CN113200635B - Circuit board etching wastewater treatment device and method - Google Patents

Circuit board etching wastewater treatment device and method Download PDF

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CN113200635B
CN113200635B CN202110669808.9A CN202110669808A CN113200635B CN 113200635 B CN113200635 B CN 113200635B CN 202110669808 A CN202110669808 A CN 202110669808A CN 113200635 B CN113200635 B CN 113200635B
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tank
copper
water
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etching
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CN113200635A (en
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徐鸿顺
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Guangdong Qinhua Intelligent Environment Technology Co.,Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46145—Fluid flow
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/043—Treatment of partial or bypass streams

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Abstract

The invention belongs to the field of circuit boards (PCB), and particularly relates to a device and a method for treating circuit board etching wastewater, wherein the device comprises the following steps: a concentrate tank configured to collect etching waste water; a copper removal apparatus configured to remove copper ions in the etching wastewater; a copper-free water tank; the adjusting tank is configured with an electrolytic tank for adjusting the pH value of the etching wastewater, and comprises a tank body, an anode plate, a cathode plate and at least one electrode plate n (n is more than or equal to 1), the electrolytic tank is used for converting ammonia nitrogen into nitrogen gas through electrolysis, two ball valves, a diaphragm pump and a flowmeter are arranged between the adjusting tank and the electrolytic tank, the diaphragm pump is arranged between the two ball valves, after the water inlet flow of the electrolytic tank, the interval width t of the electrode plates, the voltage value V and the target water outlet ammonia nitrogen concentration b are obtained, the current value I is obtained through inquiry, the electrolytic tank is controlled by the controller to start electrolysis, the treatment load of a biochemical tank is reduced, and the total nitrogen and ammonia nitrogen treatment standard pressure of a wastewater station is effectively reduced.

Description

Circuit board etching wastewater treatment device and method
Technical Field
The invention belongs to the field of circuit boards (PCBs), and particularly relates to a device and a method for treating circuit board etching wastewater.
Background
Pcb (printed circuit board), which is called printed circuit board (pcb) and is also called printed circuit board (pcb), is an important electronic component, which is a support for electronic components and is a carrier for electrical connection of electronic components. It is called a "printed" circuit board because it is made using electronic printing.
The PCB production process reaches 20 times, and waste liquid is generated in most processes, wherein the etching waste liquid (ammonia nitrogen waste water) is the main waste liquid generated in the PCB production process. At present, the treatment method of PCB etching waste liquid at home and abroad mostly adopts a neutralization precipitation method, an electrolysis method, an oxidation-reduction method, an evaporation crystallization method, a solvent extraction method and the like.
The neutralization precipitation method is used as a main flow for treating the etching waste liquid, so that the consumption of acid or alkali is high, the treatment cost is very high, the waste liquid treatment stations of some enterprises are in the same design, and the ammonia salt pollution is serious after the heavy metal is removed.
The solvent extraction method for treating the PCB etching waste liquid can recover copper and recycle the etchant at the same time, and has the advantages of good separation effect, low reagent consumption, high productivity, high direct yield, low secondary pollution and the like. But the search for suitable extractants and extraction processes has just begun.
Although the treatment methods such as an electrolysis method, a redox method, an evaporative crystallization method and the like can recover metals such as copper and the like, the treatment methods all have the defects of large reagent consumption, high treatment cost (mostly 20-30 yuan/ton), low purity of the recovered copper, incapability of recovering ammonia, incapability of recycling the treated wastewater and discharging the wastewater, and the like, so that the economic benefit is not obvious, and the serious problem of secondary pollution exists to different degrees. At present, the electrolytic method is widely applied, and the technology is continuously explored in the industry.
Chinese patent CN110422948A discloses a process for recovering metallic copper from copper sulfate electroplating wastewater, which comprises the steps of inputting copper-containing electroplating wastewater into a first-stage NF system for filtering, separating fresh water and concentrated solution, further performing advanced treatment on the fresh water through an RO system, inputting the concentrated solution into an electrodialyzer for electrolyzing the fresh water and the concentrated solution, circularly inputting the fresh water into a raw water bucket for storage, inputting the concentrated solution into a centrifugal electrolyzer for separating out electrolytic copper, and reusing the electrolytic copper in a copper plating bath. Adopt the RO system to filter in this scheme, the cost is very high, hardly uses to the trade that circuit board waste water produced the height, moreover, does not consider the electrically conductive efficiency and the work efficiency who removes the copper process.
Chinese patent CN106006856A discloses a system for treating ammonia nitrogen in ammoniacal cupric chloride wastewater by an electrolytic catalytic oxidation method, which continuously deposits metal copper powder on a cathode titanium mesh plate, part of the metal copper powder is oxidized into copper oxide by a strong oxidizer in a solution and suspended in the solution, the copper oxide is filtered by a filter device, and the ammonia nitrogen is oxidized into nitrogen by the electrolytic catalytic oxidation method and discharged. According to the technical scheme, the copper removal process and the ammonia nitrogen removal process are carried out simultaneously, and the difference of the pH value of the wastewater in the copper removal process and the pH value in the electrolysis process in the optimal effect is not considered.
Disclosure of Invention
The invention aims to provide a device and a method for treating circuit board etching wastewater, the device can efficiently remove copper in the front-end treatment process and ammonia nitrogen in the rear-end treatment process, and compared with the prior art, the device and the method can achieve the purposes of better environment-friendly effect and cost saving.
In order to achieve the purpose, the invention adopts the following technical scheme:
a circuit board etching wastewater treatment device comprises:
a concentrate tank configured to collect etching wastewater;
the copper removing equipment is configured for removing copper ions in the etching wastewater, and comprises a plurality of electrode plates, anode plates, cathode plates and rectifiers which are arranged in parallel, wherein the copper removing equipment is used for circularly removing copper after the PH value of the etching wastewater is adjusted to reach a set range, and the rectifiers are used for converting alternating current into direct current; the upper end of the copper removing equipment is connected with the waste gas tower through an interface, and the lower end of the copper removing equipment is connected with the aeration pipe, the salt tank and the alkali tank through interfaces; the copper removing equipment is also provided with an internal circulation structure, and the internal circulation structure comprises two manual ball valves and a circulating pump; two manual ball valves are arranged between the concentrated liquid tank and the copper removing equipment, and a diaphragm pump is arranged between the two manual ball valves;
the input end of the copper-free water tank is connected with a copper removal device, the etching wastewater treated by the copper removal device is stored in the copper-free water tank, and the output end of the copper-free water tank is connected with the adjusting groove;
the adjusting tank is configured for adjusting the pH value of the etching wastewater, two manual ball valves, a flow pump and a flow meter are arranged between the copper-free water tank and the adjusting tank, and the flow pump is arranged between the two manual ball valves; the upper end of the adjusting tank is also provided with an interface which is respectively connected with a salt tank and an alkali tank and is used for adding salt and alkali into the adjusting tank; the adjusting tank, the salt tank and the alkali tank are respectively connected with an aeration pipe; the salt tank and the alkali tank are also respectively connected with a tap water pipe;
the controller comprises a memory, and all the flow meters are in signal connection with the controller;
the electrolytic cell comprises a cell body, an anode plate, a cathode plate and at least one electrode plate n (n is more than or equal to 1), the electrolytic cell is used for converting ammonia nitrogen into nitrogen through electrolysis, two ball valves, a diaphragm pump and a flowmeter are arranged between the adjusting cell and the electrolytic cell, and the diaphragm pump is arranged between the two ball valves; the upper surface of the electrolytic bath is also provided with an exhaust port connected with a waste gas tower, and the lower surface is provided with a discharge port and a sewage draining outlet; the specific reaction process of the electrolytic cell is as follows:
(1) direct oxidation of ammonia to nitrogen for NH removal3+3OH-→1/2N2+3H2O+2e-
(2) The ammonia is indirectly electrically oxidized, oxidizing substances are generated through electrode reaction, and the oxidizing substances react with the ammonia, so that the ammonia is degraded and removed.
Usually, a certain amount of salt is added into the wastewater to increase the conductivity of the solution, Cl-discharges at the anode to generate a chlorine oxidant, and the oxidation of the anode is enhanced, so that the removal effect is improved, wherein electrolyte substances need to be added due to front-end electrolysis, and the conductivity substances need to be reduced by homogenizing the water quality or precipitating with other low-conductivity wastewater before entering biochemistry, and the reaction process is as follows:
2CL-→CL2+2e
Figure BDA0003118669150000031
CL2+H2O→HOCL+H++CL
CL2+2NaOH→NaCL+NaCLO+H2O
2NH4++3HOCL→N2+3H2O+5H++3CL3NaClO+2NH3→N2+3NaCL+H2O。
tap water and alkali treatment waste gas are input into the waste gas tower;
the tank body is provided with a water inlet and a water outlet, the water inlet is arranged at one corner of the tank body, and the water outlet is arranged at an oblique angle on the same plane with the water inlet; inflow q and total area S of electrode plateGeneral assemblySatisfies the relationship of SGeneral assemblyA numerical proportionality of (4-5) q, wherein SGeneral assemblyIs an electrode plate SSheetSum of areas of (1) n × SSheetUnit m of2(ii) a And (3) detecting by using a flowmeter to obtain inflow q, unit: l/min;
further, the electrolysis current I and the water inlet flow q satisfy a functional relation: k is1×q3+k2×q2+k3X q + p, wherein k1、k2、k3Fitting coefficients of a cubic function for least squares, said functional relation and said coefficients being stored in a controllerA memory;
after the water inlet flow of the electrolytic cell, the interval width t of the electrode plates, the voltage value V and the target effluent ammonia nitrogen concentration b are obtained, inquiring to obtain a current value I, and controlling the electrolytic cell to start electrolysis by the controller.
Preferably, the copper removing equipment is used for removing copper through the internal circulation structure after adjusting the NaCl concentration to a target value through a salt tank and adjusting the PH to be between 8 and 9 through inputting NaOH through an alkali tank.
Preferably, the adjusting tank adjusts the NaCl concentration to a target value through a salt tank and adjusts the PH to be between 11 and 12 through inputting NaOH through an alkali tank, and then inputs the etching waste water into the electrolytic tank.
Preferably, the electrolysis current of the electrolytic cell is set within the range of 200A-220A, and the anode plate voltage of the electrolytic cell is set within the range of 3-5V.
Preferably, the electrode plate in the copper removing equipment is a ruthenium-iridium electrode plate.
The invention also discloses a treatment method applied to the circuit board etching wastewater treatment device, and the implementation process comprises the following steps:
s1: the waste water to be treated in the etching water washing section enters a concentrated solution tank;
s2: after water in the etching water washing section normally enters a concentrated solution tank, a manual water inlet valve and a diaphragm pump between the concentrated solution tank and the copper removing equipment are opened, the diaphragm pump and a ball valve are closed after the water inflow of the copper removing equipment reaches an upper scale mark, NaOH is added into an adjusting groove by a salt groove and an alkali groove to maintain the PH between 8 and 9, and a rectifier and a circulating pump of an internal circulating structure of the copper removing equipment are opened;
s3: after the copper content is less than 50ppm, closing the rectifier, opening a ball valve between the circulating pump and the copper-free water tank, and closing a circulating valve on the copper removal equipment;
s4: opening a ball valve between the copper-free water tank and the adjusting tank, and starting the flow pump;
s5: the wastewater after passing through the copper-free water tank enters an adjusting tank, a ball valve between a salt tank and an alkali tank to the adjusting tank is kept normally open, NaOH is added into the adjusting tank to maintain the PH value between 11 and 12, and the concentration and the stock of NaCl solution are ensured within a set range at regular time; if the volume of the adjusting tank is insufficient due to overlarge water inflow of the adjusting tank, the adjusting tank is adjusted by a manual valve in front of a flow meter in front of the adjusting tank;
s6: sequentially opening a manual valve and an electrolytic cell water inlet pump between the adjusting cell and the electrolytic cell to enable water in the adjusting cell to flow to the electrolytic cell, and determining the number of electrode plates based on the inflow rate; acquiring the water inlet flow of the electrolytic cell, the interval width t of the electrode plates, the voltage value V and the ammonia nitrogen concentration b of target outlet water, inquiring to obtain a current value I, and starting a rectifier to start electrolysis;
s7: and opening a normal drain valve to start normal discharge after reaching the standard.
The invention has the beneficial effects that: 1. the front end is used for removing copper, the back end is used for electrically removing ammonia nitrogen, the design is carried out according to different PH value requirements in the efficient treatment process of the two treatment modes, and the effect is superior to that of the conventional integrated design for removing copper and ammonia nitrogen; 2. an internal circulation treatment structure is arranged in the copper removing equipment, so that the copper content in the wastewater is greatly reduced; 3. the relationship between the area of the electrode plate and the water inlet flow and the relationship between the current of the electrode plate of the electrolytic cell and the water inlet flow are optimized, the electrolytic treatment effect is obviously improved, and the pollution discharge effect is optimized; 4. the whole scheme does not adopt equipment with high cost, has the effect of low cost and is beneficial to popularization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be briefly described below. It is obvious that the drawings described below are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a front view of a circuit board etching wastewater treatment apparatus according to the present invention;
FIG. 2 is a plan view of the circuit board etching wastewater treatment apparatus of the present invention;
FIG. 3 is a schematic view of the apparatus for treating waste water from circuit board etching according to the present invention;
FIG. 4 is a graph showing a fit of the current versus flow of the present invention;
FIG. 5 is a flow chart showing the apparatus for treating waste water from etching circuit boards according to the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Wherein the showings are for the purpose of illustration only and are shown by way of illustration only and not in actual form, and are not to be construed as limiting the present patent; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
Fig. 1 to 2 show a circuit board etching wastewater treatment apparatus, wherein fig. 1 is a front view of the apparatus of the present invention, and fig. 2 is a top view of the apparatus of the present invention. The circuit board etching effluent treatment plant specifically includes: a concentrate tank 1 configured to collect etching waste water; the copper removing equipment 2 is configured for removing copper ions in the etching wastewater, and comprises a plurality of electrode plates, anode plates, cathode plates and rectifiers which are arranged in parallel, the copper removing operation is performed in a circulating mode after the pH value of the etching wastewater is adjusted to reach a set range, the electrode plates in the copper removing equipment 2 are ruthenium-iridium electrode plates, and the rectifiers are used for converting alternating current into direct current.
As a preferred embodiment, the copper removing device 2 removes copper through the internal circulation structure after adjusting NaCl concentration to a target value through a salt tank and adjusting PH to be between 8 and 9 through NaOH input through an alkali tank.
The reaction process of the copper removing equipment 2 comprises the following steps of: the metal ion gains an electron at the cathode to form the metal Me + (aq) + e → Me(s);
and (3) anode reaction: the electrons obtained from the cathode need to be balanced by the electrons lost from the anode.
In fact, there are several possible reactions in the anode, such as 2H2O-O2(g) +4H + +4e, when the metal concentration in the electrolyte is reduced, it is difficult to ensure that the metal is reduced at the cathode without further reaction.
The most easily occurring chemical reaction at low metal concentrations is the generation of oxygen, as follows: 2H + (aq) +2 e-. Two ball valves are arranged between the concentrated solution tank 1 and the copper removing equipment 2, a diaphragm pump is arranged between the two ball valves, and after the ball valves are opened, etching wastewater is introduced into the copper removing equipment through the diaphragm pump. The upper end of the copper removing equipment 2 is connected with a waste gas tower 6 through an interface, waste gas is discharged through the waste gas tower 6, and the lower end of the copper removing equipment 2 is connected with an aeration pipe, a salt tank and an alkali tank through an interface.
The copper removing equipment 2 is also provided with an internal circulation structure, and the internal circulation structure comprises a ball valve, a circulating valve (the circulating valve is a ball valve) and a circulating pump; before internal circulation, a ball valve in front of a copper-free water tank needs to be closed, then etching wastewater in the copper removing equipment is subjected to internal circulation through a circulating pump, the etching wastewater is controlled to have ammonia nitrogen concentration of 2000ppm and copper content of 50ppm through an internal circulation structure of the copper removing equipment 2, an alkali source is added at the same time, under the electrolysis effect of enhancing conductivity, copper ions in the etching wastewater are reduced into copper simple substances at an anode and a cathode, copper flocculation flocculate precipitates in an electrolytic tank and is not attached to an electrolytic plate, the copper content substances are guaranteed to be greatly reduced, and copper flocculation precipitate substances are cleaned and discharged to comprehensive wastewater through weekly maintenance and are collected and disposed.
Further, ammonia nitrogen wastewater discharged from the copper removing equipment 2 enters a copper-free water tank 3, etching wastewater treated by the copper removing equipment is stored in the copper-free water tank, and the output end of the copper-free water tank 3 is connected with an adjusting groove 4.
Further, ammonia nitrogen wastewater discharged from the copper removing equipment 2 enters an adjusting tank 4, and the adjusting tank 4 is configured to adjust the pH value of the etching wastewater, so that the concentration suitable for electrolysis of the electrolytic tank 5 is preliminarily adjusted, and the electrolysis effect is enhanced.
Preferably, two ball valves, a flow pump and a flowmeter are arranged between the copper-free water tank 3 and the adjusting tank 4, and the flow pump is arranged between the two ball valves; the upper end of the adjusting tank is also provided with an interface which is respectively connected with the salt tank and the alkali tank and is used for adding salt and alkali into the adjusting tank and further adjusting the concentration of the proper electrolyte; the adjusting tank 4, the salt tank and the alkali tank are respectively connected with an aeration pipe; the salt tank and the alkali tank are also respectively connected with a tap water pipe.
The electrolytic cell 5 of the embodiment comprises a cell body, an anode plate, a cathode plate and at least one electrode plate n (n is more than or equal to 1), wherein the electrolytic cell 5 is used for converting ammonia nitrogen into nitrogen gas through electrolysis, two ball valves, a diaphragm pump, a flow meter and an ammonia nitrogen concentration detection device are arranged between an adjusting tank 4 and the electrolytic cell 5, and the diaphragm pump is arranged between the two ball valves; the upper surface of the electrolytic bath 5 is also provided with an exhaust port connected with a waste gas tower, and the lower surface is provided with a discharge port and a sewage draining exit.
Tap water and alkali treatment waste gas are input into the waste gas tower 6, and the collected waste gas is further treated into gas reaching the standard and discharged.
In some embodiments, the copper removal equipment 2 removes copper through the internal circulation structure after adjusting the NaCl concentration to a target value through a salt tank and adjusting the PH to be between 8 and 9 through NaOH input through an alkali tank.
In some embodiments, the adjusting tank 4 inputs the etching wastewater into the electrolytic tank 5 after adjusting the NaCl concentration to a target value by the salt tank and adjusting the pH to between 11 and 12 by the NaOH input from the alkali tank.
In some embodiments, the electrode plate in the copper removing apparatus 2 is a ruthenium-iridium electrode plate.
And the controller comprises a memory, and all the flow meters are in signal connection with the controller.
In the embodiment, the tank body is provided with a water inlet and a water outlet, the water inlet is arranged at one corner of the tank body, and the water outlet is arranged at an oblique angle on the same plane with the water inlet; inflow q and total area S of electrode plateGeneral assemblySatisfies the relationship of SGeneral assemblyA numerical proportionality of (4-5) q, wherein SGeneral assemblyIs an electrode plate SSheetSum of areas of (1) n × SSheetUnit m of2(ii) a And (3) detecting by using a flowmeter to obtain inflow q, unit: l/min; the area of the electrode plate needs to be adapted to the size of the inflow, and when the inflow is large, the corresponding electrolysis area is large, so that the high-efficiency electrolysis speed can be obtained.
In some embodiments, the water intake is between 2.8L/min and 8.4L/min.
In some embodiments, the length L of the bottom surface of the electrolytic cell is 3-5 times of the total thickness of the electrode plate, and the height of the electrolytic cell is 1.1-1.3 times of the height of the electrode plate;
in the application, the spacing width t of the electrode plates is between 0.1 and 4 cm.
In fact, the electrolysis efficiency is influenced by both the current and the voltage of the electrolysis, the electrolysis efficiency is high when the current and the voltage are increased within a certain range, but if the current and the voltage are increased beyond a certain range, the improvement of the electrolysis efficiency is not obvious enough, and the cell voltage is further increased, so that the power consumption is increased, the cell temperature is increased, and the electrolysis efficiency is influenced in turn.
When the interval width t of the electrode plate is fixed, the electrolytic current I is in a proportional relation with the inflow q, and I is k1×q+b1The voltage V of the anode plate and the inflow water flow q are in a proportional relation, and I is k1×q3+k2×q2+k3X q + p, wherein k1、 k2、k3P is a cubic function coefficient fitted by a least square method;
after the inflow ammonia nitrogen concentration a of the electrolytic cell 5, the inflow flow q of the electrolytic cell, the interval width t of the electrode plates, the voltage value V and the target outflow ammonia nitrogen concentration b are obtained, inquiring a memory in the controller to obtain a current value I, and starting electrolysis.
Table 1 shows that the influent ammonia nitrogen concentration a is 2000ppm, and the effluent ammonia nitrogen concentration is gradually increased with the increase of the influent flow rate under the condition that the fixed electrode plate interval width t is 2cm, the voltage is 5V and the current is 201A.
TABLE 1
Figure BDA0003118669150000071
Table 2 shows the adjusted current values when the feed water ammonia nitrogen concentration a is 2000ppm, the fixed electrode plate interval width t is 2cm, the voltage is 5V, and the target value of the feed water ammonia nitrogen concentration b is 50 ppm:
TABLE 2
Figure BDA0003118669150000072
Under the condition that the voltage value V is 5V and the electrode plate interval t is 2cm, the relation between the electrolysis effect and the current is very close and important, when the inlet water ammonia nitrogen concentration a is 2000ppm and the target outlet water ammonia nitrogen concentration b is 50ppm, the current is adjusted to meet the requirement of the target outlet water ammonia nitrogen concentration b at different water inflow, and the optimal effect is achieved.
Based on the above, the relationship between the current of the electrode plate of the electrolytic cell 5 and the inflow water flow rate is set to reach the target value, and the electrolytic current I and the inflow water flow rate q in the table 2 are fitted to a cubic function by the least square method, wherein I is k1×q3+k2×q2+k3X q + p, the fit result is: i ═ 0.27 Xq3+3.1×q210.6 × q +211.86, as shown in the example fitting result shown in fig. 4, with fitting constants k1 ═ 0.27, k2 ═ 3.1, and k3 ═ 211.86. For other different ammonia nitrogen concentrations of inlet water and target ammonia nitrogen concentrations of outlet water, the optimal current values are also different, and are not described herein again.
And continuously adjusting the current according to different water inflow q at different electrode plate intervals t and voltages V to meet the requirement of the ammonia nitrogen concentration b of the target effluent water, fitting a cubic function by a least square method when the optimal effect is achieved to obtain the optimal current value under the current target condition, storing the obtained fitting constant in a memory, and adjusting the optimal current state when the inflow rate changes to obtain the good electrolysis effect.
In some embodiments, the electrolysis current of the cell is set in the range of 200A-220A, and the anode plate voltage of the cell is set in the range of 3-5V.
The etching wastewater is electrolyzed by the electrolytic bath, ammonia nitrogen is converted into nitrogen and a small amount of hydrogen, and the concentration of the ammonia nitrogen in the wastewater is greatly reduced. The etching wastewater treatment device can reduce the treatment load of a biochemical tank, effectively reduce the pressure of standard reaching of total nitrogen and ammonia nitrogen treatment of a wastewater station, exhaust gas generated in the electrolysis process is pumped to an exhaust gas tower by a waste gas pipeline, and the ammonia nitrogen wastewater after electrolysis is reduced to about 50ppm and is discharged into a comprehensive wastewater collecting tank, so that the device can participate in a wastewater treatment system after meeting the environmental protection requirement.
The embodiment also discloses a treatment method applied to the circuit board etching wastewater treatment device, and the implementation process comprises the following steps:
s1: the waste water to be treated in the etching water washing section enters a concentrated solution tank;
s2: after water in the etching water washing section normally enters a concentrated solution tank, a manual water inlet valve and a diaphragm pump between the concentrated solution tank and the copper removing equipment are opened, the diaphragm pump and the manual valve are closed after the water inflow of the copper removing equipment reaches an upper scale mark, NaOH is added into an adjusting groove by a salt groove and an alkali groove to maintain the PH between 8 and 9, and a rectifier and a circulating pump of an internal circulating structure of the copper removing equipment are opened;
s3: after the copper content is less than or equal to 50ppm, closing the rectifier, opening a ball valve between the circulating pump and the copper-free water tank, and closing a circulating valve on the copper removal equipment;
s4: opening a ball valve between the copper-free water tank and the adjusting tank, and starting the flow pump;
s5: the wastewater after passing through the copper-free water tank enters an adjusting tank, a ball valve between a salt tank and an alkali tank to the adjusting tank is kept normally open, NaOH is added into the adjusting tank to maintain the PH value between 11 and 12, and the concentration and the stock of NaCl solution are ensured within a set range at regular time; if the volume of the adjusting tank is insufficient due to the overlarge water inflow of the adjusting tank, adjusting the water inflow through a ball valve in front of a flow meter in front of the adjusting tank;
s6: sequentially opening a ball valve and an electrolytic cell water inlet pump between the adjusting cell and the electrolytic cell to enable water in the adjusting cell to flow to the electrolytic cell, and determining the number of electrode plates based on the inflow flow; acquiring the water inlet flow q of the electrolytic cell, the interval width t of the electrode plates, the voltage value V and the ammonia nitrogen concentration b of target outlet water, inquiring to obtain a current value I, and starting a rectifier to start electrolysis;
s7: and opening a normal drain valve to start normal discharge after reaching the standard.
The invention has the beneficial effects that: 1. the front end is used for removing copper, the back end is used for electrically removing ammonia nitrogen, the design is carried out according to different PH value requirements in the efficient treatment process of the two treatment modes, and the effect is superior to that of the conventional integrated design for removing copper and ammonia nitrogen; 2. an internal circulation treatment structure is arranged in the copper removing equipment, so that the copper content in the wastewater is greatly reduced; 3. the relationship between the area of the electrode plate and the water inlet flow and the relationship between the current of the electrode plate of the electrolytic cell and the water inlet flow are optimized, the electrolytic treatment effect is obviously improved, and the pollution discharge effect is optimized; 4. the whole scheme does not adopt high-cost equipment, has the effect of low cost and is favorable for popularization.
It should be understood that the above-described embodiments are merely preferred embodiments of the invention and the technical principles applied thereto. It will be understood by those skilled in the art that various modifications, equivalents, changes, and the like can be made to the present invention. However, such variations are within the scope of the invention as long as they do not depart from the spirit of the invention. In addition, certain terminology used in the description and claims of the present application is not limiting, but is used for convenience only.

Claims (6)

1. A circuit board etching wastewater treatment device comprises:
a concentrate tank (1) configured to collect etching waste water;
the copper removing equipment (2) is configured for removing copper ions in the etching wastewater, comprises a plurality of electrode plates, anode plates, cathode plates and rectifiers which are arranged in parallel, and performs circular copper removing operation after the pH value of the etching wastewater is adjusted to reach a set range; the rectifier is used for converting alternating current into direct current; the upper end of the copper removing equipment (2) is connected with the waste gas tower through an interface, and the lower end of the copper removing equipment is connected with the aeration pipe, the salt tank and the alkali tank through interfaces; the copper removing equipment (2) is also provided with an internal circulation structure, and the internal circulation structure comprises a ball valve, a circulation valve and a circulation pump; two water inlet valves are arranged between the concentrated liquid tank and the copper removing equipment, and a diaphragm pump is arranged between the two water inlet valves;
the input end of the copper-free water tank (3) is connected with the copper removal equipment (2), the etching wastewater treated by the copper removal equipment (2) is stored in the copper-free water tank (3), and the output end of the copper-free water tank is connected with the adjusting tank;
the adjusting tank (4) is configured for adjusting the pH value of the etching wastewater, two ball valves, a flow pump and a flowmeter are arranged between the copper-free water tank (3) and the adjusting tank (4), and the flow pump is arranged between the two ball valves; the upper end of the adjusting tank (4) is also provided with an interface which is respectively connected with a salt tank and an alkali tank and is used for adding salt and alkali into the adjusting tank (4); the adjusting tank, the salt tank and the alkali tank are respectively connected with an aeration pipe; the salt tank and the alkali tank are also respectively connected with a tap water pipe;
the electrolytic tank (5) comprises a tank body, an anode plate, a cathode plate and at least one electrode plate n (n is more than or equal to 1), the electrolytic tank (5) is used for converting the etching wastewater ammonia into nitrogen through electrolysis, two ball valves, a diaphragm pump and a flowmeter are arranged between the adjusting tank (4) and the electrolytic tank (5), and the diaphragm pump is arranged between the two ball valves; the upper surface of the electrolytic bath (5) is also provided with an exhaust port connected with a waste gas tower, and the lower surface is provided with a discharge port and a sewage draining outlet; an ammonia nitrogen concentration detection device is also arranged between the electrolytic tank (5) and the adjusting tank (4);
the waste gas tower (6) is used for inputting tap water and waste gas generated by electrolysis of the alkali treatment electrolytic cell (5);
the circuit board etching wastewater treatment device also comprises a controller, the controller comprises a memory, and the ammonia nitrogen concentration detection device and all the flow meters are in signal connection with the controller;
the method is characterized in that:
the tank body is provided with a water inlet and a water outlet, the water inlet is arranged at one corner of the tank body, and the water outlet is arranged at an oblique angle on the same plane with the water inlet; the water inlet flow q of the water inlet and the total area S of the electrode plateGeneral assemblySatisfies the relationship of SGeneral assemblyA numerical proportionality of (4-5) q, wherein SGeneral assemblyIs an electrode plate SSheetSum of areas of (1) n × SSheetArea unit m2(ii) a Detecting by a flowmeter between the electrolytic cell (5) and the adjusting cell (4) to obtain inflow q, wherein the flow is in L/min;
further, the electrolysis current I and the water inlet flow q satisfy the following functional relation: k is1×q3+k2×q2+k3X q + p, wherein k1、k2、k3Fitting coefficients of a cubic function for a least squares method, the functional relation and the coefficients being stored in a memory of a controller;
after the inflow ammonia nitrogen concentration a, the inflow flow rate, the interval width t of the electrode plates, the voltage value V and the target outflow ammonia nitrogen concentration b of the electrolytic tank (5) are obtained, the current value I is obtained through inquiry, and the electrolytic tank (5) is controlled by the controller to start electrolysis.
2. The apparatus for treating wastewater from etching a circuit board according to claim 1, wherein: and the copper removing equipment (2) adjusts the NaCl concentration to a target value through a salt tank and adjusts the pH to be between 8 and 9 through inputting NaOH through an alkali tank, and then removes copper through the internal circulation structure.
3. The apparatus for treating waste water from etching circuit boards according to claim 1 or 2, wherein: the adjusting tank (4) adjusts the NaCl concentration to a target value through a salt tank and adjusts the pH value to be between 11 and 12 through inputting NaOH through an alkali tank, and then inputs the etching waste water into the electrolytic tank (5).
4. The apparatus for treating waste water from etching circuit boards according to claim 1 or 2, wherein: the electrolytic current of the electrolytic tank (5) is set within the range of 200A-220A, and the voltage of the anode plate of the electrolytic tank (5) is set within the range of 3-5V.
5. The apparatus for treating waste water from etching circuit boards according to claim 1 or 2, wherein: the electrode plate in the copper removing equipment is a ruthenium-iridium electrode plate.
6. A treatment method applied to the circuit board etching wastewater treatment device of claim 1, characterized in that:
s1: the waste water to be treated in the etching water washing section enters a concentrated solution tank;
s2: after water in the etching water washing section normally enters a concentrated solution tank, a water inlet valve and a diaphragm pump between the concentrated solution tank and the copper removal equipment are opened, the diaphragm pump and the water inlet valve are closed after the water inflow of the copper removal equipment reaches an upper scale mark, NaOH is added into an adjusting groove by a salt groove and an alkali groove to maintain the pH value between 8 and 9, and a circulating pump and a circulating valve of an internal circulating structure of a rectifier and the copper removal equipment are opened to start internal circulating copper removal;
s3: after the copper content is less than or equal to 50ppm, closing the rectifier, opening a ball valve between the circulating pump and the copper-free water tank, and closing a circulating valve on the copper removal equipment;
s4: opening a ball valve between the copper-free water tank and the adjusting tank, and starting the flow pump;
s5: the wastewater after passing through the copper-free water tank enters an adjusting tank, a ball valve between a salt tank and an alkali tank to the adjusting tank is kept normally open, NaOH is added into the adjusting tank to maintain the pH value between 11 and 12, and the concentration and the stock of NaCl solution are ensured within a set range at regular time; if the volume of the adjusting tank is insufficient due to the overlarge water inflow of the adjusting tank, adjusting the water inflow through a ball valve in front of a flow meter in front of the adjusting tank;
s6: opening a ball valve and an electrolytic cell water inlet pump between the adjusting cell and the electrolytic cell in sequence to enable water in the adjusting cell to flow to the electrolytic cell, and determining the total area of the electrode plate based on the inflow flow; acquiring the water inlet flow q of the electrolytic cell, the interval width t of the electrode plates, the voltage value V and the ammonia nitrogen concentration b of target outlet water, inquiring to obtain a current value I, and starting a rectifier to start electrolysis;
s7: and opening a normal drain valve to start normal discharge after reaching the standard.
CN202110669808.9A 2021-06-17 2021-06-17 Circuit board etching wastewater treatment device and method Active CN113200635B (en)

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4280887A (en) * 1979-04-30 1981-07-28 Siemens Aktiengesellschaft Method of regenerating ammoniacal etching solutions useful for etching metallic copper
JP2004344819A (en) * 2003-05-23 2004-12-09 Sanyo Electric Co Ltd Water treatment device
CN102321908A (en) * 2011-09-02 2012-01-18 广州市天承化工有限公司 Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution
CN102428587A (en) * 2010-03-18 2012-04-25 松下电器产业株式会社 Current Control Element, Memory Element, Memory Device, And Production Method For Current Control Element
FR2993877A1 (en) * 2012-07-24 2014-01-31 Jean-Francois Bouyssou Installation, useful for treating an aqueous effluent charged with nitrogen from e.g. aquarium, comprises a reactor comprising catalyst, and a unit for pumping a part of recirculating flow of fluid from fluid chamber towards chamber
CN105523668A (en) * 2015-12-04 2016-04-27 陈丽珊 PCB ammonia-nitrogen wastewater zero discharge treatment method and device thereof
CN106006856A (en) * 2016-07-11 2016-10-12 苏州美源达环保科技股份有限公司 System for treating ammonia nitrogen in ammoniacal copper chloride wastewater through electrolytic catalytic oxidation method
CN107043185A (en) * 2017-06-19 2017-08-15 深圳慧欣环境技术有限公司 A kind of circuitboard etching waste liquid ammonia nitrogen processing method for resource recovery and system
CN107326388A (en) * 2017-06-30 2017-11-07 北京瑞和益生科技有限公司 A kind of evaluation method that Controlling model is electrolysed suitable for hypochlorous acid
CN108950564A (en) * 2018-08-27 2018-12-07 安徽绿洲危险废物综合利用有限公司 A kind of alkali etching electrolysis cycle regenerative system and electrolysis cycle regeneration method
CN210764480U (en) * 2019-04-23 2020-06-16 深圳市泓达环境科技有限公司 Treatment system for copper-containing ammonia nitrogen wastewater
CN112225302A (en) * 2020-08-31 2021-01-15 金禄电子科技股份有限公司 Ammonia nitrogen wastewater treatment method and system

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4280887A (en) * 1979-04-30 1981-07-28 Siemens Aktiengesellschaft Method of regenerating ammoniacal etching solutions useful for etching metallic copper
JP2004344819A (en) * 2003-05-23 2004-12-09 Sanyo Electric Co Ltd Water treatment device
CN102428587A (en) * 2010-03-18 2012-04-25 松下电器产业株式会社 Current Control Element, Memory Element, Memory Device, And Production Method For Current Control Element
CN102321908A (en) * 2011-09-02 2012-01-18 广州市天承化工有限公司 Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution
FR2993877A1 (en) * 2012-07-24 2014-01-31 Jean-Francois Bouyssou Installation, useful for treating an aqueous effluent charged with nitrogen from e.g. aquarium, comprises a reactor comprising catalyst, and a unit for pumping a part of recirculating flow of fluid from fluid chamber towards chamber
CN105523668A (en) * 2015-12-04 2016-04-27 陈丽珊 PCB ammonia-nitrogen wastewater zero discharge treatment method and device thereof
CN106006856A (en) * 2016-07-11 2016-10-12 苏州美源达环保科技股份有限公司 System for treating ammonia nitrogen in ammoniacal copper chloride wastewater through electrolytic catalytic oxidation method
CN107043185A (en) * 2017-06-19 2017-08-15 深圳慧欣环境技术有限公司 A kind of circuitboard etching waste liquid ammonia nitrogen processing method for resource recovery and system
CN107326388A (en) * 2017-06-30 2017-11-07 北京瑞和益生科技有限公司 A kind of evaluation method that Controlling model is electrolysed suitable for hypochlorous acid
CN108950564A (en) * 2018-08-27 2018-12-07 安徽绿洲危险废物综合利用有限公司 A kind of alkali etching electrolysis cycle regenerative system and electrolysis cycle regeneration method
CN210764480U (en) * 2019-04-23 2020-06-16 深圳市泓达环境科技有限公司 Treatment system for copper-containing ammonia nitrogen wastewater
CN112225302A (en) * 2020-08-31 2021-01-15 金禄电子科技股份有限公司 Ammonia nitrogen wastewater treatment method and system

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