CN103451675B - Printed circuit board etching waste liquid processes system and method - Google Patents
Printed circuit board etching waste liquid processes system and method Download PDFInfo
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- CN103451675B CN103451675B CN201210178721.2A CN201210178721A CN103451675B CN 103451675 B CN103451675 B CN 103451675B CN 201210178721 A CN201210178721 A CN 201210178721A CN 103451675 B CN103451675 B CN 103451675B
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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
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Abstract
The present invention relates to a kind of printed circuit board etching waste liquid and process system and method。This printed circuit board etching waste liquid processes system and includes reservoir, vaporising device, cooling bath, precipitation separation device, the first electrolysis dashpot, electrolysis bath, ion-exchange membrane electrolyzer, filtering ponds and the second electrolysis dashpot。After said system and etching line are connected with each other, realize the recovery of copper by the mode of electrolysis after first evaporating, and in the electrolytic process of electrolysis bath and ion-exchange membrane electrolyzer, reclaim alkali。
Description
Technical field
The present invention relates to printed circuit board (PCB) production field, particularly relate to process system and the processing method of a kind of printed circuit board etching waste liquid containing copper chloride。
Background technology
In printed circuit board processing technology, the reclaiming of acid copper chloride etching liquid annoyings printed substrate enterprise all the time, every liter of copper containing about 100 grams to 180 grams in non-renewable acid copper chloride etching liquid, only the copper content of this kind of spent etching solution that Guangdong Province produces every month just has more than thousands of tons of, if reclaiming this kind of metallic copper and the use of spent etching solution circular regeneration necessarily being had very great economic benefit and the value of environmental protection。
Traditional printed board etching waste liquor processing method only single extraction copper, and after carrying copper, waste liquid directly discharges, and other compositions in etching solution is not reclaimed, and causes secondary pollution problems。
Summary of the invention
Based on this, it is necessary to provide one can reclaim copper, but also the process system of recyclable other compositions of printed circuit board etching waste liquid and processing method。
A kind of printed circuit board etching waste liquid processes system, including: reservoir, vaporising device, cooling bath, precipitation separation device, the first electrolysis dashpot, electrolysis bath, ion-exchange membrane electrolyzer, filtering ponds and the second electrolysis dashpot, wherein,
Described reservoir is used for memory print plate etching waste liquor, and the composition of described printed circuit board etching waste liquid includes copper chloride, hydrogen chloride and sodium chloride；
Described vaporising device is connected with described reservoir, separates for being evaporated by the hydrogen chloride in described printed circuit board etching waste liquid；
Described cooling bath is connected with described vaporising device, for receiving the hydrogen chloride gas that described vaporising device produces, forms hydrochloric acid after condensed absorbent；
Described precipitation separation device is connected with described vaporising device, and the partial oxidation copper removed in the printed circuit board etching waste liquid after hydrogen chloride is converted into Copper hydrate precipitation at described precipitation separation device, and makes precipitation and solution separating；
Described first electrolysis dashpot is connected with described precipitation separation device, separates the Copper hydrate precipitation obtained and enters described first electrolysis dashpot, and is converted into cupric ammine complex at described first electrolysis dashpot；
Described electrolysis bath is connected with described first electrolysis dashpot, and described cupric ammine complex is copper simple substance and ammonia at described electrolytic tank electrolysis；
Described ion-exchange membrane electrolyzer includes anode region, relief area and cathode chamber, described anode region and described relief area are separated by anionic membrane, described relief area and described cathode chamber are separated by cationic membrane, described relief area is for receiving from the solution after the removal Copper hydrate precipitation of described precipitation separation device, described anode region produces to pass into the chlorine of described cooling bath for electrolysis, and described cathode chamber produces copper simple substance and sodium hydroxide solution for electrolysis；
Described filtering ponds are connected with described ion-exchange membrane electrolyzer, are used for collecting by filtration described copper simple substance；
Described second electrolysis dashpot is connected with described filtering ponds, is used for collecting described sodium hydroxide solution。
Wherein in an embodiment, described electrolysis bath is connected with described first electrolysis dashpot, and the ammonia that described electrolytic tank electrolysis produces enters described first electrolysis dashpot, makes Copper hydrate precipitation be converted into cupric ammine complex。
Wherein in an embodiment, described first electrolysis dashpot is connected with described ion-exchange membrane electrolyzer, the interior electrolyte after described electrolytic tank electrolysis of described first electrolysis dashpot is injected separately into anode region and the relief area of described ion-exchange membrane electrolyzer, and the electrolyte after ion-exchange membrane electrolyzer electrolysis injects described first electrolysis dashpot。
Wherein in an embodiment, described second electrolysis dashpot is connected with described precipitation separation device, and described sodium hydroxide solution is injected precipitation separation device, the partial oxidation copper in the printed circuit board etching waste liquid after described removal hydrogen chloride to be converted into Copper hydrate precipitation。
Wherein in an embodiment, described second electrolysis dashpot is connected with described ion-exchange membrane electrolyzer, and the sodium hydroxide solution in described second electrolysis dashpot injects the cathode chamber of described ion-exchange membrane electrolyzer。
A kind of printed circuit board etching waste liquid processing method, comprises the steps:
Using reservoir memory print plate etching waste liquor, the composition of described printed circuit board etching waste liquid includes copper chloride and hydrogen chloride and sodium chloride；
Printed circuit board etching waste liquid in described reservoir being injected vaporising device, makes the hydrogen chloride evaporation in printed circuit board etching waste liquid separate, the hydrogen chloride gas obtained is passed in cooling bath, forms hydrochloric acid after condensed absorbent；
Printed circuit board etching waste liquid after removing hydrogen chloride is injected precipitation separation device, and partial oxidation copper is converted into Copper hydrate precipitation, separate, obtain the solution after removing Copper hydrate precipitation；
Described Copper hydrate precipitation is proceeded to the first electrolysis dashpot, reacts generation cupric ammine complex with ammonia or ammonium salt；
Described cupric ammine complex is injected electrolysis bath, and electrolysis produces copper simple substance and ammonia；
Solution after being precipitated by described removal Copper hydrate injects the relief area of ion-exchange membrane electrolyzer, and the anode region electrolysis at described ion-exchange membrane electrolyzer produces chlorine, forms hydrochloric acid after condensed absorbent；Make the cathode chamber being positioned at the copper ion of the electrolyte of described relief area and the sodium ion described ion-exchange membrane electrolyzer of entrance, produce copper simple substance and sodium hydroxide solution in the electrolysis of described cathode chamber；
Filtering ponds are used to collect by filtration described copper simple substance；And
The second electrolysis dashpot is used to collect described sodium hydroxide solution。
Wherein in an embodiment, the ammonia that described electrolytic tank electrolysis produces enters described first electrolysis dashpot, makes Copper hydrate precipitation be converted into cupric ammine complex。
Wherein in an embodiment, the molten anode region being injected separately into described ion-exchange membrane electrolyzer after described electrolytic tank electrolysis and relief area in described first electrolysis dashpot, the electrolyte after ion-exchange membrane electrolyzer electrolysis injects described first electrolysis dashpot and is circulated。
Wherein in an embodiment, the described sodium hydroxide solution in described second electrolysis dashpot injects described precipitation separation device, so that the partial oxidation copper in the printed circuit board etching waste liquid after described removal hydrogen chloride to be converted into Copper hydrate precipitation。
Wherein in an embodiment, the described sodium hydroxide solution in described second electrolysis dashpot injects the cathode chamber of described ion-exchange membrane electrolyzer and is circulated。
A kind of printed circuit board etching waste liquid processes system, including:
Reservoir；
Vaporising device with reservoir fluid communication；
With the cooling bath that vaporising device fluid communication extracts boil-off gas；
With vaporising device fluid communication to extract through remaining after evaporation liquid and in the precipitation separation device that precipitation wherein occurs；
Precipitate, with what will precipitation separation device produce, the first electrolysis dashpot collected with precipitation separation device fluid communication；
Electrolysis bath with the first electrolysis dashpot circulation；
With precipitation separation device fluid communication so that remaining liq after precipitation is extracted in the ion-exchange membrane electrolyzer that electrolysis wherein occurs；And
The second electrolysis dashpot with ion-exchange membrane electrolyzer fluid communication。
Wherein in an embodiment, described second electrolysis dashpot and precipitation separation device fluid communication are with liquid needed for supplying precipitation to precipitation separation device。
Wherein in an embodiment, described ion-exchange membrane electrolyzer and the first electrolysis dashpot fluid communication, to extract liquid in the first dashpot, are further provided with filtering ponds between ion-exchange membrane electrolyzer and the second electrolysis dashpot。
Wherein in an embodiment, described ion-exchange membrane electrolyzer includes anode region, cathode chamber and the relief area between anode region and cathode chamber, separated by anionic membrane between anode region and relief area, separated by cationic membrane between cathode chamber and relief area, described cooling bath and anode region fluid communication, described precipitation separation device and relief area fluid communication, the first electrolysis dashpot and anode region and relief area fluid communication simultaneously。
Wherein in an embodiment, described ion-exchange membrane electrolyzer farther includes the temporary tank of and anode region fluid communication, temporary tank further with the first electrolysis dashpot fluid communication。
Wherein in an embodiment, with ion-exchange membrane electrolyzer fluid communication to collect the gas that electrolysis produces the while of described cooling bath。
After said system and printed panel etching line are connected with each other, realize the recovery of copper by the mode of electrolysis after first evaporating, alkali can be reclaimed in electrolytic process simultaneously。
Accompanying drawing explanation
Fig. 1 is the Organization Chart of the process system of the printed circuit board etching waste liquid of an embodiment；
Fig. 2 is the flow chart of the processing method of the printed circuit board etching waste liquid of an embodiment。
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail。Elaborate a lot of detail in the following description so that fully understanding the present invention。But the present invention can implement being much different from alternate manner described here, and those skilled in the art can do similar improvement when without prejudice to intension of the present invention, therefore the present invention is by the following public restriction being embodied as。
In order to solve traditional printed board etching waste liquor processing method only single extraction copper, and waste liquid directly discharges after carrying copper, other compositions in etching solution are not reclaimed, cause secondary pollution problems, this programme adopts electrolysis, electrodialytic technique, can not only be reclaimed by the copper in etching solution, and adopts method other compositions such as also recyclable HCl, NaOH etc. of electrolysis with ion-exchange film, whole system does not produce secondary pollution, and etching solution obtains resource circulation utilization。
In the following description, " liquid adapter " refer to the pipeline that a kind of liquid can therefrom flow；" gas adapter " refers to the pipeline that a kind of gas can therefrom flow。In the present invention, no matter the pipeline between two equipment is transmission gas or liquid all can be understood as fluid communication。The mode such as the pressurization such as through driving device or decompression that flows of liquid or gas realizes, and in order to better illustrate principles of the invention, the description of these driving devices is omitted。
Fig. 1 shows the configuration diagram of the process system of the printed circuit board etching waste liquid of an embodiment。Referring to Fig. 1, the process system 100 of the printed circuit board etching waste liquid of an embodiment includes: reservoir 10, vaporising device 20, cooling bath 30, precipitation separation device the 40, first electrolysis dashpot 50, electrolysis bath 60, ion-exchange membrane electrolyzer 70, filtering ponds 80 and the second electrolysis dashpot 90。
Printed circuit board etching waste liquid flows into and is stored in from the etching line producing printed circuit board (PCB) reservoir 10。The composition of described printed circuit board etching waste liquid mainly includes copper chloride, hydrogen chloride and sodium chloride。Difference according to etching waste liquor, it is also possible to include other metal ions such as potassium, ferrum, nickel。
Vaporising device 20 and reservoir 10 are by liquid adapter 11 fluid communication, and pass through gas adapter 21 and cooling bath 30 fluid communication。It is provided with heater in vaporising device 20, the printed circuit board etching waste liquid entering vaporising device 20 from reservoir 10 can be heated, such as it is heated to 50 DEG C, so that the partial oxidation hydrogen in printed circuit board etching waste liquid separates after flashing to gas, and is entered in cooling bath 30 by gas adapter 21。
Cooling bath 30 be arranged over two condensers (sign), the temperature of the hydrogen chloride gas passed into from gas adapter 21 can be cooled to 5 ~ 10 DEG C within the condenser, and after being condensed into liquid, hydrogen chloride gas knows from experience the absorbed formation hydrochloric acid of water in cooled groove 30。
Precipitation separation device 40, by liquid adapter 23 and vaporising device 20 fluid communication, is removed the residue printed circuit board etching waste liquid after hydrogen chloride and is entered in precipitation separation device 40 by liquid adapter 23。When toward when putting into alkali liquor (such as NaOH) in precipitation separation device 40, the partial oxidation copper in printed circuit board etching waste liquid can be converted into Copper hydrate precipitation, it is then passed through separating and obtains Copper hydrate and precipitate and rich in the supernatant solution of NaCl。In order to accelerate transformation efficiency, in precipitation separation device 40, it is additionally provided with agitating device (sign)。
Reaction equation is: CuCl2+2NaOH→2Cu(OH)2↓+NaCl
First electrolysis dashpot 50 is by liquid adapter 41 and precipitation separation device 40 fluid communication。Precipitation separation device 40 separates the Copper hydrate precipitation obtained by after liquid adapter 41 entrance the first electrolysis dashpot 50, under the ammonia of outside interpolation or the effect of ammonium salt (such as ammonium sulfate), it is possible to be converted into cupric ammine complex。
Reaction equation is: Cu (OH)2+4NH3→[Cu(NH3)4]2++2OH-
Electrolysis bath 60 is by liquid adapter 51 and the first electrolysis dashpot 50 fluid communication。Electrolysis is there is in the cupric ammine complex formed in the first electrolysis dashpot 50 after entering electrolysis bath 60。
Cathode reaction: (Cu (NH3)4〕2++2e-→Cu+4NH3
Copper simple substance and ammonia is thus produced on cathode chamber。In the present embodiment, the copper simple substance of generation adheres on the cathode electrode with the form of copper coin, therefore can pass through the mode changing electrode and be taken out by copper simple substance。
Anode reaction: 2NH3+2H2O→2(NH4)++2OH-
2OH-→1/2O2+H2O+2e-
In the present embodiment, electrolysis bath 60 is also by gas adapter 61 and the first electrolysis dashpot 50 fluid communication。The ammonia that the cathode chamber of electrolysis bath 60 produces enters the first electrolysis dashpot 50 by gas adapter 61, thus Copper hydrate precipitation is converted into cupric ammine complex, to realize recycling of ammonia。It is appreciated that then gas adapter 61 also can be omitted if the ammonia passing into the first electrolysis dashpot 50 is introduced from outside into。
Ion-exchange membrane electrolyzer 70 includes anode region 72, relief area 74 and cathode chamber 76。Anode region 72 and relief area 74 are separated by anionic membrane 721, and relief area 74 and cathode chamber 76 are separated by cationic membrane 761。Anionic membrane 721 can make anion by and stop cation to be passed through；Cationic membrane 761 can make cation by and stop anion to be passed through。Ion-exchange membrane electrolyzer 70 also includes temporary tank 78。Temporary tank 78 is communicated by liquid adapter (sign) with anode region 72, for storing the electrolyte after the electrolysis of anode region 72。
The relief area 74 of ion-exchange membrane electrolyzer 70 is by liquid adapter 42 and precipitation separation device 40 fluid communication。A large amount of NaCl and a small amount of CuCl is comprised in precipitation separation device 402Solution can pass through liquid adapter 42 entrance relief area 74, and spread to anode region 72 and cathode chamber 76 under the effect of cationic membrane 761 and anionic membrane 721。Concrete, chloride ion will enter anode region 72, and copper ion and sodium ion will enter cathode chamber 76。
When there is electrolysis, there is following chemical reaction in cathode chamber 76:
Cu2++2e-→Cu
Cu++e-→Cu
2H2O+2e-→H2+2OH-
OH-+Na+→NaOH
Thus produce copper simple substance and sodium hydroxide。In the present embodiment, the copper ion owing to entering cathode chamber 76 is less, and the copper simple substance therefore produced is present in electrolyte with the form of copper powder。
There is following chemical reaction in anode region 72:
H2O→1/2O2+2H++2e-
2Cl-→Cl2+2e-
2Cl2+H2O→2HClO+2HCl
The gas that anode region 72 produces (is mainly Cl2And HCl) by connecting the gas adapter 34 entrance cooling bath 30 of ion-exchange membrane electrolyzer 70 and cooling bath 30, and absorption becomes hydrochloric acid under the effect of condenser。
After the electrolysis of anode region 72, remaining electrolyte enters temporary tank 78 by liquid adapter。In the present embodiment, temporary tank 78 is by liquid adapter 52 and the first electrolysis dashpot 50 fluid communication, and the first electrolysis dashpot 50 passes through anode region 72 and relief area 74 fluid communication of liquid adapter 53 and the first electrolysis dashpot 50。In first electrolysis dashpot 50, the electrolyte after electrolysis bath 60 electrolysis is injected separately into anode region 72 and relief area 74 by liquid adapter 53, and the electrolyte after ion-exchange membrane electrolyzer 70 electrolysis is injected in the first electrolysis dashpot 50 by liquid adapter 52, it is consequently formed circulation。It is appreciated that liquid adapter 52 and liquid adapter 53 also can be omitted if being made without repeatedly circulating。
The cathode chamber 76 of filtering ponds 80 and ion-exchange membrane electrolyzer 70 is by liquid adapter 82 fluid communication, and collects by filtration copper powder。
Second electrolysis dashpot 90 is by liquid adapter 92 and filtering ponds 80 fluid communication, and collects sodium hydroxide solution。
In the present embodiment, the second electrolysis dashpot 90 is also by cathode chamber 76 fluid communication of liquid adapter 94 with ion-exchange membrane electrolyzer 70, and the continuous cathode chamber 76 that sodium hydroxide solution injects ion-exchange membrane electrolyzer 70, with the moisture that supplementary cathode chamber 76 consumes。It is appreciated that liquid adapter 94 also can be omitted if supplementing the moisture that cathode chamber 76 consumes by other means。
In the present embodiment, second electrolysis dashpot 90 is also by liquid adapter 96 and precipitation separation device 40 fluid communication, and sodium hydroxide solution is injected precipitation separation device 40, so that the partial oxidation copper in the printed circuit board etching waste liquid after removal hydrogen chloride is converted into Copper hydrate precipitation。It is appreciated that then liquid adapter 96 also can be omitted if adopting the NaOH of extraneous introducing。
Refer to Fig. 2, the processing method of the printed circuit board etching waste liquid of an embodiment, comprise the steps:
Step S101, use reservoir memory print plate etching waste liquor, the composition of described printed circuit board etching waste liquid includes copper chloride and hydrogen chloride and sodium chloride。
Such as, printed circuit board etching waste liquid can be stored in reservoir 10。
Step S102, by described reservoir printed circuit board etching waste liquid inject vaporising device, make in printed circuit board etching waste liquid hydrogen chloride evaporation separate, the hydrogen chloride gas obtained, be passed in cooling bath, after condensed absorbent formed hydrochloric acid。
Such as, can be injected in vaporising device 20 by liquid adapter 11 by the printed circuit board etching waste liquid in reservoir 10 to be heated processing, so that the partial oxidation hydrogen in printed circuit board etching waste liquid separates after flashing to gas, and entering in cooling bath 30 by gas adapter 21, condensation forms hydrochloric acid。
Step S103, inject precipitation separation device by removing the printed circuit board etching waste liquid after hydrogen chloride, and partial oxidation copper is converted into Copper hydrate precipitation, separate, obtain the solution after removing Copper hydrate precipitation。
Such as, can the printed circuit board etching waste liquid after removing hydrogen chloride be entered in precipitation separation device 40 by liquid adapter 23, then in precipitation separation device 40, alkali liquor (such as NaOH) is put into, make the partial oxidation copper in printed circuit board etching waste liquid can be converted into Copper hydrate precipitation, be then passed through separating and obtain Copper hydrate precipitation and the supernatant solution rich in NaCl。Copper hydrate precipitation enters step S104, solution enters step S106。
Step S104, by described Copper hydrate precipitation proceed to the first electrolysis dashpot, with ammonia or ammonium salt react generate cupric ammine complex。
Such as, precipitation separation device 40 separates the Copper hydrate precipitation obtained by after liquid adapter 41 entrance the first electrolysis dashpot 50, it is possible under the effect of ammonia or ammonium salt (such as ammonium sulfate), be converted into cupric ammine complex。
Step S105, described cupric ammine complex being injected electrolysis bath, electrolysis produces copper simple substance and ammonia。
Such as, there is electrolysis, produce copper simple substance and ammonia respectively on cathode chamber and anode region in the cupric ammine complex formed in the first electrolysis dashpot 50 after entering electrolysis bath 60 by liquid adapter 51。
In the present embodiment, the ammonia that the cathode chamber of electrolysis bath 60 produces enters the first electrolysis dashpot 50 by gas adapter 61, thus Copper hydrate precipitation is converted into cupric ammine complex, to realize recycling of ammonia。
Step S106, described removal Copper hydrate is precipitated after solution inject the relief area of ion-exchange membrane electrolyzer, the anode region electrolysis at described ion-exchange membrane electrolyzer produces chlorine, forms hydrochloric acid after condensed absorbent；Make the cathode chamber being positioned at the copper ion of the electrolyte of described relief area and the sodium ion described ion-exchange membrane electrolyzer of entrance, produce copper simple substance and sodium hydroxide solution in the electrolysis of described cathode chamber。
Such as, a large amount of NaCl and a small amount of CuCl is comprised in precipitation separation device 402Solution can pass through liquid adapter 42 and enter relief area 74, and spread to anode region 72 and cathode chamber 76 under the effect of cationic membrane 761 and anionic membrane 721, chloride ion will enter anode region 72, and copper ion and sodium ion will entrance cathode chambers 76。During electrolysis, cathode chamber 76 produces copper simple substance and sodium hydroxide；Anode region 72 produces chlorine。The gas that anode region 72 produces enters cooling bath 30 by connecting the gas adapter 34 of ion-exchange membrane electrolyzer 70 and cooling bath 30, and absorption becomes hydrochloric acid under the effect of condenser。
After the electrolysis of anode region 72, remaining electrolyte enters temporary tank 78。In the present embodiment, in first electrolysis dashpot 50, the electrolyte after electrolysis bath 60 electrolysis is injected separately into anode region 72 and relief area 74 by liquid adapter 53, and the electrolyte after electrolysis bath 60 electrolysis is injected in the first electrolysis dashpot 50 by liquid adapter 52, it is consequently formed circulation。
Step S107, use filtering ponds collect by filtration described copper simple substance。
Such as, the copper simple substance generated on cathode chamber 76 enters filtering ponds 80 by liquid adapter 82, and in the filtered collection of filtering ponds 80。
Step S108, use second electrolysis dashpot collect described sodium hydroxide solution。
Such as, the sodium hydroxide generated on cathode chamber 76 enters the second electrolysis dashpot 90 by liquid adapter 92, obtains, thus collecting at the second electrolysis dashpot 90, the sodium hydroxide solution that concentration is about 25%。
Preferably, the cathode chamber 76 that the sodium hydroxide solution in the second electrolysis dashpot 90 enters into ion-exchange membrane electrolyzer 70 by liquid adapter 94 is circulated, with the moisture of supplementary consumption。
Preferably, sodium hydroxide solution is injected precipitation separation device 40 also by liquid adapter 96 by the second electrolysis dashpot 90, so that the partial oxidation copper in the printed circuit board etching waste liquid after removal hydrogen chloride is converted into Copper hydrate precipitation。
In said method, step S103 ~ S105 is the main recycling channel of Cu, and step S106 ~ S108 is the main recycling channel of Na, and two groups of steps both can sequentially carry out, it is also possible to carry out simultaneously。
After said system and etching line are connected with each other, circulation running, HCl and NaOH can be obtained while Footwall drift copper, restored acid can send in real time etching line again with, the alkali of recovery does corresponding storage。Whole process is without any waste water, waste gas and waste discharge, it is to avoid secondary pollution, and whole etching work and recovery system are fully achieved Automated condtrol, it is ensured that whole system is stable, periodic duty safely。
When etching solution entrance vaporising device 20 is evaporated, it is possible to by CuCl2Separate with acidic materials HCl therein, reduce the acidity of etching solution, the precipitation of the copper in promotion electrolysis bath 60。On the other hand, chlorine extraction in the ammonia in electrolysis bath 60 and ion-exchange membrane electrolyzer 70 can be strengthened Cu2+And Cu+Redox reaction between chemical potential energy poor, promote copper electrolysis。
Embodiment described above only have expressed the several embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention。It should be pointed out that, for the person of ordinary skill of the art, without departing from the inventive concept of the premise, it is also possible to making some deformation and improvement, these broadly fall into protection scope of the present invention。Therefore, the protection domain of patent of the present invention should be as the criterion with claims。
Claims (12)
1. a printed circuit board etching waste liquid processes system, it is characterised in that including: reservoir, vaporising device, cooling bath, precipitation separation device, the first electrolysis dashpot, electrolysis bath, ion-exchange membrane electrolyzer, filtering ponds and the second electrolysis dashpot, wherein,
Described reservoir is used for memory print plate etching waste liquor, and the composition of described printed circuit board etching waste liquid includes copper chloride, hydrogen chloride and sodium chloride；
Described vaporising device is connected with described reservoir, separates for being evaporated by the hydrogen chloride in described printed circuit board etching waste liquid；
Described cooling bath is connected with described vaporising device, for receiving the hydrogen chloride gas that described vaporising device produces, forms hydrochloric acid after condensed absorbent；
Described precipitation separation device is connected with described vaporising device, and the partial oxidation copper removed in the printed circuit board etching waste liquid after hydrogen chloride is converted into Copper hydrate precipitation at described precipitation separation device, and makes precipitation and solution separating；
Described first electrolysis dashpot is connected with described precipitation separation device, separates the Copper hydrate precipitation obtained and enters described first electrolysis dashpot, and is converted into cupric ammine complex at described first electrolysis dashpot；
Described electrolysis bath is connected with described first electrolysis dashpot, and described cupric ammine complex is copper simple substance and ammonia at described electrolytic tank electrolysis；
Described ion-exchange membrane electrolyzer includes anode region, relief area and cathode chamber, described anode region and described relief area are separated by anionic membrane, described relief area and described cathode chamber are separated by cationic membrane, described relief area is for receiving from the solution after the removal Copper hydrate precipitation of described precipitation separation device, described anode region produces to pass into the chlorine of described cooling bath for electrolysis, and described cathode chamber produces copper simple substance and sodium hydroxide solution for electrolysis；
Described filtering ponds are connected with described ion-exchange membrane electrolyzer, are used for collecting by filtration described copper simple substance；
Described second electrolysis dashpot is connected with described filtering ponds, is used for collecting described sodium hydroxide solution；
Described electrolysis bath is connected with described first electrolysis dashpot, and the ammonia that described electrolytic tank electrolysis produces enters described first electrolysis dashpot, makes Copper hydrate precipitation be converted into cupric ammine complex；
Described second electrolysis dashpot is connected with described precipitation separation device, and described sodium hydroxide solution is injected precipitation separation device, so that the partial oxidation copper in the printed circuit board etching waste liquid after described removal hydrogen chloride to be converted into Copper hydrate precipitation。
2. printed circuit board etching waste liquid according to claim 1 processes system, it is characterized in that, described first electrolysis dashpot is connected with described ion-exchange membrane electrolyzer, the interior electrolyte after described electrolytic tank electrolysis of described first electrolysis dashpot is injected separately into anode region and the relief area of described ion-exchange membrane electrolyzer, and the electrolyte after ion-exchange membrane electrolyzer electrolysis injects described first electrolysis dashpot。
3. printed circuit board etching waste liquid according to claim 1 processes system, it is characterized in that, described second electrolysis dashpot is connected with described ion-exchange membrane electrolyzer, and the sodium hydroxide solution in described second electrolysis dashpot injects the cathode chamber of described ion-exchange membrane electrolyzer。
4. a printed circuit board etching waste liquid processing method, it is characterised in that comprise the steps:
Using reservoir memory print plate etching waste liquor, the composition of described printed circuit board etching waste liquid includes copper chloride and hydrogen chloride and sodium chloride；
Printed circuit board etching waste liquid in described reservoir being injected vaporising device, makes the hydrogen chloride evaporation in printed circuit board etching waste liquid separate, the hydrogen chloride gas obtained is passed in cooling bath, forms hydrochloric acid after condensed absorbent；
Printed circuit board etching waste liquid after removing hydrogen chloride is injected precipitation separation device, and partial oxidation copper is converted into Copper hydrate precipitation, separate, obtain the solution after removing Copper hydrate precipitation；
Described Copper hydrate precipitation is proceeded to the first electrolysis dashpot, reacts generation cupric ammine complex with ammonia or ammonium salt；
Described cupric ammine complex is injected electrolysis bath, and electrolysis produces copper simple substance and ammonia；
Solution after being precipitated by described removal Copper hydrate injects the relief area of ion-exchange membrane electrolyzer, and the anode region electrolysis at described ion-exchange membrane electrolyzer produces chlorine, forms hydrochloric acid after condensed absorbent；Make the cathode chamber being positioned at the copper ion of the electrolyte of described relief area and the sodium ion described ion-exchange membrane electrolyzer of entrance, produce copper simple substance and sodium hydroxide solution in the electrolysis of described cathode chamber；
Filtering ponds are used to collect by filtration described copper simple substance；And
The second electrolysis dashpot is used to collect described sodium hydroxide solution。
5. printed circuit board etching waste liquid processing method according to claim 4, it is characterised in that the ammonia that described electrolytic tank electrolysis produces enters described first electrolysis dashpot, makes Copper hydrate precipitation be converted into cupric ammine complex。
6. printed circuit board etching waste liquid processing method according to claim 5, it is characterized in that, the molten anode region being injected separately into described ion-exchange membrane electrolyzer after described electrolytic tank electrolysis and relief area in described first electrolysis dashpot, the electrolyte after ion-exchange membrane electrolyzer electrolysis injects described first electrolysis dashpot and is circulated。
7. printed circuit board etching waste liquid processing method according to claim 4, it is characterized in that, described sodium hydroxide solution in described second electrolysis dashpot injects described precipitation separation device, so that the partial oxidation copper in the printed circuit board etching waste liquid after described removal hydrogen chloride to be converted into Copper hydrate precipitation。
8. printed circuit board etching waste liquid processing method according to claim 4, it is characterised in that the described sodium hydroxide solution in described second electrolysis dashpot injects the cathode chamber of described ion-exchange membrane electrolyzer and is circulated。
9. a printed circuit board etching waste liquid processes system, it is characterised in that including:
Reservoir；
Vaporising device with reservoir fluid communication；
With the cooling bath that vaporising device fluid communication extracts boil-off gas；
With vaporising device fluid communication to extract through remaining after evaporation liquid and in the precipitation separation device that precipitation wherein occurs；
Precipitate, with what will precipitation separation device produce, the first electrolysis dashpot collected with precipitation separation device fluid communication；
Electrolysis bath with the first electrolysis dashpot circulation；
With precipitation separation device fluid communication so that remaining liq after precipitation is extracted in the ion-exchange membrane electrolyzer that electrolysis wherein occurs；And
The second electrolysis dashpot with ion-exchange membrane electrolyzer fluid communication；
Described second electrolysis dashpot and precipitation separation device fluid communication are with liquid needed for supplying precipitation to precipitation separation device；
Described ion-exchange membrane electrolyzer and the first electrolysis dashpot fluid communication, to extract liquid in the first dashpot, are further provided with filtering ponds between ion-exchange membrane electrolyzer and the second electrolysis dashpot。
10. printed circuit board etching waste liquid according to claim 9 processes system, it is characterized in that: described ion-exchange membrane electrolyzer includes anode region, cathode chamber and the relief area between anode region and cathode chamber, separated by anionic membrane between anode region and relief area, separated by cationic membrane between cathode chamber and relief area, described cooling bath and anode region fluid communication, described precipitation separation device and relief area fluid communication, the first electrolysis dashpot and anode region and relief area fluid communication simultaneously。
11. printed circuit board etching waste liquid according to claim 10 process system, it is characterised in that: described ion-exchange membrane electrolyzer farther includes the temporary tank of and anode region fluid communication, temporary tank further with the first electrolysis dashpot fluid communication。
12. printed circuit board etching waste liquid according to claim 9 processes system, it is characterised in that: with ion-exchange membrane electrolyzer fluid communication to collect the gas that electrolysis produces the while of described cooling bath。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178721.2A CN103451675B (en) | 2012-06-01 | 2012-06-01 | Printed circuit board etching waste liquid processes system and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178721.2A CN103451675B (en) | 2012-06-01 | 2012-06-01 | Printed circuit board etching waste liquid processes system and 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 |
| CN106587105B (en) * | 2016-12-15 | 2018-07-20 | 赣州明高科技股份有限公司 | The recovery method of copper chloride acid etching liquid in a kind of printed circuit board |
| CN107385445A (en) * | 2017-07-27 | 2017-11-24 | 四会富士电子科技有限公司 | A kind of method that circuitboard etching waste liquid recycles |
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| CN101003394A (en) * | 2006-01-16 | 2007-07-25 | 陈尚林 | System and method for treating waste solution from acidity etching printed circuit board |
| TW200906737A (en) * | 2007-08-07 | 2009-02-16 | Trinity Resources Technology Holding Inc | Recycling method for copper resource in process |
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| CN101748430A (en) * | 2009-09-23 | 2010-06-23 | 王红华 | Copper recovery system of printed board acid etching waste solution and etching solution regeneration method |
| CN101988200A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Cyclic regeneration and metal reclamation equipment for acid chloride-containing etchant |
| CN202643846U (en) * | 2012-06-01 | 2013-01-02 | 库特勒自动化系统(苏州)有限公司 | Etching waste liquid treatment system of printing plate |
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| CN101003394A (en) * | 2006-01-16 | 2007-07-25 | 陈尚林 | System and method for treating waste solution from acidity etching printed circuit board |
| TW200906737A (en) * | 2007-08-07 | 2009-02-16 | Trinity Resources Technology Holding Inc | Recycling method for copper resource in process |
| JP2010059502A (en) * | 2008-09-04 | 2010-03-18 | Takuo Kawahara | Treatment method and device for copper etching waste solution |
| CN101988200A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Cyclic regeneration and metal reclamation equipment for acid chloride-containing etchant |
| CN101748430A (en) * | 2009-09-23 | 2010-06-23 | 王红华 | Copper recovery system of printed board acid etching waste solution and etching solution regeneration method |
| CN202643846U (en) * | 2012-06-01 | 2013-01-02 | 库特勒自动化系统(苏州)有限公司 | Etching waste liquid treatment system of printing plate |
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