CN209412325U - A kind of device of efficient activated acid etching solution - Google Patents

A kind of device of efficient activated acid etching solution Download PDF

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Publication number
CN209412325U
CN209412325U CN201821995824.7U CN201821995824U CN209412325U CN 209412325 U CN209412325 U CN 209412325U CN 201821995824 U CN201821995824 U CN 201821995824U CN 209412325 U CN209412325 U CN 209412325U
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China
Prior art keywords
cylinder
chlorine
pipeline
absorption
absorbs
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CN201821995824.7U
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陈丽珊
潘清儒
陈达祁
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Zhuhai Wisdom Chemical Co Ltd
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Zhuhai Wisdom Chemical Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The utility model discloses a kind of device of efficient activated acid etching solution, which includes etch system, electrolysis system, regenerated liquid storage tank, multistage absorption system and exhaust gas processing device;The etch system, electrolysis system, regenerated liquid storage tank are sequentially connected with by pipeline and form circulation loop, the chlorine that the electrolysis system generates successively is passed through in the multistage absorption system and exhaust gas processing device by pipeline, the acidic etching liquid of the etch system by tube overflow into the multistage absorption system, and in the multistage absorption system acidic etching liquid overflow direction it is opposite with the flow direction of chlorine;The multistage absorption system is connected to etch system by pipeline, so that the acidic etching liquid reuse after activation is into the etch system.The device absorbs chlorine by setting multistage absorption system and the reverse circuit of air-liquid, and to the good absorption effect of chlorine, regenerated liquid reclamation rate is up to 95% or more, realizes resource maximization and recycles, operating cost is low.

Description

A kind of device of efficient activated acid etching solution
Technical field
The utility model relates to printed circuit board etching solution technical fields, and in particular to a kind of efficient activated acid etching solution Device.
Background technique
Etching is the important process in printed circuit board processing procedure, and wherein acid etching is because of the small, fine etching with lateral erosion Ability is used widely with the advantages that easily controllable rate by force.Cu in acidic copper chloride etching process, in etching solution2+ With oxidisability, and the copper on circuit board has reproducibility, and following chemical reaction occurs for the two contact:
CuCl2+Cu→2CuCl↓
The stannous chloride CuCl of slightly solubility can circuit board surface formed thin film, and then prevent reaction continuation into Row, but since there are a large amount of chloride ions in etching solution, chloride ion can generate complex ion in conjunction with CuCl, to make CuCl It is dissolved down from copper surface to maintain erosion copper reaction.The CuCl of indissoluble is converted into soluble complex ion, and it is anti-that following complexing occurs It answers:
2CuCl+4Cl-→2[CuCl3]2-
But the reaction speed is relatively slow, the Cu with the progress of erosion copper reaction, in solution2+Concentration will constantly decline, and The Cu of accumulation+More and more, solution O RP (oxidation-reduction potential) is decreased, and shows as etching speed rapid decrease, etching energy Power decrease fast, etch effect deterioration, until finally losing efficiency.To continue to keep the erosion copper ability of medical fluid, need to etching Liquid carries out activating and regenerating, makes Cu+It is transformed into Cu as early as possible2+, the ORP of solution is improved, to maintain the etching speed of normal table.
Comprehensively consider the factors such as manufacturing cost and environmental pollution, it is electricity that industry application, which obtains more regeneration techniques method, at present Acidic etching liquid is passed through diaphragm cell by solution, copper ion is reduced into metallic copper recycling under applying direct current effect, Regenerated liquid (i.e. electrolyte) after supplemental oxidant and hydrochloric acid again reuse to etching line.Main electrodes reaction is as follows:
Anode reaction: Cu+-e-→Cu2+
2Cl--2e-→Cl2
Cathode reaction: Cu2++e-→Cu+
Cu++e-→Cu0
The advantages of electrolysis method is can directly to recycle copper extra in etching solution, while anode can make part Cu in solution again+It is oxidized to Cu2+It is regenerated, the ORP of electrolyte is made to have a degree of promotion, be conducive to the oxidisability for improving regenerated liquid.But Fail really effectively to recycle chlorine caused by electrolytic process using the prior art of electrolysis method described above at present: Typically by electrolysis generate chlorine be passed through regeneration fluid cylinder or be passed directly into production line etching fluid cylinder, due in regenerated liquid itself Can be seldom by the univalent copper ion of chlorine oxidation, while solution acidity is higher after electrolysis, it is also limited to the absorption dissolution of chlorine, because This is poor to the assimilation effect of chlorine;Although such as chlorine, which is passed directly into etching solution, has more univalent copper ion can be by chlorine Gas oxidation utilizes, but actual production process can be mixed with the copper sheet of different-thickness often and need to etch, and etching solution is to thick copper and thin The amount of oxidant consumed by copper is different, that is to say, that in etching process chlorine as oxidant, etching solution is to chlorine Uptake be not it is constant, that is, it is more to absorb chlorine when etching thick copper, it is few that chlorine is absorbed when etching thin copper, but electrolysis installation generates Amount of chlorine be substantially it is constant, both result in not matching in this way, it is unstable or even etching matter occurs etching speed occur Amount accident.For the continuous-stable for maintaining etching speed, just need constantly additionally to add oxidant and hydrochloric acid when producing thick copper, this side Method will cause etching solution and constantly expand, and regenerated liquid utilization rate reduces.It can be seen that in the prior art either generate electrolysis Chlorine be passed through single or multiple regeneration fluid cylinders be still passed directly into producing line etching fluid cylinder, can not all change chlorine absorption it is poor, regenerate The low problem of liquid reclamation rate.
Whether chlorine is sufficiently the key that regenerated liquid reclamation rate height as its recycling of oxidant, according to industry practice Situation, the existing usual reclamation rate of electrolytic regeneration reuse technology only have 50%-60%, and immediate cause is exactly chlorine not by abundant benefit It is recycled with returning in etch systems, causes the loss and thus bring high consumption, environmental pollution and vent gas treatment of chlorine The problems such as increased costs, is unable to reach the purpose that resource makes full use of and production process is environmentally friendly, safe.
Utility model content
For overcome the deficiencies in the prior art, the purpose of this utility model is to provide a kind of efficient activated acid etching solutions Device, which absorbs chlorine by setting multistage absorption system and the reverse circuit of air-liquid, to the good absorption effect of chlorine, Regenerated liquid reclamation rate is up to 95% or more simultaneously, realizes resource maximization and recycles, supplies consumption is few, and operating cost is low.
To solve the above problems, technical solution used by the utility model is as follows:
A kind of device of efficient activated acid etching solution comprising etch system, electrolysis system, regenerated liquid storage tank, multistage Absorption system and exhaust gas processing device;The etch system, electrolysis system, regenerated liquid storage tank are sequentially connected with and are formed by pipeline Circulation loop, the chlorine that the electrolysis system generates successively are passed through the multistage absorption system and exhaust gas processing device by pipeline In, the acidic etching liquid of the etch system passes through tube overflow into the multistage absorption system, and the multistage absorption system The overflow direction of acidic etching liquid is opposite with the flow direction of chlorine in system;The multistage absorption system and etch system pass through pipe Road connection, so that the acidic etching liquid reuse after activation is into the etch system.
As the utility model preferred embodiment, the multistage absorption system includes the n grades of absorption cylinders being sequentially connected in series, N >=2, and n is positive integer.
As the utility model preferred embodiment, the electrolysis system passes through the pipeline with centrifugal pump and ejector The bottom for absorbing cylinder with the first order be connected to, the first order absorb the top of cylinder by pipeline with centrifugal pump and ejector and The second level absorbs the bottom connection of cylinder, and the second level absorbs the top of cylinder by having the pipeline of centrifugal pump and ejector under The bottom of first order absorption cylinder is connected to, and so on, the bottom that cylinder absorbs cylinder with n-th grade, which is absorbed, until (n-1)th grade is connected to, it is described The top of n-th grade of absorption cylinder is connected to by pipeline with the exhaust gas processing device, to form gas flow path.
As the utility model preferred embodiment, the etch system absorbs cylinder with described n-th grade by pipeline Top connection, the bottom that the top of n-th grade of absorption cylinder absorbs cylinder with described (n-1)th grade are connected to, (n-1)th grade of absorption cylinder Top with described the n-th -2 grades absorb cylinders bottom be connected to, and so on, until the second level absorb cylinder and the first order absorption The bottom of cylinder is connected to, and the bottom that the first order absorbs cylinder is connected to the etch system, to form liquid flow path.
As the utility model preferred embodiment, the etch system includes etching cylinder and is connected to the etching cylinder Waste collection slot, the waste collection slot passes through pipeline and the electrolysis system and multistage absorption system connectivity respectively, described Multistage absorption system is connected to by pipeline with the etching cylinder, and the regenerated liquid storage tank is connected to by pipeline with the etching cylinder.
As the utility model preferred embodiment, the electrolysis system includes sequentially connected filter device, electrolysis Slot and copper device is mentioned, the filter device is connected to the waste collection slot, and the electrolytic cell is connected to the regenerated liquid storage tank.
As the utility model preferred embodiment, it is provided with diaphragm in the electrolytic cell, the diaphragm is by the electricity Solution slot is separated into cathode chamber and anode chamber, and anode plate is equipped in the anode chamber, is equipped with cathode plate in the cathode chamber;Institute Anode chamber is stated by pipeline and the multistage absorption system connectivity, the cathode chamber, which is connected with, described mentions copper device;The regeneration Blender is equipped in liquid storage tank.
As the utility model preferred embodiment, the device of the utility model further includes having central control system, it is described in Control system passes through the ORP and specific gravity data of etching solution in etch system described in real-time monitoring, to control the activated acidity The reuse amount of etching solution and regenerated liquid.
The utility model additionally provides a kind of method of efficient activated acid etching solution, applies device as described above, It is obtained the following steps are included: cathode and anode liquid is uniformly mixed by the acidic etching liquid in waste collection slot after electrolysis mentions copper Regenerated liquid, by regenerated liquid reuse into etch system;The chlorine that electrolysis system generates successively is passed through in multistage absorption system, finally Into being handled in exhaust gas processing device;Acidic etching liquid in the waste collection slot is to flow to opposite flowing with chlorine Successively into the multistage absorption system, the acidic etching liquid in the last multistage absorption system is delivered to described for overflow in direction It is recycled in etch system.
As the utility model preferred embodiment, method described in the utility model specifically includes the following steps:
S1, the acidic etching liquid that the etch system generates is collected into the waste collection slot;
S2, progress electricity in the electrolysis system will be delivered to after the filtering of the partially acidic etching solution in the waste collection slot Copper is solved and mentioned, the cathode and anode liquid stream after mentioning copper is electrolysed and enters in regenerated liquid storage tank, stirring is uniformly mixed it, obtains low-gravity Regenerated liquid, regenerated liquid are recycled by pipeline into the etch system;
S3, the indoor chlorine of electrolysis system Anodic are sent into the first order by closed conduit and are absorbed in cylinder, and described the The gaseous mixture isolated at the top of first order absorption cylinder is sent into the second level and is absorbed in cylinder, isolates at the top of the second level absorption cylinder mixed Gas is closed then to be sent into next stage absorption cylinder, and so on, the gaseous mixture isolated at the top of cylinder is absorbed until n-th grade to be sent at tail gas Manage device;
Another part acidic etching liquid overflow in S4, the waste collection slot is into n-th grade of absorption cylinder, n-th grade of absorption In the supreme first order absorption cylinder of acidic etching liquid overflow in cylinder, and so on, up to acidic etching liquid overflow to the first order It absorbs in cylinder, the acidic etching liquid that the first order absorbs in cylinder, which is delivered in the etch system, to be recycled.
Compared with prior art, the utility model has the beneficial effects that:
The chlorine that the device of efficient activated acid etching solution described in the utility model is generated based on acidic etching liquid electrolysis The principle of univalent copper ion can be aoxidized, is designed multistage absorption system (series n >=2), and constructs and flows to opposite chlorine circulation Gas flow path and acidic etching liquid circulating liquid flow path, it is ensured that chlorine can be absorbed utilization to the maximum extent, inhale the first order The solution height activation in cylinder is received, reaches the first order and absorbs in cylinder Cu in solution2+Content highest, Cu+At least n-th grade of content The minimum effect even without chlorine discharge of the amount of chlorine of cylinder discharge is absorbed, while cooperating etching solution in on-line monitoring etch system Specific gravity and ORP regulate and control the usage amount that the activating solution in regenerated liquid and first order absorption cylinder is back to etch system, to realize Regeneration etching matches with electrolysis system, is back to use electrolysate all sufficiently in etch systems, effectively maintains etching speed It is stable and continuous, meet the requirement of online etching, electrolysis and reuse, realizes that resource maximization recycles, greatly improve regeneration The reclamation rate of liquid, efficiently solve the chlorine that the prior art fails to make full use of electrolysis to generate and caused by regenerated liquid reclamation rate It is low, etching speed is unstable, the high consumption of operation and the problems such as environmental pollution.
Device described in the utility model has the following beneficial effects:
1, opposite chlorine recyclegas flow path and acidic etching liquid circulating liquid flow path are flowed to by construction, utilizes multistage The reverse back dissolving of air-liquid absorbs chlorine, and the chlorine for generating electrolysis is recycled to greatest extent;
2, regulate and control the work in regenerated liquid and first order absorption cylinder by the specific gravity and ORP of etching solution in control etch system Change liquid and be back to the usage amount in etch system, the control model of biliquid addition be effectively guaranteed etching speed stability and Continuity;
3, the utility model can enable chlorine adequately absorb reuse, be reduced as far as chlorine in whole system Loss effectively prevents medical fluid expansion to reduce the additional magnitude of recruitment of hydrochloric acid and oxidant, and environment protecting is significant;
4, electrolysate is sufficiently back to etch systems, realizes that resource maximization recycles, regenerated liquid reclamation rate is high Up to 95% or more, compared to the regenerated liquid reclamation rate of prior art 50%-60%, improvement is significant;
5, the material balance for keeping electrolytic regeneration and reuse process to the maximum extent, greatly reduces other supplies consumptions, transports Row overall cost reduces 45% compared with the prior art;
6, since chlorine is recycled to greatest extent, therefore the tail gas that generates of etch system is few even without discharge, To further decrease the processing pressure and cost of tail gas, resultant effect is more preferably.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the device of efficient activated acid etching solution described in the utility model;
Fig. 2 is the process flow chart of the method for efficient activated acid etching solution described in the utility model;
Fig. 3 is the structural schematic diagram of device described in the utility model embodiment 1;
Fig. 4 is the structural schematic diagram of device described in the utility model embodiment 2;
Fig. 5 is the structural schematic diagram of device described in the utility model embodiment 3;
Fig. 6 is the structural schematic diagram of device described in the utility model comparative example 1;
Fig. 7 is the structural schematic diagram of device described in the utility model comparative example 2.
In attached drawing, solid line modesty arrow is gas flow path, and solid line filled arrows are that liquid flows to path, and dotted line is solid Arrow is the control path of central control system.
Specific embodiment
The utility model is described in further detail with reference to the accompanying drawings and detailed description.
As shown in Figure 1, the device of efficient activated acid etching solution described in the utility model includes etch system, electrolysis system System, regenerated liquid storage tank, multistage absorption system, exhaust gas processing device and central control system;Wherein, etch system mainly utilizes acid erosion Carve etching of the liquid completion to electronic circuit board;Electrolysis system is used to copper ion extra in acidic etching liquid being changed into metallic copper And it is extracted from cathode, while regenerate the univalent copper ion in solution in anodic conversion bivalent cupric ion;Regenerated liquid storage Slot obtains regenerated liquid for anolyte and catholyte to be uniformly mixed;Multistage absorption system is used to dissolve the chlorine that electrolysis generates, Guarantee that chlorine can be absorbed dissolution to the maximum extent, so that acidic etching liquid is sufficiently activated;Exhaust gas processing device is for locating Manage a small amount of chlorine not absorbed by multistage absorption system;Central control system is used to monitor on-line the ratio of acidic etching liquid in etch system Regulate and control the usage amount that the activating solution in regenerated liquid and multistage absorption system is back in etch system with ORP again.Etch system, Electrolysis system, regenerated liquid storage tank are sequentially connected with by pipeline and are formed circulation loop, and the chlorine that electrolysis system generates passes through pipeline It is successively passed through in multistage absorption system and exhaust gas processing device, the acidic etching liquid of etch system is inhaled by tube overflow to multistage In receipts system, and in multistage absorption system acidic etching liquid overflow direction it is opposite with the flow direction of chlorine;Multistage absorption system System is connected to etch system by pipeline, so that the acidic etching liquid reuse being activated is into etch system.
Specifically, etch system includes etching cylinder and waste collection slot, electrolysis system are by filter device, electrolytic cell and to mention The closed system that copper device is constituted, etching cylinder, waste collection slot, filter device, electrolytic cell and regenerated liquid storage tank are suitable by pipeline Secondary connection simultaneously forms circulation loop.Acidic etching liquid in etching fluid cylinder enters waste collection slot, waste collection slot by overflow Part etching solution enter in electrolytic cell by certain flow rate from low level after filter device filters;Filter device is common cotton core mistake Filter, effect is the solid impurity filtered out in etching solution;Diaphragm is provided in electrolytic cell, electrolytic cell is separated into yin by diaphragm Pole room and anode chamber are equipped with anode plate in anode chamber, are equipped with cathode plate in cathode chamber;Anode chamber passes through pipeline and multistage suction System connectivity is received, cathode chamber is connect with copper device is mentioned.When the etching solution of high copper separately flows into cathode chamber from bottom of electrolytic tank Behind anode chamber, under direct current electro ultrafiltration, following variation will occur for cathode and anode:
Cathode: the copper ion in solution obtains electronics from cathode and is reduced into elemental copper, then is periodically mentioned by mentioning copper device Commercially valuable metallic copper is obtained, and drops the catholyte after copper and then flows into regenerated liquid storage tank, specific electrode from a cathode high position It reacts as follows:
Cu2++e-→Cu+
Cu++e-→Cu0
Anode: the univalent copper ion in solution preferentially loses electronics in anode and is oxidized to bivalent cupric ion, with electrolysis The progress of reaction, bivalent cupric ion is continuously increased in solution, and univalent copper ion is gradually decreased or disappeared, solution etch capabilities also with Enhancing, obtaining can be with the regenerated liquid of reuse, simultaneously because there are a large amount of chloride ions in solution, with mentioning for solution oxide Height, a large amount of chloride ions will lose electronics in anode surface and chlorine are precipitated, and main electrodes reaction is as follows:
Cu+-e-→Cu2+
2Cl--2e-→Cl2
It is electrolysed the cathode and anode liquid after mentioning copper and flows into regenerated liquid storage tank from an electrolytic cell high position, be equipped with stirring in regenerated liquid storage tank Device carries out sufficiently balanced mixing to electrolyte, thus obtains low-gravity regenerated liquid, regenerated liquid circulating and recovering to etch system In.
Specifically, it is positive integer that multistage absorption system, which includes the n grades of absorption cylinders being sequentially connected in series, n >=2, and n,.Every grade of absorption The bottom of cylinder, which is contacted, a centrifugal pump and an ejector and constitutes circuit, next stage absorb the ejector of cylinder by pipeline with Upper level absorbs the top connection of cylinder, by taking the first order absorbs cylinder as an example: one end connection first order absorption cylinder, another of first-stage centrifugal pump End connection level-one ejector, level-one ejector are respectively communicated with the bottom of anode chamber and first order absorption cylinder by closed conduit, work as sun Extremely indoor chlorine enters level-one ejector by closed conduit, and first-stage centrifugal pump takes out the acidity come from first order absorption cylinder at this time Etching solution also enters level-one ejector, and under flow at high speed and suction function, the air-liquid stream to meet in level-one ejector is mixed High speed injection is exported into first order absorption cylinder from ejector together afterwards, and the chlorine not being absorbed is logical at the top of first order absorption cylinder Piping enters in secondary jets device, absorbs after the acidic etching liquid for taking out to come in cylinder mixes with two stage centrifugal pump from second level and sprays together It is mapped to second level to absorb in cylinder, second level, which absorbs the chlorine not being absorbed in cylinder and absorbs from second level, enters three-level by pipeline at the top of cylinder In ejector, and so on, until the pipeline that the unabsorbed chlorine of minute quantity absorbs at the top of cylinder through n-th grade enters vent gas treatment It is recycled in device, gas flow path is consequently formed.Partially acidic etching solution in waste collection slot passes through tube overflow Into n-th grade of absorption cylinder, n-th grade absorb cylinder in solution by tube overflow to (n-1)th grade absorb cylinder bottom, (n-1)th grade The bottom that the solution in cylinder absorbs cylinder by tube overflow to the n-th -2 grades is absorbed, and so on, until the second level absorbs in cylinder Solution is absorbed in cylinder by tube overflow to the first order, and the bottom that the first order absorbs cylinder is connected to etch system, is made by multistage The activating solution that absorption system is handled is back in etch system, and liquid flow path is consequently formed.As shown in the above, chlorine The direction and acidic etching liquid for flowing into multistage absorption system overflow to the flow direction of multistage absorption system just on the contrary, specifically such as Under:
Air-flow:
The first order absorbs cylinder → second level and absorbs n-th grade of absorption cylinder → exhaust gas processing device of cylinder →...
Liquid stream:
N-th grade of absorption cylinder ... → third level absorbs cylinder → second level and absorbs cylinder → first order absorption cylinder.
The principle that above-mentioned air-liquid reverse-engineers is: the target for activating etching solution seeks to reduce copper extra in solution, together When by Cu therein+It is converted into Cu2+, to restore the activity of etching solution.It, can be by the Cu in etching solution using chlorine as oxidant+ It is oxidized to Cu2+, etching solution is made to obtain activating and regenerating, priming reaction formula are as follows:
Cl2+2Cu+→2Cu2++2Cl-
The utility model mentions copper by electrolysis and realizes drop copper, by multistage absorption system in the condition for not consuming extra resource Lower realization Cu+To Cu2+Conversion.For liquid flow path, the solution absorbed in cylinder due to n-th grade is directly from waste collection slot Etching waste liquor, the Cu in the solution+Content highest, part Cu after being passed through chlorine+It is oxidized to Cu2+, absorbed from n-th grade Cylinder overflow enters the solution that (n-1)th grade absorbs in cylinder part Cu again+It is oxidized to Cu2+, illustrate in (n-1)th grade of absorption cylinder in solution Cu+Content absorbs the Cu in cylinder in solution than n-th grade+Content is few, and similarly, when the second level absorbs the solution in cylinder, overflow enters again After the first order absorbs cylinder, and there is part Cu+It is oxidized Cu2+, illustrate that the first order absorbs the Cu in cylinder in solution+Content is relatively other It is least for absorbing cylinder.For gas flow path, whenever the first order absorb the obtained chlorine of cylinder be all it is most sufficient, because This, the utility model reverse-engineers the Cu that the first order can be made to absorb in cylinder in solution by air-liquid+Almost all is by chlorine oxygen Turn to Cu2+, the solution sufficiently activated, then by central control system real-time monitoring etch cylinder in etching solution specific gravity and ORP come Control this activating solution is recycled back to dosage, to achieve the purpose that resource makes full use of.
The regenerated liquid specific gravity that electrolysis system obtains is generally lower, is unfavorable for direct reuse, it usually needs additional addition oxidation Agent improves etching solution activity;And the utility model is exactly that can obtain activating in first order absorption cylinder using multistage absorption system filling Divide, the high ORP activating solution that oxidisability is good, returns to etch system using activating solution cooperation electrolytic regeneration liquid and use, it can be preferably Stablize etching speed, the magnitude of recruitment of oxidant is greatly decreased and thus bring medical fluid increment wastes, remarkable in economical benefits.Together When, the amount of chlorine that n-th grade of absorption cylinder obtains is minimum, and the discharge rate of chlorine is also minimum after absorbing, or even is discharged without chlorine;Seldom The chlorine of amount first passes through the absorption of the ferrous iron solution in exhaust gas processing device, finally thoroughly recycles tail gas by lye aeration tower again, Ensure non-pollutant discharge, safety and environmental protection.
Specifically, central control system by setting densimeter and ORP analyzer real-time monitoring etch cylinder in solution specific gravity and ORP value, central control system control the reuse amount of regenerated liquid and activating solution by the solenoid valve on control pipeline again.
Correspondingly, the utility model additionally provides what application device as described above efficiently activated acidic etching liquid Method, as shown in Fig. 2, this method is mainly by the acidic etching liquid in waste collection slot after electrolysis mentions copper, then by yin, yang Pole liquid is uniformly mixed, and regenerated liquid is obtained, by regenerated liquid reuse into etch system;The chlorine that electrolysis system generates successively is passed through more In grade absorption system, finally enters in exhaust gas processing device and handled;Acidic etching liquid in waste collection slot with chlorine Flow to successively acidic etching liquid conveying of the overflow into multistage absorption system, in last multistage absorption system of opposite flow direction It is recycled into etch system.Specific step is as follows:
S1, the acidic etching liquid that etch system generates is collected into waste collection slot;
S2, it will be delivered in electrolysis system after the partially acidic etching solution filtering in waste collection slot and be electrolysed and mentioned Copper is electrolysed the cathode and anode liquid stream after mentioning copper and enters in regenerated liquid storage tank, and stirring is uniformly mixed it, obtains low-gravity regenerated liquid, Regenerated liquid is recycled by pipeline into etch system;
S3, the indoor chlorine of electrolysis system Anodic are sent into the first order by closed conduit and are absorbed in cylinder, and the first order absorbs The gaseous mixture isolated at the top of cylinder is sent into the second level and is absorbed in cylinder, under the gaseous mixture isolated at the top of second level absorption cylinder is then sent into In first order absorption cylinder, and so on, the gaseous mixture isolated at the top of cylinder is absorbed until n-th grade is sent into exhaust gas processing device;
Another part acidic etching liquid overflow in S4, waste collection slot is into n-th grade of absorption cylinder, in n-th grade of absorption cylinder The supreme first order absorption cylinder of acidic etching liquid overflow in, and so on, until acidic etching liquid overflow to the first order absorb cylinder in, The acidic etching liquid that the first order absorbs in cylinder, which is delivered in etch system, to be recycled.
The rule that the method for the utility model is mutually converted based on each substance of acidic etching liquid electrolytic process, comprehensive analysis acid Property etching solution transformation rule of various ions and the characteristics of various absorbing mediums in etching, regeneration and electrolytic process, using gas, The design and device of the reverse multistage absorption of liquid double fluid, construct the gas flow path and liquid flow path of reverse and each self-loopa, really respectively Having protected chlorine can be absorbed utilization to the maximum extent, reach the first order and absorb solution in cylinder and be able to overactive purpose, make Obtain Cu in the solution in first order absorption cylinder2+Content highest, Cu+Content is minimum, and n-th grade of absorption cylinder discharge amount of chlorine it is minimum, It is even discharged without chlorine, dexterously solves Cu under the conditions of not consuming extra resource as far as possible+Gradually to Cu2+The problem of conversion, The etching solution with high activity and circulating and recovering are finally obtained, to realize that regeneration etching matches with electrolysis system, effectively The stability and continuity of etching speed are maintained, a kind of etching solution regeneration method that online etching, electrolysis and reuse require is met.
Through implementing to verify, it was demonstrated that the above-mentioned apparatus and method of the utility model are maintaining acid etching, On-line electrolytic dissolution regeneration And reuse process generates good result: be electrolysed generation chlorine it is substantially all recycled, the reclamation rate of regenerated liquid Reach 95% or more, integrated operation cost reduces by 45%, while reduce pollutant emission, ensure production process safety and environmental protection and Resource maximization, which recycles etc., all obtains significant effect.
In order to verify the beneficial effects of the utility model, the utility model is made into one below with reference to embodiment and comparative example The explanation of step.
In order to make to be comparable between each embodiment and comparative example, all electrolysis in each embodiment and comparative example System, ejector, centrifugal pump, central control system are all made of same model specification and setting, and exhaust gas processing device is all made of protochloride Ferrous solution absorbs, and finally thoroughly recycles tail gas by lye aeration tower again, it is ensured that non-pollutant discharge, safety and environmental protection, and same Implement operation in one etch system.Wherein, the difference of Examples 1 to 3 and comparative example 1 is only that the multistage absorption for absorbing chlorine The series of dissolver is different, at the multistage absorption system for passing through different series with the chlorine that the electrolysis of proving and comparisom etching solution generates The recovering effect of reason and the difference of regenerated liquid reclamation rate and the variation for etching producing line overall cost.Embodiment 2 and comparative example 2 Difference to be only that the air-liquid of comparative example 2 flows to identical, in order to verify air-liquid flow direction to recovering effect and regenerated liquid The influence of reclamation rate, overall cost.
Embodiment 1: second level counter-current absorption electrolytic regeneration method
As shown in figure 3, etching the etching solution in cylinder through tube overflow into waste collection slot, then in the present embodiment Part etching solution enters electrolytic cell from low level after filter device filters solid impurity, by certain flow rate, and diaphragm divides electrolytic cell It is divided into cathode chamber and anode chamber, wherein cathode chamber is connect with copper device is mentioned, for extracting the elemental copper of cathode precipitation;Anode chamber Top is connect by closed conduit with first order ejector, for the chlorine of precipitation to be drained in first order ejector;So Cathode and anode liquid after being electrolysed and mentioning copper flows into regenerated liquid storage tank from an electrolytic cell high position, and cathode and anode liquid mixes in regenerated liquid storage tank Low-gravity regenerated liquid is obtained after closing uniformly, regenerated liquid is by pipeline reuse into etching cylinder.
Part etching solution overflow to the second level absorbs in cylinder, then absorbs cylinder overflow to the first order from the second level and absorb in cylinder, As the absorption dissolving medium of chlorine;The first order absorb cylinder and the second level absorb cylinder respectively with corresponding centrifugal pump, ejector Each self-forming liquid stream circuit after series connection, wherein first order ejector is connected to anode chamber, and second level ejector is connected to the first order and absorbs Cylinder, when the indoor chlorine of anode enters first order ejector through closed conduit, chlorine with by first order centrifugal pump from first The first order is sprayed back together after the etching solution mixing that grade absorption cylinder pumping is come to absorb in cylinder, is inhaled the first order using the oxidisability of chlorine Receive the Cu in cylinder in solution+It is oxidized to Cu2+, and the chlorine not being absorbed from the first order absorb cylinder top via pipeline into Enter second level ejector, chlorine with absorbed by second level centrifugal pump from the second level taken out in cylinder come etching solution mix after spray together It is emitted back towards the second level to absorb in cylinder, equally by part Cu+It is oxidized to Cu2+, since air-liquid inversely shunts step by step, finally make the first order The activity for absorbing solution in cylinder improves, and can cooperate electrolytic regeneration liquid reuse.The top that the second level absorbs cylinder is connected to vent gas treatment Device, the second level absorb the chlorine not absorbed in time in cylinder and flow into exhaust gas processing device recycling completely by pipeline.It is following Loopback use during, using central control system real-time monitoring etching cylinder in etching solution specific gravity and ORP come control electrolytic regeneration liquid and The usage amount of activating solution.
Embodiment 2: three-level counter-current absorption electrolytic regeneration method
As shown in figure 4, the present embodiment the difference from embodiment 1 is that: multistage absorption system altogether include three-level absorb cylinder, The part etching solution overflow of waste collection slot to the third level absorbs in cylinder, then absorbs cylinder overflow from the third level and enters second level absorption In cylinder, then cylinder overflow is absorbed from the second level and is entered in first order absorption cylinder, as the absorption dissolving medium of chlorine;Absorption cylinders at different levels Respectively with each self-forming liquid stream circuit after corresponding centrifugal pump, ejector series connection, wherein first order ejector is connected to anode chamber, the Secondary jets device is connected to the first order and absorbs cylinder, and third level ejector is connected to the second level and absorbs cylinder, and the chlorine for being electrolysed generation will be at different levels Absorb the part Cu in cylinder+It is oxidized to Cu2+Afterwards, the chlorine that cylinder absorbs in time is not absorbed by the third level and absorbs cylinder via the third level To flow into exhaust gas processing device recycling clean at top.Other are same as Example 1.
Embodiment 3: four-stage counter-current absorbs electrolytic regeneration method
As shown in figure 5, the present embodiment the difference from embodiment 1 is that: multistage absorption system altogether include level Four absorb cylinder, The part etching solution overflow of waste collection slot to the fourth stage absorbs in cylinder, then absorbs cylinder overflow from the fourth stage and enters third level absorption In cylinder, then cylinder overflow is absorbed from the third level and is entered in second level absorption cylinder, then absorb cylinder overflow from the second level and enter first order absorption cylinder In, as the absorption dissolving medium of chlorine;Each self-forming after absorption cylinders at different levels are connected with corresponding centrifugal pump, ejector respectively Liquid stream circuit, wherein first order ejector is connected to anode chamber, and second level ejector is connected to the first order and absorbs cylinder, third level ejector It is connected to the second level and absorbs cylinder, fourth stage ejector is connected to the third level and absorbs cylinder, when the indoor chlorine of anode enters through closed conduit When first order ejector, chlorine with by first order centrifugal pump from the first order absorb cylinder take out come etching solution mix after spray together It returns the first order to absorb in cylinder, the first order is absorbed to the Cu in cylinder in solution using the oxidisability of chlorine+It is oxidized to Cu2+, other suctions It receives cylinder similarly, i.e., absorbs the conduit that the chlorine not being absorbed in cylinder is connected at the top of this grade absorption cylinder in this grade and enter next stage Ejector sprays back in next stage absorption cylinder together after the etching solution for taking out to come in cylinder mixes with absorbing from next stage, utilizes chlorine Oxidisability by the part Cu in absorption cylinders at different levels in solution+It is oxidized to Cu2+, so circulation progress.Cylinder is not absorbed by the fourth stage The chlorine absorbed in time flows into exhaust gas processing device recycling completely via the top that the fourth stage absorbs cylinder.Other with embodiment 1 It is identical.
Comparative example 1: single-stage absorption cylinder electrolytic regeneration method
As shown in fig. 6, the etching solution etched in cylinder enters waste collection slot by connecting pipe overflow, so in comparative example 1 Part etching solution is after filter device filters solid impurity afterwards, enters electrolytic cell from low level by certain flow rate, and diaphragm is by electrolytic cell It is divided into cathode chamber and anode chamber, wherein cathode chamber is connect with copper device is mentioned, for extracting the elemental copper of cathode precipitation;Anode chamber Top connect with ejector by closed conduit, for the chlorine of precipitation to be drained in ejector;So copper is mentioned through electrolysis Cathode and anode liquid afterwards flows into regenerated liquid storage tank from an electrolytic cell high position, and cathode and anode liquid obtains after mixing in regenerated liquid storage tank To low-gravity regenerated liquid, regenerated liquid is by pipeline reuse into etching cylinder.
Then overflow extremely absorbs the absorption dissolving medium in cylinder as chlorine to part etching solution;Absorb cylinder and centrifugal pump, jet stream Device liquid stream circuit in series, wherein ejector is connected to anode chamber, and the indoor chlorine of anode enters ejector, chlorine through closed conduit Gas with by centrifugal pump from absorb cylinder take out come etching solution mix after spray together resorption receipts cylinder in, utilize chlorine oxidisability general Absorb the Cu in cylinder in solution+It is oxidized to Cu2+, solution O RP increased, and the reuse of electrolytic regeneration liquid can be cooperated to etching cylinder In;The chlorine for not being absorbed cylinder absorption flows into exhaust gas processing device recycling completely by pipeline;During circulating and recovering, utilize Central control system real-time monitoring etches the specific gravity and ORP of etching solution in cylinder to control the usage amount of electrolytic regeneration liquid and activating solution.
Comparative example 2: three-level absorbs electrolytic regeneration method in the same direction
As shown in fig. 7, etching the etching solution in cylinder through tube overflow into waste collection slot, then in comparative example 2 Part etching solution enters electrolytic cell from low level after filter device filters solid impurity, by certain flow rate, and diaphragm divides electrolytic cell It is divided into cathode chamber and anode chamber, wherein cathode chamber is connect with copper device is mentioned, for extracting the elemental copper of cathode precipitation;Anode chamber Top is connect by closed conduit with first order ejector, for the chlorine of precipitation to be drained in first order ejector;So Cathode and anode liquid after being electrolysed and mentioning copper flows into regenerated liquid storage tank from an electrolytic cell high position, and cathode and anode liquid mixes in regenerated liquid storage tank Low-gravity regenerated liquid is obtained after closing uniformly, regenerated liquid is by pipeline reuse into etching cylinder.
Part etching solution overflow to the first order absorbs in cylinder, then absorbs cylinder overflow to the second level from the first order and absorbs cylinder In, then absorb cylinder overflow to the third level from the second level and absorb in cylinder, as the absorption dissolving medium of chlorine;The first order absorbs Cylinder, the second level absorb cylinder and third absorbs each self-forming liquid stream circuit after cylinder is connected with corresponding centrifugal pump, ejector respectively, Middle first order ejector is connected to anode chamber, and second level ejector is connected to the first order and absorbs cylinder, and third level ejector is connected to the second level Absorb cylinder, when the indoor chlorine of anode enters first order ejector through closed conduit, chlorine with by first order centrifugal pump from The first order is absorbed after cylinder takes out the etching solution mixing come and spray back in first order absorption cylinder together, using the oxidisability of chlorine by first Grade absorbs the Cu in cylinder in solution+It is oxidized to Cu2+, and the chlorine not being absorbed absorbs the top of cylinder via pipeline from the first order Into second level ejector, chlorine with by second level centrifugal pump from the second level absorb cylinder in take out come etching solution mix after together The second level is sprayed go back to absorb part Cu in cylinder+It is oxidized to Cu2+, the chlorine that has not been absorbed equally absorbs the top of cylinder from the second level Portion enters third level ejector via pipeline, chlorine with absorbed by third level centrifugal pump from the third level taken out in cylinder come etching solution The third level is sprayed back after mixing together to absorb part Cu in cylinder+It is oxidized to Cu2+.Air-liquid flow path is in the same direction in comparative example 2, finally Solution cooperation electrolytic regeneration liquid in cylinder is absorbed using the third level to be back to use in etch system.The top that the third level absorbs cylinder is connected to tail Flash Gas Compression Skid System, it is dry by pipeline inflow exhaust gas processing device recycling that the third level absorbs the chlorine not absorbed in time in cylinder Only.During circulating and recovering, electrolysis is controlled again using the specific gravity and ORP of etching solution in central control system real-time monitoring etching cylinder The usage amount of raw liquid and activating solution.
In implementing operational process, taken at regular intervals Examples 1 to 3 and comparative example 1~2 are molten into and out of absorption cylinders at different levels respectively The ORP of liquid (reflects Cu in solution2+Content, i.e. ORP value is bigger, Cu2+Content is higher, illustrates that solution activation is more abundant, oxidation Property is better, etch capabilities are stronger), the absorption concentration of cylinder import and export chlorine at different levels, the etching speed of etching line, regenerated liquid reuse The data such as rate and etching overall cost, the results are shown in Table 1.
As shown in Table 1, comparative example 1 is compared with Examples 1 to 3, although its etching solution ORP higher for absorbing cylinder outlet, It is that the chlorine gas concentration that it is exported is above Examples 1 to 3, while corresponding etching speed is far below Examples 1 to 3;Comparative example 2 Compared with Example 2, although its etching solution ORP higher for absorbing cylinder outlet, its chlorine gas concentration exported is much higher than implementation Example 2, while corresponding etching speed is also far below embodiment 2, it can be seen that, Examples 1 to 3 maintain acid etching speed and More significant effect is all obtained to abundant recycle of chlorine.
1 Examples 1 to 3 of table and 1~2 operational effect tracking table record of comparative example
In conclusion the utility model is by multistage absorption system (series n >=2) and flows to opposite chlorine recyclegas Flow path and acidic etching liquid circulating liquid flow path effectively ensure that chlorine can be absorbed utilization to the maximum extent, regenerated liquid Reclamation rate reaches 95% or more, and integrated operation cost reduces by 45%, realizes the abundant recycling of electrolysate, effectively maintains erosion The stabilization of speed and continuous is carved, meets the requirement of online etching, electrolysis and reuse, realizes that resource maximization recycles, safety Environmental protection, efficiently solve the chlorine that the prior art fails to make full use of electrolysis to generate and caused by regenerated liquid reclamation rate is low, etching The problems such as speed is unstable, operation height consumes and environmental pollution.
Above embodiment is only preferred embodiments of the present invention, cannot be protected with this to limit the utility model Range, the variation of any unsubstantiality that those skilled in the art is done on the basis of the utility model and replacement belong to In the utility model range claimed.

Claims (8)

1. a kind of device of efficient activated acid etching solution, it is characterised in that: including etch system, electrolysis system, regenerated liquid storage Slot, multistage absorption system and exhaust gas processing device;The etch system, electrolysis system, regenerated liquid storage tank are sequentially connected by pipeline Circulation loop is connect and is formed, the chlorine that the electrolysis system generates successively is passed through the multistage absorption system and tail gas by pipeline In processing unit, the acidic etching liquid of the etch system passes through tube overflow into the multistage absorption system, and described more The overflow direction of acidic etching liquid is opposite with the flow direction of chlorine in grade absorption system;The multistage absorption system and etching are System is connected to by pipeline, so that the acidic etching liquid reuse after activation is into the etch system.
2. the device of efficient activated acid etching solution according to claim 1, it is characterised in that: the multistage absorption system The absorption cylinder being sequentially connected in series including n grades, n >=2, and n are positive integer.
3. the device of efficient activated acid etching solution according to claim 2, it is characterised in that: the electrolysis system passes through Pipeline with centrifugal pump and ejector is connected to the bottom that the first order absorbs cylinder, and the first order, which absorbs, passes through band at the top of cylinder The bottom for having the pipeline of centrifugal pump and ejector to absorb cylinder with the second level is connected to, and the second level absorbs the top of cylinder by having The pipeline of centrifugal pump and ejector is connected to the bottom that next stage absorbs cylinder, and so on, until (n-1)th grade of absorption cylinder and n-th Grade absorbs the bottom connection of cylinder, and the top of n-th grade of absorption cylinder is connected to by pipeline with the exhaust gas processing device, to be formed Gas flow path.
4. the device of efficient activated acid etching solution according to claim 3, it is characterised in that: the etch system passes through The top that pipeline absorbs cylinder with described n-th grade is connected to, the top and the bottom of described (n-1)th grade absorption cylinder of n-th grade of absorption cylinder Portion's connection, the bottom that the top of (n-1)th grade of absorption cylinder absorbs cylinder with described the n-th -2 grades are connected to, and so on, until described The second level absorbs cylinder to be connected to the bottom that the first order absorbs cylinder, and the first order absorbs the bottom of cylinder and the etch system connects It is logical, to form liquid flow path.
5. the device of efficient activated acid etching solution according to claim 1 or 2, it is characterised in that: the etch system Including etching cylinder and the waste collection slot being connected to the etching cylinder, the waste collection slot passes through pipeline and the electrolysis respectively System and multistage absorption system connectivity, the multistage absorption system are connected to by pipeline with the etching cylinder, the regenerated liquid storage Slot is connected to by pipeline with the etching cylinder.
6. the device of efficient activated acid etching solution according to claim 5, it is characterised in that: the electrolysis system includes Sequentially connected filter device, electrolytic cell and copper device is mentioned, the filter device is connected to the waste collection slot, the electrolysis Slot is connected to the regenerated liquid storage tank.
7. the device of efficient activated acid etching solution according to claim 6, it is characterised in that: setting in the electrolytic cell There is diaphragm, the electrolytic cell is separated into cathode chamber and anode chamber by the diaphragm, and anode plate is equipped in the anode chamber, described Cathode plate is installed in cathode chamber;The anode chamber passes through pipeline and the multistage absorption system connectivity, the cathode chamber connection Copper device is mentioned described in having;Blender is equipped in the regenerated liquid storage tank.
8. the device of efficient activated acid etching solution according to claim 1 or 2, it is characterised in that: further include having middle control System, the central control system passes through the ORP and specific gravity data of etching solution in etch system described in real-time monitoring, to control the warp The acidic etching liquid of activation and the reuse amount of regenerated liquid.
CN201821995824.7U 2018-11-29 2018-11-29 A kind of device of efficient activated acid etching solution Withdrawn - After Issue CN209412325U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109252168A (en) * 2018-11-29 2019-01-22 珠海市智宝化工有限公司 A kind of devices and methods therefor of efficient activated acid etching solution

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109252168A (en) * 2018-11-29 2019-01-22 珠海市智宝化工有限公司 A kind of devices and methods therefor of efficient activated acid etching solution
CN109252168B (en) * 2018-11-29 2024-01-12 珠海市智宝化工有限公司 Device and method for efficiently activating acidic etching solution

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