least, and this ionogen is acid, alkali or salt.For instance, aqueous electrolyte liquid can be potassium hydroxide aqueous solution, ammonium hydroxide aqueous solution or the two mixture, aqueous ammonium chloride solution, aqueous sulfuric acid or aqueous hydrochloric acid.
In the specific embodiment of the invention, first and second used positively charged ion dialysis membrane can be respectively perfluoro sulfonic acid membrane, perfluorocarboxylic acid film, perfluorinated sulfonic acid/perfluorocarboxylic acid composite membrane or carbon polymer film.
In the specific embodiment that the present invention chooses wantonly, when switching on step, make that negative electrode and positive interpolar potential difference are the 5-20 volt.In addition, when switching on step, negative electrode and positive interpolar current density are the 500-2000 amperes per square meter.
The specific embodiment of choosing wantonly according to the present invention, used anode can be insoluble anode; On the other hand, used negative electrode can be titanium, copper or the above-mentioned combination of nickel, iron, stainless steel, graphite, carbon steel, nickel plating.
The specific embodiment of choosing wantonly according to the present invention when carrying out described treatment process, can be controlled in the reactive tank temperature inside 5-30 ℃.
In the specific embodiment that the present invention chooses wantonly, the reactive tank that uses a kind of two membranes and three chambers electrodialysis equipment to be used as carrying out above-mentioned processing.
The specific embodiment of choosing wantonly according to the present invention sustainablely carries out above-mentioned energising step, and the copper-containing etching waste solution in the liquid waste disposal chamber becomes till the low copper containing amount treatment solution (concentration of cupric ion is smaller or equal to 1ppm); At this moment, can collect this low copper containing amount treatment solution.Generally speaking, the concentration expressed in percentage by weight at above-mentioned low copper containing amount treatment solution hydrogen peroxide is 3-6%.In addition, above-mentioned ammonium hydroxide aqueous solution can be added in the low copper containing amount treatment solution of collecting, to obtain regeneration soln.Moreover, can utilize above-mentioned regeneration soln to prepare an etching solution.For instance, nitric acid can be added in the above-mentioned regeneration soln to make etching solution.
In the further optional embodiment of the present invention, can be collected in the copper, cupric oxide and/or the Red copper oxide that produce in the cathode compartment.
In another real-time mode of the present invention, the treatment process of copper-containing etching waste solution has been proposed.Above-mentioned copper-containing etching waste solution comprises cupric ion, ammonium ion and hydrogen peroxide at least.This treatment process not only can obtain the copper of economically valuable, and the various products that produce in the reaction process also have the value of recycling respectively.In addition, above-mentioned treatment process can also keep the hydrogen peroxide in the etching waste liquor.
According to the specific embodiment of the invention, above-mentioned treatment process comprises electrodialysis step and reduction step at least.In the electrodialysis step, by the driving of impressed voltage, by removing cupric ion and ammonium ion in the copper-containing etching waste solution, to obtain the low copper containing amount treatment solution of copper ion concentration smaller or equal to about 1ppm.In reduction step, above-mentioned cupric ion reduction is produced copper, cupric oxide and/or Red copper oxide, and above-mentioned ammonium ion reduction is produced ammonia.
In the specific embodiment that the present invention chooses wantonly, the concentration expressed in percentage by weight of hydrogen peroxide is 3-6% in the above-mentioned low copper containing amount treatment solution.
The further optional specific embodiment according to the present invention, but the above-mentioned copper, cupric oxide and/or the Red copper oxide that produce in the collection and treatment process.
In the specific embodiment that the present invention chooses wantonly, also comprise and carry out regeneration step.Particularly, can add the formed ammonium hydroxide aqueous solution that contains in the ammonia that produces in the treating processes or the water-soluble solution of ammonia in low copper containing amount treatment solution, obtaining a regeneration solution, and above-mentioned regeneration soln can be in order to the preparation etching solution.For instance, nitric acid can be added in the above-mentioned regeneration soln to make etching solution.
The another embodiment according to the present invention has proposed a kind of renovation process of cupric etching solution.Above-mentioned copper-containing etching waste solution comprises cupric ion, ammonium ion and hydrogen peroxide at least.This treatment process not only can obtain the copper of economically valuable, and the various products that produce in the reaction process also have the value of recycling respectively.In addition, above-mentioned treatment process can also keep the hydrogen peroxide in the etching waste liquor.
According to the specific embodiment of the invention, aforesaid method is included in two membranes and three chambers electrodialysis equipment at least and carries out a plurality of steps.Above-mentioned two membranes and three chambers electrodialysis equipment comprise the liquid waste disposal chamber, wherein contain pending copper-containing etching waste solution, and this copper-containing etching waste solution comprise cupric ion, ammonium ion and hydrogen peroxide at least; Cathode compartment wherein contains aqueous electrolyte liquid and is provided with negative electrode; First perfluoro sulfonic acid membrane is located between cathode compartment and the liquid waste disposal chamber; Wherein contain the sulphuric acid soln of the about 2-20% of concentration expressed in percentage by weight and be provided with anode the anolyte compartment; And second perfluoro sulfonic acid membrane, be located between anolyte compartment and the liquid waste disposal chamber.
The step of being carried out comprises following steps at least.At first, anticathode and anodal closure are so that negative electrode and positive interpolar potential difference are about the 5-20 volt; Negative electrode and positive interpolar current density are about the 500-1500 amperes per square meter; Carry out oxidizing reaction in the anolyte compartment; Above-mentioned ammonium ion and cupric ion pass first perfluoro sulfonic acid membrane and enter cathode compartment under the driving of above-mentioned potential difference, and in cathode compartment, carry out reduction reaction, to produce ammonia and copper, cupric oxide and/or Red copper oxide respectively, wherein ammonia is partially soluble at least in the aqueous electrolyte liquid and contains the ammonium hydroxide aqueous solution so that it becomes.In the process of switching on, the temperature of electrodialysis device interior is controlled in about 5-30 ℃.When the copper-containing etching waste solution in the liquid waste disposal chamber becomes low copper containing amount treatment solution (concentration of cupric ion is smaller or equal to about 1ppm), collect this low copper containing amount treatment solution, the concentration expressed in percentage by weight of hydrogen peroxide is about 3-6% in above-mentioned low copper containing amount treatment solution.Ammonium hydroxide aqueous solution is added in the low copper containing amount treatment solution of collecting, and to obtain regeneration soln, above-mentioned regeneration soln can be in order to the preparation etching solution.
Hence one can see that, and the treatment process of using the present invention's proposition has following advantage at least:
(1) efficiently in the Treatment of Copper etching waste liquor, to reclaim the wherein copper of economically valuable;
(2) can keep the most chemical constitutions that belong in the copper-containing etching waste solution in the original etching solution, comprise hydrogen peroxide and etching reagent, for utilizing again; And
(3) the various products that produce in the treating processes, by product (as ammonia, oxygen, hydrogen etc.) are difficult for causing adverse influence to environment, and have the value of recycling.
After consulting hereinafter embodiment, the persond having ordinary knowledge in the technical field of the present invention is when can understanding essence spirit of the present invention and other goal of the invention easily, and the technology used in the present invention means and embodiment.
Description of drawings
For above and other objects of the present invention, feature, advantage and embodiment can be become apparent, appended the description of the drawings is as follows:
Fig. 1 is a summary accompanying drawing, illustrates in order to implement the illustration reactive tank according to the treatment process of the specific embodiment of the invention.
[primary clustering nomenclature]
100 reactive tanks
102 negative electrodes
104 anodes
110 cathode compartments
112 cathode compartments inlet
The outlet of 114 cathode compartments
Liquid waste disposal chambers 120
122 liquid waste disposal chamber inlets
Liquid waste disposal chambers 124 outlet
130 anolyte compartments
132 anolyte compartments inlet
The outlet of 134 anolyte compartments
140 first positively charged ion dialysis membranes
150 second positively charged ion dialysis membranes
Embodiment
Hereinafter describe embodiments of the present invention and specific embodiment, censure similar parts with similar element numbers in each accompanying drawing with reference to appended drawings.
In the numerous embodiments of the present invention, the treatment process of copper-containing etching waste solution has been proposed.Generally speaking, copper-containing etching waste solution comprises cupric ion, ammonium ion, hydrogen peroxide and other at least and is contained in chemical substance in the original etching solution.The treatment process that the present invention proposes not only can obtain the copper of economically valuable, and the various products that produce in the reaction process also have the value of recycling respectively.In addition, above-mentioned treatment process more can keep most of chemical constitutions that belong in the original etching solution in the etching waste liquor, and the use of can regenerating, and avoid meaningless waste.
One embodiment of the present invention has proposed the treatment process of copper-containing etching waste solution.
According to the specific embodiment of the invention, above-mentioned treatment process comprises electrodialysis step and reduction step at least.In the electrodialysis step, by the driving of impressed voltage, by removing cupric ion and ammonium ion in the copper-containing etching waste solution, to obtain the low copper containing amount treatment solution of copper ion concentration smaller or equal to about 1ppm.In reduction step, above-mentioned cupric ion reduction is produced copper, cupric oxide and/or Red copper oxide, and above-mentioned ammonium ion reduction is produced ammonia.
According to the specific embodiment of the invention, copper, cupric oxide and/or the Red copper oxide that can collect in the reduction step to be produced.Above-mentioned copper may be with metal or form of powder, through after the suitable refinery procedure, can become the product that possesses high economic worth.Red copper oxide is then applied to purposes such as coating, anti-mycotic agent, corrosion inhibitor widely.
According to principle of the present invention and spirit, when utilizing the electrodialysis method to handle etching waste liquor, can keep that great majority still can be used for etched chemical substance in the etching waste liquor.With the hydrogen peroxide is example, in the specific embodiment of the invention, in the resulting low copper containing amount treatment solution, can possess the hydrogen peroxide of the about 3-6% of concentration expressed in percentage by weight.
Further, still contain the number of chemical material in the above-mentioned low copper containing amount treatment solution, these chemical substances all are composition part contained in the original etching solution basically, because in the electrodialysis step, have almost removed cupric ion and the ammonium ion that is produced in the etching process in fact.
In other words, treatment process according to specific embodiment of the invention proposition, can keep composition part numerous in the etching solution (for example hydrogen peroxide and various etching additive), only wherein the shared concentration expressed in percentage by weight of each composition may be different with original etching solution.In known liquid waste disposal process, above-mentioned composition may be destroyed, or can discharge along with waste water.Yet the treatment process that the embodiment of the invention proposes makes these wastes to be reused, and has produced new value.
Therefore, the another specific embodiment according to the present invention can be mixed with above-mentioned low copper containing amount treatment solution one regeneration solution, and can further adjust the proportioning of each composition part in this regeneration soln, to obtain can be used for the etching solution of etch process.
For instance, can produce ammonia in reduction process, these ammonias may form ammonium hydroxide aqueous solution in the water-soluble solution, or with the form loss of gas.At this moment, can collect above-mentioned ammonium hydroxide aqueous solution or ammonia, and it is added in the above-mentioned low copper containing amount treatment solution, to obtain regeneration soln.
In addition, in the etching solution that industry is used always, can contain nitric acid at present.Therefore, can an amount of nitric acid be added above-mentioned regeneration soln, to obtain the having suitable etching solution of forming part proportioning according to the proportioning of original etching solution.According to principle of the present invention and spirit, nitric acid described herein only is illustration, and the persond having ordinary knowledge in the technical field of the present invention selects suitable chemical substance and its addition when visual required etching solution composition.
Another embodiment of the present invention has proposed to carry out the treatment process of copper-containing etching waste solution in reactive tank.
Fig. 1 is a summary accompanying drawing, and it has illustrated can be in order to the real reactive tank 100 of making the treatment process of the specific embodiment of the invention.The illustration reactive tank 100 that Fig. 1 illustrated is a kind of electrodialysis equipment of two membranes and three chambers, as shown in the figure, the first positively charged ion dialysis membrane 140 separates into reactive tank 100 three compartments such as cathode compartment 110, liquid waste disposal chamber 120 and anolyte compartment 130 with the second positively charged ion dialysis membrane 150, and wherein the first positively charged ion dialysis membrane 140 is located between cathode compartment 110 and the liquid waste disposal chamber 120; And the second positively charged ion dialysis membrane 150 is located between liquid waste disposal chamber 120 and the anolyte compartment 130.Be respectively equipped with negative electrode 102 and anode 104 in cathode compartment 110 and the anolyte compartment 130.
According to the specific embodiment of the invention, the treatment process of carrying out copper-containing etching waste solution in above-mentioned reactive tank comprises following steps at least.
To carry out the required solution of electrodialysis at first, respectively and inject suitable reaction chamber.Particularly, aqueous electrolyte liquid is injected cathode compartment 110 via cathode compartment inlet 112; Copper-containing etching waste solution is injected liquid waste disposal chamber 120 via liquid waste disposal chamber inlet 122; And sulphuric acid soln injected anolyte compartments 130 via anolyte compartment inlet 132.
Thereafter, negative electricity and the positive electricity with external dc power (not illustrating) is connected to negative electrode 102 and anode 104 and energising respectively; At this moment, the reaction that is taken place in each reaction chamber is as mentioned below.
In anolyte compartment 130, water molecules can carry out oxidizing reaction, and produces oxygen, and these oxygen can export 134 and discharge by the anolyte compartment.
Because oxygen also has certain utility value, therefore in the further embodiment of the present invention, can collect these oxygen, for other application.On the other hand, because oxygen there is no adverse influence to environment, therefore also can directly discharge it is entered in the Atmosphere System.
In liquid waste disposal chamber 120, cupric ion in the copper-containing etching waste solution and ammonium ion can be under the drivings of extra electric field, pass the first positively charged ion dialysis membrane 140 and enter cathode compartment 110.
In the further embodiment of the present invention, along with increase conduction time, the copper ion concentration in the copper-containing etching waste solution can reduce gradually, when the concentration of cupric ion is reduced to smaller or equal to 1ppm, can obtain a low copper containing amount treatment solution.In addition, in above-mentioned low copper containing amount treatment solution, the concentration expressed in percentage by weight of hydrogen peroxide is about 3-6%.Above-mentioned low copper containing amount treatment solution can be discharged by liquid waste disposal chamber outlet 124, utilizes for follow-up again.
In cathode compartment 110, cupric ion and ammonium ion can carry out reduction reaction, can produce hydrogen, ammonia and copper bearing material in above-mentioned reduction reaction, as copper, cupric oxide and/or Red copper oxide.Above-mentioned hydrogen and ammonia may be discharged by cathode compartment outlet 114 with the form of gas; Or have the ammonia of part may be dissolved in the electrolytic solution of cathode compartment, and make it become ammonium hydroxide aqueous solution.
In the further embodiment of the present invention, because hydrogen can be used as the fuel of fuel cell or steam boiler, therefore collect the hydrogen that is produced, also can produce extra economic worth.In addition, owing to contain ammonium ion in the original etching solution, therefore in the further embodiment of the present invention, can collect the ammonia or the above-mentioned ammonium hydroxide aqueous solution of discharge, to be used for allocating etching solution.As for above-mentioned copper, cupric oxide and/or Red copper oxide, after through collection and/or purifying, can apply to various uses.
One specific embodiment according to the present invention can be prepared into above-mentioned low copper containing amount treatment solution one regeneration solution.For instance, above-mentioned ammonium hydroxide aqueous solution or ammonia can be added in the low copper containing amount treatment solution, to obtain regeneration soln.
In the further specific embodiment of the present invention, can in above-mentioned regeneration soln, add suitable chemical classes and quantity, it is prepared into suitable etching solution.For instance, can an amount of nitric acid be added above-mentioned regeneration soln, to obtain the having suitable etching solution of forming part proportioning according to the proportioning of original etching solution.The above only is an illustration, and the persond having ordinary knowledge in the technical field of the present invention forms when visual required etching solution and to add suitable chemical substance.
According to the specific embodiment of the invention, the concentration expressed in percentage by weight of the sulphuric acid soln in the anolyte compartment 130 is about 2-20%, particularly, the concentration expressed in percentage by weight of sulphuric acid soln is about 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20%.
According to principle of the present invention and spirit, the aqueous electrolyte liquid that makes an addition in the cathode compartment 110 comprises an ionogen at least, and above-mentioned ionogen can be acid, alkali or salt.Particularly, aqueous electrolyte liquid can be potassium hydroxide aqueous solution, ammonium hydroxide aqueous solution or above-mentioned mixture; In certain embodiments, above-mentioned aqueous electrolyte liquid can be an aqueous ammonium chloride solution; In further embodiments, above-mentioned aqueous electrolyte liquid can be aqueous sulfuric acid or aqueous hydrochloric acid.What is more, can also utilize pure water as above-mentioned aqueous electrolyte liquid.Or be to comprise above-mentioned copper-containing etching waste solution in the above-mentioned aqueous electrolyte liquid.
According to the specific embodiment of the invention, when carrying out the electrodialysis processing, the potential difference that negative electrode 102 and anode are 104 is about the 5-20 volt; Or above-mentioned potential difference is about the 10-15 volt.Particularly, above-mentioned potential difference can be about 5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 volts.
In addition, in actually operating, extra electric field in the current density of negative electrode 102 and 104 formation of anode approximately less than 2000 amperes per square meter.According to some specific embodiment, above-mentioned current density is about the 500-1500 amperes per square meter.
The further specific embodiment according to the present invention, above-mentioned treatment process at least also comprise reactive tank 110 temperature inside and are controlled at about 5-30 ℃.From real the work, in the too high environment of temperature, hydrogen peroxide decomposes easily and produces bubble and block the positively charged ion dialysis membrane and thereby reduce its exchange efficiency.Otherwise in the low excessively environment of temperature, ion is difficult for can reducing exchange efficiency too by the positively charged ion dialysis membrane.Therefore in an embodiment who chooses wantonly, can utilize extra temperature controlling instruments (as refrigerating unit) to control reactive tank 110 temperature inside.Refrigerating unit equipment described herein only is illustration, in real the work, can utilize any known technology, material and equipment to carry out said temperature control.
According to the specific embodiment of the invention, the material of each composition portion is as described below in the above-mentioned reactive tank 110.
The first positively charged ion dialysis membrane 140 and the second positively charged ion dialysis membrane 150 can be respectively perfluoro sulfonic acid membrane, perfluorocarboxylic acid film, perfluorinated sulfonic acid/perfluorocarboxylic acid composite membrane or carbon polymer film.
The material of anode 104 can be insoluble anode (dimensionally stable anode is called for short DSA).Generally speaking, above-mentioned insoluble anode comprises a metal base and a catalytic film at least, and wherein above-mentioned catalytic film is positioned at least one surface of metal base.For instance, the kind of above-mentioned metal base includes but not limited to titanium, tantalum, nickel or its equipollent; And the material of above-mentioned catalytic film includes but not limited to the oxide compound of metals such as titanium, tantalum, ruthenium, yttrium or zirconium or the equipollent of organic compound or above-mentioned materials.
The material of negative electrode 102 can be titanium, copper or the above-mentioned combination of nickel, iron, stainless steel, graphite, carbon steel, nickel plating.In the present invention's one specific embodiment, the material of negative electrode 102 is a copper.
Though above describe how to implement treatment process of the present invention with a kind of electrodialysis equipment of two membranes and three chambers, the present invention is not limited to this.Otherwise the system that can utilize any other single equipment or a plurality of equipment to combine implements treatment process of the present invention.
When implementing treatment process of the present invention, visual practical situation is selected in various embodiment by mentioned earlier, material, parameter or its equipollent and is met demander, and combination obtains treatment process of the present invention.In addition, and visual demand determines whether adopting some optional step, as whether collecting a certain reaction product, whether will controlling reactive tank temperature etc.
For instance, one specific embodiment according to the present invention can carry out the manipulation of regeneration of copper-containing etching waste solution in a kind of two membranes and three chambers electrodialysis equipment.
Above-mentioned two membranes and three chambers electrodialysis equipment comprise at least: cathode compartment wherein is provided with negative electrode; The liquid waste disposal chamber; First perfluoro sulfonic acid membrane is located between cathode compartment and the liquid waste disposal chamber; The anolyte compartment wherein is provided with anode; And second perfluoro sulfonic acid membrane, be located between anolyte compartment and the liquid waste disposal chamber.Above-mentioned copper-containing etching waste solution comprises cupric ion, ammonium ion and hydrogen peroxide at least, and above-mentioned manipulation of regeneration comprises following steps at least.
Respectively with the sulphuric acid soln of copper-containing etching waste solution, aqueous electrolyte liquid and the about 2-20% of concentration expressed in percentage by weight, inject liquid waste disposal chamber, cathode compartment and anolyte compartment.
Thereafter, to above-mentioned negative electrode and this anodal closure, so that negative electrode and positive interpolar potential difference are about the 5-20 volt, and negative electrode and positive interpolar current density are about the 500-1500 amperes per square meter.Under the situation of energising, can carry out oxidizing reaction in the anolyte compartment; And ammonium ion in the copper-containing etching waste solution and cupric ion can pass first perfluoro sulfonic acid membrane under the driving of potential difference and enter cathode compartment, and in cathode compartment, carry out a reduction reaction.In the above-mentioned reduction reaction, can produce ammonia and copper, cupric oxide and/or Red copper oxide, wherein this ammonia is partially soluble at least in this aqueous electrolyte liquid and contains the ammonium hydroxide aqueous solution so that it becomes one.In the process of energising, the temperature of control electrodialysis device interior remains in about 5-30 ℃ with it.
Continue energising, when copper-containing etching waste solution becomes a low copper containing amount treatment solution (concentration of cupric ion is smaller or equal to about 1ppm) in the liquid waste disposal chamber, collect this low copper containing amount treatment solution.At this moment, the concentration expressed in percentage by weight of hydrogen peroxide is about 3-6% in the above-mentioned low copper containing amount treatment solution.
Ammonium hydroxide aqueous solution is added in this low copper containing amount treatment solution, and to obtain a regeneration solution, this regeneration soln can be in order to prepare an etching solution.For instance, nitric acid commonly used in the etching solution can be added in the above-mentioned regeneration soln with the preparation etching solution.
In addition, can collect copper, this cupric oxide and/or this Red copper oxide that produces in the cathode compartment.
In the present embodiment, anode material is an insoluble anode, and cathode material can be copper or stainless steel.Above-mentioned insoluble anode is to be base material with the titanium, and the catalytic film that applies on it is made up of ru oxide, yttrium oxide or its combination institute.
More specifically, in one embodiment, pass area in matter and be about 0.05m
2Electrodialysis equipment in, add the sulphuric acid soln of copper-containing etching waste solution, aqueous electrolyte liquid and the about 4-10% of concentration expressed in percentage by weight of about 10L according to mode mentioned above.
Thereafter, to above-mentioned negative electrode and this anodal closure, so that negative electrode and positive interpolar potential difference are about the 10-15 volt, and negative electrode and positive interpolar current density are about the 500-1500 amperes per square meter.Continue about 10 hours of energising, and control the temperature of electrodialysis device interior in the galvanization, it is remained in about 5-30 ℃.
Thus, the concentration expressed in percentage by weight of hydrogen peroxide is about 6% in the resulting low copper containing amount treatment solution, and the concentration of cupric ion is less than 1ppm.
Above narrated the multiple specific embodiment of each embodiment of the present invention.The persond having ordinary knowledge in the technical field of the present invention is when infering, and when carrying out the electrodialysis reaction, the service efficiency of positively charged ion dialysis membrane has been played the part of crucial role.To contain the aqueous solution of hydrogen peroxide, if hydrogen peroxide is because of the improper ion-exchange capacity that will influence the positively charged ion dialysis membrane of operating environment control.More specifically, hydrogen peroxide decomposes the generation bubble easily and blocks the positively charged ion dialysis membrane in the environment of alkalescence.Therefore, technical field of the present invention viewpoint is for a long time thought, should not utilize the electrodialysis method to handle the aqueous solution that contains hydrogen peroxide.
Yet, according to principle of the present invention and spirit, in above-mentioned a plurality of embodiments and embodiment, by one or more parameters in the control electrodialysis process, a kind of comparatively ideal technical scheme is provided, not only can utilize the electrodialysis method to handle the copper-containing etching waste solution that contains the hydrogen peroxide composition, reduce the concentration of cupric ion and keep hydrogen peroxide, and solved the durability and the low problem of service efficiency of positively charged ion dialysis membrane in the past.For instance, according to the embodiment of the invention, owing to can produce hydrogen ion at anode (anolyte compartment), make hydrogen peroxide be in the relatively low sour environment of pH value, thus, hydrogen peroxide is difficult for decomposing and produces bubble, therefore can avoid or slow down the disappearance that hydrogen peroxide reduces positively charged ion dialysis membrane exchange efficiency.
Though the present invention discloses as above with embodiment; right its is not in order to qualification the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention is as the criterion when looking the scope that claims define.
Claims (20)
1. the treatment process of a copper-containing etching waste solution is characterized in that, comprises at least:
One reactive tank is provided, and it comprises at least:
One cathode compartment wherein contains an aqueous electrolyte liquid and is provided with a negative electrode;
One liquid waste disposal chamber wherein contain a pending copper-containing etching waste solution, and this copper-containing etching waste solution comprises cupric ion, ammonium ion and hydrogen peroxide at least;
One first positively charged ion dialysis membrane is located between this cathode compartment and this liquid waste disposal chamber;
One anolyte compartment, wherein to contain a concentration expressed in percentage by weight be the sulphuric acid soln of 2-20% and be provided with an anode; And
One second positively charged ion dialysis membrane is located between this anolyte compartment and this liquid waste disposal chamber;
And
To this negative electrode and this anodal closure, so that:
Water molecules in this anolyte compartment carries out an oxidizing reaction; And
This ammonium ion and this cupric ion pass this first positively charged ion dialysis membrane and enter this cathode compartment, and in this cathode compartment, carry out a reduction reaction, to produce ammonia and copper, cupric oxide and/or Red copper oxide respectively, wherein this ammonia is partially soluble at least in this aqueous electrolyte liquid and contains the ammonium hydroxide aqueous solution so that it becomes one.
2. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, the concentration expressed in percentage by weight of this sulphuric acid soln is 4-10%.
3. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, this aqueous electrolyte liquid comprises an ionogen at least, and this ionogen is acid, alkali or salt.
4. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, this aqueous electrolyte liquid is potassium hydroxide aqueous solution, ammonium hydroxide aqueous solution, aqueous ammonium chloride solution, aqueous sulfuric acid or aqueous hydrochloric acid.
5. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, this first with this second positively charged ion dialysis membrane be a perfluoro sulfonic acid membrane, a perfluorocarboxylic acid film, one perfluorinated sulfonic acid/perfluorocarboxylic acid composite membrane or a carbon polymer film.
6. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, in this energising step, this negative electrode and this sun interpolar one potential difference are the 5-20 volt.
7. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, in this energising step, this negative electrode and this sun interpolar one current density are the 500-2000 amperes per square meter.
8. the treatment process of copper-containing etching waste solution according to claim 1, it is characterized in that, this anode is an insoluble anode, and it comprises a metal base and a catalytic film that is positioned at least one surface of this metal base at least, and wherein this metal base is titanium, tantalum or nickel; And a material of this catalytic film can be the oxide compound or the organic compound of titanium, tantalum, ruthenium, yttrium or zirconium.
9. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, a material of this negative electrode is the titanium of nickel, iron, stainless steel, graphite, carbon steel, nickel plating, copper or above-mentioned combination.
10. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, a temperature that at least also comprises this reactive tank inside is controlled in 5-30 ℃.
11. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, this reactive tank is one or two membranes and three chambers electrodialysis equipment.
12. the treatment process of copper-containing etching waste solution according to claim 1 is characterized in that, wherein:
When this copper-containing etching waste solution in this liquid waste disposal chamber becomes a low copper containing amount treatment solution, collect this low copper containing amount treatment solution, wherein the concentration of cupric ion is 3-6% smaller or equal to the concentration expressed in percentage by weight of 1ppm and hydrogen peroxide in this low copper containing amount treatment solution; And
This ammonium hydroxide aqueous solution is added in this low copper containing amount treatment solution of collecting, and to obtain a regeneration solution, this regeneration soln can be in order to prepare an etching solution.
13. the treatment process of copper-containing etching waste solution according to claim 12 is characterized in that, at least also comprises a nitric acid is added in this regeneration soln to prepare this etching solution.
14. the treatment process of copper-containing etching waste solution according to claim 12 is characterized in that, at least also comprises to be collected in this copper, this cupric oxide and/or this Red copper oxide that produces in this cathode compartment.
15. the treatment process of a copper-containing etching waste solution is characterized in that, this copper-containing etching waste solution comprises cupric ion, ammonium ion and hydrogen peroxide at least, and this method comprises at least:
One electrodialysis step so that can be under the driving of an impressed voltage, by removing this cupric ion and this ammonium ion in this copper-containing etching waste solution, to obtain a low copper containing amount treatment solution, wherein in this low copper containing amount treatment solution the concentration of cupric ion smaller or equal to 1ppm; And
One reduction step produce copper, cupric oxide and/or Red copper oxide with this cupric ion reduction that will remove, and this ammonium ion that will remove reduces and the generation ammonia.
16. the treatment process of copper-containing etching waste solution according to claim 15 is characterized in that, the concentration expressed in percentage by weight of hydrogen peroxide is 3-6% in this low copper containing amount treatment solution.
17. the treatment process of copper-containing etching waste solution according to claim 15 is characterized in that, at least also comprises to collect this copper, cupric oxide and/or Red copper oxide.
18. the treatment process of copper-containing etching waste solution according to claim 15, it is characterized in that, at least also comprise a regeneration step, it is to add this ammonia or this ammonia is dissolved in the formed ammonium hydroxide aqueous solution that contains in the aqueous solution in this low copper containing amount treatment solution, to obtain a regeneration solution, this regeneration soln can be in order to prepare an etching solution.
19. the treatment process of copper-containing etching waste solution according to claim 18 is characterized in that, at least also comprises a nitric acid is added in this regeneration soln to prepare this etching solution.
20. the renovation process of a cupric etching solution is characterized in that, comprises at least:
One or two membranes and three chambers electrodialysis equipment is provided, and it comprises at least:
One liquid waste disposal chamber wherein contain a pending copper-containing etching waste solution, and this copper-containing etching waste solution comprises cupric ion, ammonium ion and hydrogen peroxide at least;
One cathode compartment wherein contains an aqueous electrolyte liquid and is provided with a negative electrode;
One first perfluoro sulfonic acid membrane is located between this cathode compartment and this liquid waste disposal chamber;
Wherein contain the sulphuric acid soln of the about 2-20% of a concentration expressed in percentage by weight and be provided with an anode one anolyte compartment; And
One second perfluoro sulfonic acid membrane is located between this anolyte compartment and this liquid waste disposal chamber;
To this negative electrode and this anodal closure, so that:
This negative electrode and this sun interpolar one potential difference are about the 5-20 volt;
This negative electrode and this sun interpolar one current density are about the 500-1500 amperes per square meter;
Carry out an oxidizing reaction in this anolyte compartment;
This ammonium ion and this cupric ion pass this first perfluoro sulfonic acid membrane and enter this cathode compartment under the driving of this potential difference, and in this cathode compartment, carry out a reduction reaction, to produce ammonia and copper, cupric oxide and/or Red copper oxide respectively, wherein this ammonia is partially soluble at least in this aqueous electrolyte liquid and contains the ammonium hydroxide aqueous solution so that it becomes one;
One temperature of this electrodialysis device interior is controlled in about 5-30 ℃;
When this copper-containing etching waste solution in this liquid waste disposal chamber becomes a low copper containing amount treatment solution, collect this low copper containing amount treatment solution, wherein the concentration of cupric ion is about 3-6% smaller or equal to the concentration expressed in percentage by weight of about 1ppm and hydrogen peroxide in this low copper containing amount treatment solution; And
This ammonium hydroxide aqueous solution is added in this low copper containing amount treatment solution of collecting, and to obtain a regeneration solution, this regeneration soln can be in order to prepare an etching solution.
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| CN2009101681555A CN102002729A (en) | 2009-09-01 | 2009-09-01 | Copper-containing waste etching solution treatment method and etching solution regeneration method |
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| CN2009101681555A CN102002729A (en) | 2009-09-01 | 2009-09-01 | Copper-containing waste etching solution treatment method and etching solution regeneration method |
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| CN104630825A (en) * | 2015-01-20 | 2015-05-20 | 昆山美源达环保科技有限公司 | Device and process for electrolytically extracting copper in acidic etching liquid |
| CN105132947A (en) * | 2015-09-24 | 2015-12-09 | 苏州市铂瑞工业材料科技有限公司 | Copper-recyclable electrode set |
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| CN102626591A (en) * | 2012-04-10 | 2012-08-08 | 上海交通大学 | Method and device for purifying graphene oxide/graphite solution |
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| CN104630825A (en) * | 2015-01-20 | 2015-05-20 | 昆山美源达环保科技有限公司 | Device and process for electrolytically extracting copper in acidic etching liquid |
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| CN109208020A (en) * | 2018-11-09 | 2019-01-15 | 广东顺德西安交通大学研究院 | A kind of electrochemical appliance and method synthesizing nano cuprous oxide |
| CN109868476A (en) * | 2019-01-28 | 2019-06-11 | 湖北永绍科技股份有限公司 | A kind of etching liquid recycling and reusing method of copper ions and nitrate anion |
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| CN110055537A (en) * | 2019-05-22 | 2019-07-26 | 惠州市臻鼎环保科技有限公司 | A kind of method for reclaiming of PCB nitric acid spent solder stripper |
| CN110983375A (en) * | 2019-12-24 | 2020-04-10 | 广东臻鼎环境科技有限公司 | Method for depositing copper by using waste etching solution of electrolytic printed circuit board |
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Application publication date: 20110406 |