CN113981449A - Method for recovering and treating waste etching solution - Google Patents
Method for recovering and treating waste etching solution Download PDFInfo
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- CN113981449A CN113981449A CN202111272388.7A CN202111272388A CN113981449A CN 113981449 A CN113981449 A CN 113981449A CN 202111272388 A CN202111272388 A CN 202111272388A CN 113981449 A CN113981449 A CN 113981449A
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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Abstract
The invention provides a method for recycling and treating etching waste liquid, which comprises the following steps: introducing the collected etching waste liquid into a filter tank, and adding a filter aid for filtering to obtain filtrate and filter residues; introducing the filtrate into an electrolytic cell for electrolysis operation, wherein copper and a first solution are obtained at a cathode, and a first gas and a second solution are obtained at an anode; introducing the first solution and the second solution into a mixed spray tower to obtain a mixed solution, introducing the first gas into the mixed spray tower, and spraying the first gas by using the mixed solution to obtain a regenerated etching solution and first-stage tail gas; introducing the primary tail gas into a reaction tank, adding a sodium hydroxide solution, and reacting to obtain secondary tail gas and bleaching water; introducing the secondary tail gas into an absorption tower for absorption to obtain a tertiary tail gas; and after the third-stage tail gas is detected to reach the standard, the third-stage tail gas is discharged. The utilization rate is high.
Description
Technical Field
The invention relates to the technical field of etching waste liquid treatment, in particular to a method for recycling and treating etching waste liquid.
Background
In the process of printed wiring boards, etching waste liquid is a liquid containing a large amount of copper ions and ammonium salts generated during etching,acidic spent etching solutions typically include Cu2+、Cu+、H+、CuCl4 2-、Cl-At present, the recovery method of the commonly used etching waste liquid is a precipitation method, the required cost is often higher, and the utilization rate of the formed waste water is not high.
Disclosure of Invention
Accordingly, there is a need for a method for recovering and treating an etching waste solution.
The technical scheme for solving the technical problems is as follows: a method for recycling and treating etching waste liquid comprises the following steps:
introducing the collected etching waste liquid into a filter tank, and adding a filter aid for filtering to obtain filtrate and filter residues;
introducing the filtrate into an electrolytic cell for electrolysis operation, wherein copper and a first solution are obtained at a cathode, and a first gas and a second solution are obtained at an anode;
introducing the first solution and the second solution into a mixed spray tower to obtain a mixed solution, introducing the first gas into the mixed spray tower, and spraying the first gas by using the mixed solution to obtain a regenerated etching solution and a first-stage tail gas;
introducing the primary tail gas into a reaction tank, adding a sodium hydroxide solution, and reacting to obtain secondary tail gas and bleaching water;
introducing the secondary tail gas into an absorption tower for absorption to obtain a tertiary tail gas;
and after the tertiary tail gas is detected to reach the standard, discharging.
In one embodiment, the filter aid is at least one of diatomaceous earth, paper pulp, and slag.
In one embodiment, the reacting with the sodium hydroxide solution comprises:
the concentration of the sodium hydroxide solution is 10-16%.
In one embodiment, the passing the secondary tail gas into an absorption tower for absorption includes:
and an alkaline solution is arranged in the absorption tower.
In one embodiment, the alkaline solution is a calcium hydroxide solution.
The utility model provides an etching waste liquid recovery processing system, includes filtering ponds, electrolytic bath, mixes spray column, retort and absorption tower, the filtering ponds the electrolytic bath mix spray column the retort with the absorption tower communicates in proper order.
In one embodiment, the filtering tank is provided with a filter screen, and one surface of the filter screen, which is far away from the bottom of the filtering tank, is provided with a plurality of barbs.
In one embodiment, the side of the filter screen, which is far away from the bottom of the filter tank, is provided with an adsorption layer.
In one embodiment, the hybrid spray tower comprises a tower main body, a rotating shaft, a rotating sheet, a water pump and a plurality of nozzles, wherein a containing cavity is formed in the tower main body, the rotating shaft is rotatably arranged in the containing cavity, the rotating sheet is connected with the rotating shaft, the rotating sheet is provided with a plurality of flow guide grooves, each nozzle is respectively installed on the side wall of the containing cavity, the water pump is arranged on the tower main body, the water pump is provided with a water inlet pipe and a water outlet pipe, the water inlet pipe is communicated with the containing cavity, the water outlet pipe is communicated with each nozzle, one side of the tower main body is provided with a gas inlet pipe, the top of the tower main body is provided with a gas outlet pipe, and the gas inlet pipe and the gas outlet pipe are both communicated with the containing cavity.
In one embodiment, a mixing groove is formed in a side wall of each diversion groove, and a height of a first side wall of each mixing groove is smaller than a height of a second side wall of each mixing groove.
The invention has the beneficial effects that: the collected waste etching solution is filtered and then electrolyzed to obtain copper, the first gas obtained by the anode after electrolysis reacts with the electrolyzed mixed solution to obtain regenerated etching solution, the first-stage tail gas reacts with the sodium hydroxide solution to obtain bleaching water, the second-stage tail gas is absorbed by the absorption tower, and finally the third-stage tail gas reaching the emission standard is discharged, so that the regenerated etching solution can be formed and recycled while the copper is recovered by the waste etching solution, the bleaching water can be generated by the reaction of the regenerated etching solution and the sodium hydroxide solution, and the utilization rate is high.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a schematic flow chart showing a method for recovering and treating an etching waste liquid according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of an etching waste liquid recovery processing system according to an embodiment of the present invention;
FIG. 3 is a schematic view of a part of the structure of an etching waste liquid recovery processing system according to an embodiment;
FIG. 4 is a schematic view of a part of the structure of the etching waste liquid recovery processing system in the other direction.
In the attached drawings, 100, a filtering tank; 200. an electrolytic cell; 300. a mixed spray tower; 310. a tower main body; 320. a rotating shaft; 330. a rotating sheet; 340. a nozzle; 350. a diversion trench; 351. a mixing trough; 400. a reaction tank; 500. an absorption tower.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, as shown in fig. 1, a method for recycling and treating etching waste liquid includes the following steps:
and step 110, introducing the collected etching waste liquid into a filter tank, and adding a filter aid for filtering to obtain filtrate and filter residues.
The etching waste liquid usually comprises copper chloride, cuprous chloride, hydrogen chloride and impurities, and is filtered by putting the etching waste liquid into a filter tank, so that filtrate after filter residues are filtered out is obtained, the filtrate is convenient to continue to be recycled, and inconvenience in recycling the etching waste liquid due to the filter residues is avoided. Wherein, the filter aid can be a substance that can improve filtration efficiency, can filter organic solution and suspension with higher speed, and its itself does not contain soluble impurity, can not bring into other impurity when carrying out filtering operation, back in the filter aid adds the etching waste liquid, the filter aid can adsorb the fine solid particle of condensation, impurity in the etching waste liquid can be adsorbed and condensed promptly, thereby be convenient for filter, again because of impurity is adsorbed and condensed to the group and become the filter residue, make the filtrating change and filter, and then the recovery of the etching waste liquid of being convenient for.
In order to enable the etching waste liquid to be better filtered, in one embodiment, the filter aid is at least one of diatomite, paper pulp and slag. Specifically, the filter aid is placed in the filter tank, so that fine solid particles are adsorbed and agglomerated by the filter aid, and the filtering speed during filtering is increased, wherein when the filter aid is diatomite, the diatomite has a good microporous structure, adsorption performance and compression resistance, a good flow rate ratio of filtered liquid can be obtained, fine suspended matters can be filtered, and the clarity is guaranteed. When the diatomite is added into the etching waste liquid, impurities in the etching waste liquid are adsorbed by the microporous structure in the diatomite, so that solid impurities in the etching waste liquid are condensed into blocks, and the etching waste liquid is convenient to filter.
In order to filter the filter residue better, make filter residue and filtrating separation effect better, after collecting etching waste liquid, let in etching waste liquid in the filtering ponds, add behind the filter aid, filter screen in the filtering ponds makes bold filter residue can be blocked to the upside of filter screen, and a plurality of barbs on the filter screen make the fritter filter residue blocked to the surface of the upside of filter screen, make the filter residue can not fall into the filtrating, the filter residue of being convenient for separates with the filtrating, thereby obtains clear filtrating. In one embodiment, the filtering tank is provided with a filter screen, and one surface of the filter screen, which is far away from the bottom of the filtering tank, is provided with a plurality of barbs. Specifically, each barb evenly sets up on the filter screen, and when etching waste liquid let in the filtering ponds, etching waste liquid process filter screen, filter screen surface and barb play the barrier effect to the impurity in the etching waste liquid, avoid impurity to descend to the bottom of filtering ponds along with etching waste liquid to make filter residue and filtrating separation, obtain clear filtrating, the edulcoration of the etching waste liquid of being convenient for, thereby make the recycle of etching waste liquid more convenient.
And step 120, introducing the filtrate into an electrolytic cell for electrolysis operation, wherein the cathode obtains copper and a first solution, and the anode obtains a first gas and a second solution.
Specifically, the filtrate is introduced into an electrolytic cell, a diaphragm is arranged in the electrolytic cell, so that the electrolytic cell can be divided into a cathode area and an anode area, the cathode and the anode are both provided with electrolytic sheets, the electrolytic sheets are titanium plates with metal coatings, and the electrolytic reaction equation generated by the cathode is as follows:
Cu2++2e-→Cu
Cu++e-→Cu
thus, after the electrolysis, the cathode obtained copper and the first solution, which was the catholyte. And copper is collected, so that the economic benefit of the recovery of the etching waste liquid is improved.
Wherein, the electrolysis reaction equation of the anode is as follows:
2Cl--2e-→Cl2
after the electrolysis is completed, the anode obtains chlorine, and the anode chamber contains a first gas and a second solution, wherein the first gas is chlorine, the second solution is an anolyte, the chlorine has strong oxidizing property and can be used as an oxidant, and the chlorine can easily pollute the environment and cannot be randomly discharged into the atmosphere and needs to be treated.
In one embodiment, the cathode obtains copper and a first solution comprising: and adding an accelerant into the cathode chamber, specifically, adding the accelerant into the cathode chamber, so that the accelerant reacts with copper ions to promote the reduction of the copper ions, thereby precipitating the copper more quickly, promoting the electrolytic reaction of the cathode, and enabling the electrolyzed copper to be more convenient to collect. Further, the accelerator is a mixture of hydroxylamine and polypropylene glycol, and the mass ratio of the hydroxylamine to the polypropylene glycol is 2: 1. In particular, hydroxylamine has a strong reducing property, which may cause Cu in the catholyte2+Reduction to Cu+Therefore, the reduction process of the copper ions is faster, and the electrolysis efficiency is improved. After the polypropylene glycol is added into the cathode electrolyte, the copper can not generate dislocation, so that the copper is prevented from forming branches, the formed copper can not damage the diaphragm, the copper is easy to strip, and the collection of the copper is convenient. Therefore, after the accelerant is added into the cathode chamber, the electrolysis speed of copper ions is increased, and formed copper is convenient to collect and beneficial to recycling of etching waste liquid.
And step 130, introducing the first solution and the second solution into a mixed spray tower to obtain a mixed solution, introducing the first gas into the mixed spray tower, and spraying the first gas by using the mixed solution to obtain a regenerated etching solution and a first-stage tail gas.
Specifically, mix first solution and second solution in mixing the spray column, be about to catholyte and anolyte mix, the mixed solution after will mixing again is through mode and the first gaseous contact that sprays for the mixed solution can be enough with first gaseous reaction, cuprous ion and the chlorine that has strong oxidizing property take place the reaction promptly, and like this, cuprous ion in the mixed solution can turn into copper ion, again because of itself contains the hydrogen chloride solution in the mixed solution, thereby can obtain regeneration etching solution, the reaction equation is as follows:
Cl2+2CuCl→2CuCl2
therefore, the regenerated etching solution can be formed while consuming chlorine gas, so that the pollution of the chlorine gas is reduced, and the cost required by the etching solution is reduced.
In order to accelerate the generation of the regenerated etching solution and improve the reaction rate of the mixed solution and the first gas, in one embodiment, the first solution and the second solution are introduced into a mixed spray tower to obtain a mixed solution, the first gas is introduced into the mixed spray tower, and in the operation of spraying the first gas with the mixed solution, the mixed solution and the first gas are also stirred. In this embodiment, mix spray column includes tower main part, rotation axis, revolving fragment, water pump and a plurality of nozzle, the tower main part has been seted up and has been held the chamber, the rotation axis rotate set up in hold in the chamber, the revolving fragment with rotation axis connection, a plurality of guiding gutters have been seted up to the revolving fragment, each the nozzle is installed respectively on the lateral wall that holds the chamber, the water pump set up in on the tower main part, the water pump is provided with inlet tube and outlet pipe, the inlet tube with hold the chamber intercommunication, the outlet pipe with each the nozzle intercommunication, one side of tower main part is provided with the intake pipe, the top of tower main part is provided with the outlet duct, the intake pipe with the outlet duct all with hold the chamber intercommunication. The containing cavity is used for containing mixed liquid, the distance between the rotating shaft and the side wall of the containing cavity is greater than the distance between the rotating sheet and the side wall of the containing cavity, namely the rotating sheet is not abutted against the side wall of the containing cavity and has a gap, the tower body is provided with a driver which is in driving connection with the rotating shaft and is used for driving the rotating shaft to rotate, wherein the mode that the driver drives the rotating shaft to rotate is a mode which can be known by a person skilled in the art and can be realized, in the embodiment, the first solution and the second solution are introduced into the containing cavity to obtain the mixed liquid, the driver drives the rotating shaft to rotate, the rotating sheet rotates along with the rotating sheet, part of the mixed liquid rotates through the thrust of the rotating sheet, and as the guide groove is arranged on the rotating sheet, the other part of the mixed liquid passes through the guide groove and cannot be pushed by the rotating sheet, but passes through the guide groove, thus, part of the mixed liquid rotates along with the rotating sheet, the other part of mixed liquid flows through the guiding gutter, does not rotate with the rotor plate synchronous for mixed liquid forms relative displacement, and like this, each molecule in the mixed liquid violently collides because of the displacement difference, thereby makes mixed liquid misce bene. When the first gas is introduced into the mixing spray tower, the mixed liquid is pumped out from the containing cavity through the water inlet pipe by the water pump, and then introduced into the nozzle through the water outlet pipe, so that the nozzle sprays the mixed liquid, wherein the mode of pumping the mixed liquid by the water pump is a mode which can be known by a person skilled in the art, and can be realized, and the description of redundancy is not performed in the embodiment; when mixed liquid sprays through the water pump, still drive mixed liquid through the rotor plate and take place to rotate for the hydrone in the mixed liquid constantly splashes holding the intracavity, like this, make mixed liquid better with first gaseous contact, chlorine can react with the cuprous chloride in the mixed liquid, generate copper chloride, make mixed liquid form the displacement difference through setting up the guiding gutter on the rotor plate promptly, make the intermolecular take place violent collision, obtain regeneration etching solution, the formation of the regeneration etching solution of being convenient for.
It is worth explaining, after letting in mixed spray column with first solution and second solution, the revolving fragment plays stirring effect to mixed liquid, make mixed liquid mix more evenly, when mixed liquid sprays first gas through the water pump, guiding gutter on the revolving fragment makes each molecule in the mixed liquid take place violent collision because of the displacement difference, thereby produce not equidirectional swirl, at this moment, mixed liquid can spill, make first gas can take place to contact with more mixed liquid, and thus, can make cuprous ion in the mixed liquid fully contact with the chlorine in the first gas, thereby make cuprous ion and chlorine in first solution and the second solution can fully react and generate bivalent copper ion, be convenient for the generation of regeneration etching solution.
In order to enable the first gas to be better contacted with the mixed liquid and improve the generation rate of the regenerated etching liquid, the side wall of each diversion trench is provided with a mixed flow trench, and the height of the first side wall of each mixed flow trench is smaller than that of the second side wall of each mixed flow trench. Specifically, the direction of rotation axis is by first lateral wall towards the second lateral wall, the rotation axis is rotatory by the direction of the higher lateral wall of lower lateral wall orientation promptly, thus, when mixed liquid passes through the guiding gutter, the second lateral wall in mixed liquid groove plays the effect of blockking to partial mixed liquid, thus, make partial mixed liquid can form strand rivers in mixed liquid inslot, and strand rivers are under the condition of rotation axis fast rotation, can be thrown away from the lateral wall in mixed liquid groove, with the lateral wall that holds the chamber bump, thereby mix liquid with another part and collide, make the molecular kinetic energy increase of mixed liquid spare, thereby be convenient for mix the mixture of liquid. When first gas leads to, little burst rivers can fully contact with first gas to the area of contact of increase mixed liquid and gas, when the rotation axis was rotatory promptly, first lateral wall through the muddy groove is higher than the second lateral wall, and partial mixed liquid is intercepted by higher second lateral wall, forms little burst rivers spill, thereby makes the increase of intermolecular kinetic energy, and then better contacts mixed liquid and chlorine and reacts, improves reaction rate, obtains regeneration etching solution.
Further, the cross-sectional shape of the side wall of the mixing groove is hook-shaped. Specifically, when mixed liquid takes place to rotate along with the rotation of revolving fragment, mixed liquid flows into mixed flow groove, forms one rivers in the lateral wall in mixed flow groove, because of the mixed flow groove is for colluding the shape, it has certain degree of depth, and the rivers that hold in the mixed flow groove are more, and when the revolving fragment rotates fast, rivers will rotate thereupon, and the direction of keeping away from the rotation axis by the one side orientation that is close to the rotation axis splashes to make the mixed liquid that splashes take place violent collision with other mixed liquids, thereby make the mixed degree better. And because chlorine flows in holding the intracavity, the mixed solution that splashes out also can react with chlorine better to make chlorine and cuprous chloride's reaction more abundant. When the cross section that is about to the lateral wall in mixed flow groove sets up to colluding the shape, mixed liquid is blockked by the higher one side in mixed flow groove when the rotation axis rotates, forms the rivers that have certain degree of depth in mixed flow inslot, and more rivers splash to holding the chamber lateral wall, increase molecular kinetic energy, rivers with hold the collision of chamber lateral wall and fully react with chlorine, obtain regeneration etching solution.
And 140, introducing the primary tail gas into a reaction tank, adding a sodium hydroxide solution, and reacting to obtain secondary tail gas and bleaching water.
Specifically, the primary tail gas reacts with a sodium hydroxide solution to obtain bleaching water, and the bleaching water is a mixture containing sodium hypochlorite and sodium chloride generated by the reaction of chlorine and the sodium hydroxide solution. The reaction equation is as follows:
Cl2+2NaOH→NaCl+NaClO+H2O
the sodium hypochlorite is an effective component of the bleaching water, and the hypochlorous acid has strong oxidizing property and can oxidize colored substances, so that the bleaching purpose is achieved, the chlorine can be changed into valuables, the burden on the environment is reduced, and the economic benefit is increased after the chlorine is absorbed.
In order to achieve a better disinfection of the generated bleaching water, in one embodiment the primary off-gas is reacted with a sodium hydroxide solution, the concentration of which is 10% to 16%. Specifically, when the concentration of the sodium hydroxide solution is 10%, the sodium hydroxide solution reacts with chlorine gas, so that the concentration of the generated free alkali is low, and the generated sodium hypochlorite has good oxidizability, namely, the disinfection effect is better. Therefore, the generated bleaching water has better disinfection effect, and the recovery benefit of the etching waste liquid is improved.
And 150, introducing the secondary tail gas into an absorption tower for absorption to obtain a tertiary tail gas.
Particularly, the absorption tower is used for absorbing the secondary tail gas, the pollution of chlorine is reduced, the tail gas exhausted into the atmosphere meets the national emission standard, further, an alkaline solution is arranged in the absorption tower and can be fully contacted with the chlorine, so that the alkaline solution and the chlorine react to generate soluble salt and water, no redundant impurities are produced, the environment is protected, the safety is realized, and the emission of the chlorine is reduced. Further, the alkaline solution is set to calcium hydroxide, and the reaction equation is as follows:
2Cl2+2Ca(OH)2→CaCl2+Ca(ClO)2+2H2O
therefore, the chlorine gas can be absorbed to avoid being discharged into the atmosphere after being not absorbed to the qualified emission standard, thereby reducing the damage to the atmosphere.
In order to reduce the pollution of the tail gas, in one embodiment, the secondary tail gas is introduced into an absorption tower for absorption, and an alkaline solution is arranged in the absorption tower. Specifically, the secondary tail gas is introduced into the absorption tower, and then the chlorine gas can react with the alkaline solution, so that the chlorine gas is absorbed by the alkaline solution, and the burden on the environment is reduced. Further, the alkaline solution is a calcium hydroxide solution. Specifically, the calcium hydroxide is low in cost and easy to obtain, the cost of waste etching liquid recovery treatment is reduced to a certain extent, and when chlorine reacts with a calcium hydroxide solution, calcium hypochlorite, namely bleaching powder, is obtained, and the bleaching powder has strong oxidizing property, can be used for bleaching cotton and linen textiles, chemical fibers, paper pulp and starch, and is also used for disinfection and sterilization of drinking water and swimming pool water. Can generate certain economic benefit, thus reducing chlorine pollution and simultaneously obtaining products with economic benefit, thereby leading the recovery of the etching waste liquid to be more economic and environment-friendly.
And 160, discharging the tertiary tail gas after the tertiary tail gas is detected to reach the standard.
Specifically, when tertiary tail gas discharges, need pass through industrial waste gas on-line monitoring equipment to judge whether tertiary tail gas reaches the national emission standard, when tertiary tail gas passes through industrial waste gas on-line monitoring equipment, industrial waste gas on-line monitoring equipment carries out automatic monitoring to tertiary tail gas, thereby confirms whether to discharge tertiary tail gas, avoids not conforming to the exhaust emission to the atmosphere of national emission standard. The mode of detecting the industrial waste gas by the industrial waste gas on-line monitoring equipment is a mode which can be known by a person skilled in the art, and can be realized, and is not described redundantly in the embodiment.
In one embodiment, as shown in fig. 2, the following is a tin-stripping waste liquid recycling and regenerating treatment system portion to which the tin-stripping waste liquid recycling and regenerating treatment method is applied. The utility model provides an etching waste liquid recovery processing system, includes filtering ponds 100, electrolytic bath 200, mixes spray column 300, retort 400 and absorption tower 500, filtering ponds 100 electrolytic bath 200 mix spray column 300 retort 400 with absorption tower 500 communicates in proper order. Specifically, when the etching waste liquid is recycled, the etching waste liquid is firstly introduced into the filter tank 100 for filtering, so that filtrate and filter residue are separated, after the filter residue is separated, the filtrate is introduced into the electrolytic tank 200 from the lower part of the filter tank 100 through a first pipeline, a cathode and an anode are separated through a diaphragm, so that a cathode chamber and an anode chamber are obtained, the filtrate is respectively introduced into the cathode chamber and the anode chamber, direct current is introduced for electrolysis, after the electrolysis is finished, the cathode can obtain copper and a first solution, namely, copper and a cathode electrolyte are obtained through electrolysis in the cathode chamber, and the copper is collected; the anode obtains a first gas and a second solution, namely chlorine and anolyte are obtained by electrolysis in the anode chamber, and the first gas is collected by the gas capture device. And introducing the first solution and the second solution into the mixed spray tower 300 through a second pipeline for mixing to obtain a mixed solution, introducing the first gas into the mixed spray tower 300 through a third pipeline from the gas capture device to fully dissolve and react the first gas and the mixed solution, and introducing the regenerated etching solution obtained after reaction into an etching solution production line through a pump for etching. And the first tail gas is introduced into the reaction tank 400 through the venturi device, and the first tail gas is made to react with the sodium hydroxide solution to obtain bleaching water and secondary tail gas, and then the bleaching water is collected. After the second-stage tail gas is collected, the second-stage tail gas is introduced into the absorption tower 500 through the fourth pipeline, and the second-stage tail gas is absorbed by the alkaline solution, so that chlorine and hydrogen chloride in the second tail gas are absorbed by the alkaline solution. And finally, the third-level tail gas is led to an industrial waste gas on-line monitoring device through a fifth pipeline, and if the third-level tail gas meets the emission standard, the third-level tail gas can be led into the atmosphere.
Like this, each device communicates step by step for etching waste liquid can obtain regeneration etching solution after by the electrolysis, and the tail gas that produces during the electrolysis can be absorbed by the stratum layer, thereby when obtaining this kind of economic products of bleaching water, can also obtain the tail gas that accords with national emission standard, increases economic benefits when reducing the pollution, has reduced the acquisition cost of etching solution, thereby accomplishes etching waste liquid's recycle better.
In order to better filter the filter residue, in one embodiment, the filtering tank 100 is provided with a filter screen, and one surface of the filter screen, which is far away from the bottom of the filtering tank 100, is provided with a plurality of barbs. Specifically, each barb evenly sets up on the filter screen, and when etching waste liquid let in filtering ponds 100, etching waste liquid process filter screen, filter screen surface and barb play the barrier effect to the impurity in the etching waste liquid, avoid impurity to descend to filtering ponds 100's bottom along with etching waste liquid to make filter residue and filtrating separation, obtain clear filtrating, the edulcoration of the etching waste liquid of being convenient for, thereby make etching waste liquid's recycle more convenient.
In order to improve the filtering effect, in one embodiment, an adsorption layer is disposed on a side of the filter screen away from the bottom of the filtering tank 100. Specifically, be provided with the active carbon on the adsorbed layer, when etching waste liquid flows into filtering ponds 100 in, the adsorbed layer plays adsorption to etching waste liquid to make etching waste liquid's filter residue live by the clearance absorption of adsorbed layer, can not descend to filtering ponds 100's bottom, thereby be convenient for etching waste liquid's filtration, improve the efficiency that etching waste liquid filtered the recovery.
In order to facilitate the generation of the regenerated etching solution, as shown in fig. 3 and 4, in one embodiment, the hybrid spray tower 300 includes a tower body 310, a rotating shaft 320, a rotating plate 330, a water pump and a plurality of nozzles 340, the tower body 310 is opened with a receiving cavity, the rotating shaft 320 is rotatably disposed in the receiving cavity, the rotating plate 330 is connected to the rotating shaft 320, the rotating plate 330 is provided with a plurality of guiding grooves 350, each nozzle 340 is respectively mounted on the side wall of the accommodating cavity, the water pump is arranged on the tower main body 310, the water pump is provided with a water inlet pipe and a water outlet pipe, the water inlet pipe is communicated with the containing cavity, the water outlet pipe is communicated with each nozzle 340, an air inlet pipe is arranged on one side of the tower main body 310, an air outlet pipe is arranged at the top of the tower main body 310, and the air inlet pipe and the air outlet pipe are communicated with the accommodating cavity.
Specifically, the containing cavity is used for containing the mixed liquid, the distance between the rotating shaft 320 and the side wall of the containing cavity is greater than the distance between the rotating plate 330 and the side wall of the containing cavity, that is, the rotating plate 330 is not abutted against the side wall of the containing cavity, and a gap exists between the rotating plate 330 and the side wall of the containing cavity, the tower main body 310 is provided with a driver, the driver is in driving connection with the rotating shaft 320, and the driver is used for driving the rotating shaft 320 to rotate, wherein the driver drives the rotating shaft 320 to rotate in a manner that can be known by those skilled in the art, and can be realized, in this embodiment, without redundant description, the first solution and the second solution are introduced into the containing cavity to obtain the mixed liquid, the driver drives the rotating shaft 320 to rotate, the rotating plate 330 rotates along with the first solution, a part of the mixed liquid rotates by the thrust of the rotating plate 330, and another part of the mixed liquid passes through the guiding groove 350 and cannot be pushed by the rotating plate 330, but pass through the guiding gutter 350, like this, part mixed liquid rotates along with the rotor 330, and another part mixed liquid flows through the guiding gutter 350, does not rotate with the rotor 330 synchronous for the mixed liquid forms relative displacement, and like this, the hydrone in the mixed liquid violently collides because of the displacement difference, thereby makes the mixed liquid misce bene. When the first gas is introduced into the mixing spray tower 300, the mixed liquid is pumped out from the containing cavity by the water pump through the water inlet pipe, and then introduced into the nozzle 340 through the water outlet pipe, so that the nozzle 340 sprays the mixed liquid, wherein the way of pumping the mixed liquid by the water pump is a way which can be known by those skilled in the art, and can be realized, and the description of the redundancy is not made in the embodiment; when mixed liquid sprays through the water pump, still drive mixed liquid through rotor 330 and take place to rotate, make the hydrone in the mixed liquid constantly splash in holding the intracavity, thus, make mixed liquid better with first gaseous contact, chlorine can react with the cuprous chloride in the mixed liquid, generate copper chloride, make mixed liquid form the displacement difference through setting up guiding gutter 350 on rotor 330 promptly, make the intermolecular emergence violent collision, obtain regeneration etching solution, the formation of the regeneration etching solution of being convenient for.
Further, a mixing groove 351 is formed in a side wall of each diversion trench 350, and a height of a first side wall of each mixing groove 351 is smaller than a height of a second side wall of each mixing groove 351. Specifically, the direction of rotation axis 320 is by first lateral wall towards the second lateral wall, rotation axis 320 is rotated by the direction of the higher lateral wall of lower lateral wall orientation promptly, like this, when mixed liquid passes through guiding gutter 350, the second lateral wall of mixing gutter 351 plays the effect of blockking to partial mixed liquid, thus, make partial mixed liquid can form little rivers in mixing gutter 351, and little rivers can be thrown away from mixing gutter 351's lateral wall under the circumstances of rotation axis 320 fast turn, collide with the lateral wall that holds the chamber, thereby collide with another part mixed liquid, make the molecular kinetic energy of mixed liquid increase, thereby be convenient for the mixture of mixed liquid. When first gas leads to, little burst rivers can fully contact with first gas to increase the area of contact of mixed liquid and gas, when rotation axis 320 was rotatory promptly, first lateral wall through mixed flow groove 351 is higher than the second lateral wall, and partial mixed liquid is intercepted by higher second lateral wall, forms little burst rivers spill, thereby makes the kinetic energy increase of intermolecular, and then better contacts mixed liquid and chlorine and reacts, improves reaction rate, obtains regeneration etching solution.
Further, the side wall of the mixing groove 351 has a hook-shaped cross-sectional shape. Specifically, when the mixed liquid rotates along with the rotation of revolving fragment 330, the mixed liquid flows into mixed flow groove 351, forms a rivers in the lateral wall of mixed flow groove 351, because of mixed flow groove 351 is the hook-shaped, it has certain degree of depth, the rivers that hold in the mixed flow groove 351 are more, when revolving fragment 330 rotates fast, rivers will rotate thereupon, splash by the one side orientation that is close to rotation axis 320 far away from the direction of rotation axis 320, thereby make the mixed liquid that splashes take place violent collision with other mixed liquids, thereby make the mixed degree better. And because chlorine flows in holding the intracavity, the mixed solution that splashes out also can react with chlorine better to make chlorine and cuprous chloride's reaction more abundant. When the cross section that is about to mix the lateral wall of chute 351 sets up to colluding the shape, mixed liquid is blockked by the higher one side of mixed flow chute 351 when rotation axis 320 rotates, forms the rivers that have certain degree of depth in mixed flow chute 351, and more rivers splash to holding the chamber lateral wall, increase molecular kinetic energy, rivers with hold the collision of chamber lateral wall and fully react with chlorine, obtain regeneration etching solution.
It is worth explaining that, the revolving fragment 330 sets up to three, and each revolving fragment 330 is Y shape distribution around rotation axis 320, specifically, when the revolving fragment 330 sets up to three, each revolving fragment 330 is rotatory around rotation axis 320, and the rotation of the mixed liquid of being convenient for mixes, and distributes through Y shape for each revolving fragment 330 drives the mixed liquid rotation more simply, reduces required thrust, and is laborsaving convenient, reduces the energy consumption.
The invention is further described below with reference to specific examples.
Example 1
(1) Introducing the collected etching waste liquid into a filtering tank 100, and adding diatomite for filtering for 30min to obtain filtrate and filter residue;
(2) introducing the filtrate into an electrolytic cell 200 for electrolysis, wherein the electrolysis time is 45min, the temperature during electrolysis is controlled at 30 ℃, copper and a cathode electrolyte are obtained at a cathode, and a first gas and an anode electrolyte are obtained at an anode;
(3) introducing the catholyte and the anolyte into a mixed spray tower 300, mixing for 20min to obtain a mixed solution, introducing a first gas into the mixed spray tower 300, and spraying the first gas by using the mixed solution to obtain a regenerated etching solution and a first-stage tail gas;
(4) introducing the primary tail gas into a reaction tank 400, adding a sodium hydroxide solution, reacting for 10min to obtain secondary tail gas and bleaching water;
(5) introducing the secondary tail gas into an absorption tower 500 for absorption, and carrying out absorption reaction with a calcium hydroxide solution in the absorption tower 500 to obtain a tertiary tail gas;
(6) and detecting the tertiary tail gas by using industrial waste gas on-line monitoring equipment, and then discharging the tertiary tail gas.
Example 2
(1) Introducing the collected etching waste liquid into a filtering tank 100, and adding diatomite for filtering for 30min to obtain filtrate and filter residue;
(2) introducing the filtrate into an electrolytic cell 200 for electrolysis for 45min, controlling the temperature during electrolysis at 30 ℃, adding an accelerant into a cathode chamber, obtaining copper and a cathode electrolyte at a cathode, and obtaining a first gas and an anode electrolyte at an anode;
(3) introducing the catholyte and the anolyte into a mixed spray tower 300, mixing for 20min to obtain a mixed solution, introducing a first gas into the mixed spray tower 300, and spraying the first gas by using the mixed solution to obtain a regenerated etching solution and a first-stage tail gas;
(4) introducing the primary tail gas into a reaction tank 400, adding a sodium hydroxide solution, reacting for 10min to obtain secondary tail gas and bleaching water;
(5) introducing the secondary tail gas into an absorption tower 500 for absorption, and carrying out absorption reaction with a calcium hydroxide solution in the absorption tower 500 to obtain a tertiary tail gas;
(6) and detecting the tertiary tail gas by using industrial waste gas on-line monitoring equipment, and then discharging the tertiary tail gas.
The collected waste etching solution is filtered and then electrolyzed to obtain copper, the first gas obtained by the anode after electrolysis reacts with the electrolyzed mixed solution to obtain regenerated etching solution, the first-stage tail gas reacts with the sodium hydroxide solution to obtain bleaching water, the second-stage tail gas is absorbed by the absorption tower 500, and finally the third-stage tail gas reaching the emission standard is discharged, so that the regenerated etching solution can be formed and recycled while the copper is recovered by the waste etching solution, and the bleaching water can be generated by the reaction of the regenerated etching solution and the sodium hydroxide solution. The utilization rate is high.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above embodiments only express a few embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The method for recycling and treating the etching waste liquid is characterized by comprising the following steps of:
introducing the collected etching waste liquid into a filter tank, and adding a filter aid for filtering to obtain filtrate and filter residues;
introducing the filtrate into an electrolytic cell for electrolysis operation, wherein copper and a first solution are obtained at a cathode, and a first gas and a second solution are obtained at an anode;
introducing the first solution and the second solution into a mixed spray tower to obtain a mixed solution, introducing the first gas into the mixed spray tower, and spraying the first gas by using the mixed solution to obtain a regenerated etching solution and a first-stage tail gas;
introducing the primary tail gas into a reaction tank, adding a sodium hydroxide solution, and reacting to obtain secondary tail gas and bleaching water;
introducing the secondary tail gas into an absorption tower for absorption to obtain a tertiary tail gas;
and after the tertiary tail gas is detected to reach the standard, discharging.
2. The method for recycling and treating etching waste liquid according to claim 1, wherein the filter aid is at least one of diatomaceous earth, paper pulp and slag.
3. The method for recycling and treating etching waste liquid according to claim 1, wherein the reaction with sodium hydroxide solution comprises:
the concentration of the sodium hydroxide solution is 10-16%.
4. The method for recycling and treating the etching waste liquid according to claim 1, wherein the step of introducing the secondary tail gas into an absorption tower for absorption comprises:
and an alkaline solution is arranged in the absorption tower.
5. The method according to claim 4, wherein the alkaline solution is a calcium hydroxide solution.
6. The utility model provides an etching waste liquid recovery processing system which characterized in that, includes filtering ponds, electrolytic bath, mixes spray column, retort and absorption tower, the filtering ponds the electrolytic bath mix spray column the retort with the absorption tower communicates in proper order.
7. The etching waste liquid recovery and treatment system according to claim 6, wherein the filtering tank is provided with a filter screen, and one surface of the filter screen, which is far away from the bottom of the filtering tank, is provided with a plurality of barbs.
8. The etching waste liquid recovery and treatment system according to claim 7, wherein an adsorption layer is provided on a surface of the filter screen away from the bottom of the filter tank.
9. The etching waste liquid recovery processing system according to claim 6, wherein the mixed spray tower comprises a tower main body, a rotating shaft, a rotating plate, a water pump and a plurality of nozzles, the tower main body is provided with a containing cavity, the rotating shaft is rotatably arranged in the containing cavity, the rotating plate is connected with the rotating shaft, the rotating plate is provided with a plurality of guide grooves, each nozzle is respectively arranged on a side wall of the containing cavity, the water pump is arranged on the tower main body, the water pump is provided with a water inlet pipe and a water outlet pipe, the water inlet pipe is communicated with the containing cavity, the water outlet pipe is communicated with each nozzle, one side of the tower main body is provided with a gas inlet pipe, the top of the tower main body is provided with a gas outlet pipe, and the gas inlet pipe and the gas outlet pipe are both communicated with the containing cavity.
10. The system of claim 9, wherein a mixing groove is formed in a side wall of each of the guide grooves, and a height of a first side wall of each of the mixing grooves is smaller than a height of a second side wall of the mixing groove.
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