CN110697962A - Wastewater treatment process for etching cleaning wastewater - Google Patents
Wastewater treatment process for etching cleaning wastewater Download PDFInfo
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- CN110697962A CN110697962A CN201911069649.8A CN201911069649A CN110697962A CN 110697962 A CN110697962 A CN 110697962A CN 201911069649 A CN201911069649 A CN 201911069649A CN 110697962 A CN110697962 A CN 110697962A
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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
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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
A wastewater treatment process for etching cleaning wastewater comprises the following steps: flocculation precipitation, evaporation desalting and sludge treatment. The flocculation precipitation comprises the steps of collecting etching cleaning wastewater in a wastewater collection pool, conveying the etching cleaning wastewater to a reaction tank through a wastewater lifting pump, adding alkali into the reaction tank, adjusting the pH value to be neutral, adding a coagulant, and adding a flocculant finally; and the sediment in the reaction tank is sunk into a sludge hopper below in the sedimentation tank under the action of gravity, and the wastewater in the reaction tank flows to the clear water tank through an upper overflow weir. The wastewater treatment process for the etching cleaning wastewater disclosed by the invention is simple in process and convenient to operate, realizes zero discharge of sewage, does not generate toxic and harmful byproducts in treatment engineering, is pollution-free, and has extremely high economic benefit and environmental benefit, and the treated etching cleaning wastewater is clear in water quality, free of obvious suspended matters, less than or equal to 700us/cm in electric conductivity and wide in prospect.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a wastewater treatment process for etching cleaning wastewater.
Background
In recent years, with the rapid development of the electronic information industry, printed circuit boards (PCB for short) have also been rapidly developed as the supporting industry, and the demand is increasing. Printed circuit technology has been increasingly being implemented and used on a large scale since the mid-50 of the 20 th century. The PCB industry in China is gradually developed, and in 2006, China surpasses Japan for the first time, becomes the largest PCB manufacturing big country in the world and keeps the status for a long time.
Although the rapid development of the PCB industry drives the economic development of China, the problems of various environmental pollutions brought by the rapid development of the PCB industry are more and more serious. In the manufacture of printed circuit boards, etching is one of the indispensable processes. A large amount of waste liquid generated in the etching process contains complex components such as copper ions, ammonia water, chloride and the like. When the concentration of copper ions is gradually increased to a specific range, the copper ions become waste liquid, and particularly serious damage is brought to the human environment. Generally, the copper content is about 100-160 g/L, and the ammonia Nitrogen (NH)3And NH4 +) The content is about 150 to 200 g/L. After the waste liquid is subjected to copper recycling by the traditional method, the ammonia nitrogen concentration in the waste liquid is still very high and is about 10-50 g/L. If the etching cleaning waste liquid can be effectively recycled, the problem of current related copper supply shortage can be relieved, and environmental hazards brought by the copper supply shortage can be reduced.
Therefore, the waste etching cleaning liquid cannot be directly discharged, and must be reasonably and effectively recycled and harmlessly treated. Heretofore, the etching cleaning waste liquid is generally simply treated by conventional methods such as adsorption method, extraction method, precipitation method and liquid film separation, but these methods still have many disadvantages, such as easy secondary pollution, high treatment cost, undesirable effect and the like.
Chinese patent application No. CN201310491934.5 discloses a method for treating waste etching solution and a treatment device thereof, wherein acidic waste etching solution and alkaline waste etching solution are mixed; adjusting the pH value of the mixed etching waste liquid and heating the etching waste liquid to perform neutralization reaction; separating the precipitate and the filtrate; and adding a flocculating agent into the filtrate to flocculate suspended particles and colloidal arsenic in the filtrate, the steps are complicated, the treatment cost is high, the effect is not ideal, and the method is not beneficial to popularization.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects, the invention aims to provide the waste water treatment process for the etching cleaning waste water, which has the advantages of simple process, convenient operation, realization of zero discharge of sewage, no generation of toxic and harmful byproducts in the treatment engineering, no pollution, extremely high economic benefit and environmental benefit, clear water quality, no obvious suspended matters, electric conductivity less than or equal to 700us/cm and wide prospect.
The purpose of the invention is realized by the following technical scheme:
a wastewater treatment process for etching cleaning wastewater is characterized by comprising the following steps:
(1) flocculation and precipitation: collecting etching cleaning wastewater in a wastewater collection tank, conveying the etching cleaning wastewater to a reaction tank through a wastewater lifting pump, adding alkali into the reaction tank, adjusting the pH value to be neutral, adding a coagulant, and adding a flocculant; the sediment in the reaction tank is sunk into a sludge hopper below in the sedimentation tank under the action of gravity, and the wastewater in the reaction tank flows to a clear water tank through an upper overflow weir;
(2) evaporation and desalination: adding a defoaming agent into the wastewater in the clear water tank, and then entering an evaporation desalting system; the evaporation desalting system comprises a three-effect evaporator, a discharge pump, a crystallizing tank, a centrifugal machine, a filtrate tank, a condenser, a condensate water tank, a filter pump, a multi-medium filter tank, a clear water tank and a delivery pump; the wastewater is evaporated and crystallized through the triple-effect evaporator; the triple-effect evaporator is respectively connected with the discharge pump and the condenser; the discharge pump, the crystallizing tank and the centrifuge are sequentially connected, crystals and filtrate are obtained after the treatment of the centrifuge, and the filtrate flows to the filtrate barrel and enters the three-effect evaporator through the filtrate barrel to be treated again; the condenser, the condensate water tank, the filter pump, the multi-medium filter tank, the clear water barrel and the delivery pump are sequentially connected;
(3) sludge treatment: and (3) treating the precipitate in the sludge hopper through a plate-and-frame filter press to obtain filter residue and filtrate, and refluxing the filtrate to the wastewater collection tank for treatment again.
The wastewater treatment process for the etching cleaning wastewater mainly comprises three parts of flocculation precipitation, evaporation desalting and sludge treatment, and the treated etching cleaning wastewater has clear water quality, no obvious suspended matters and electric conductivity less than or equal to 700 us/cm.
The method comprises the steps of adding alkali to adjust the pH value to be neutral, aggregating suspended matters in wastewater under the action of a compression double-electron layer of a coagulant, mutually sticking the aggregated suspended matters into large-particle suspended matters through a flocculant, settling the suspended matters in a settling tank into a sludge hopper below under the action of gravity, treating the sludge hopper through a plate and frame filter press to obtain filter residues and filtrate, wherein the filtered water still contains a certain amount of compounds such as copper and a large amount of ammonium chloride and needs to flow back to the wastewater collection tank for treatment again, so that zero discharge of the wastewater is realized.
In the evaporation desalting process part, a triple-effect evaporator is adopted for evaporation and crystallization desalting, one side of the triple-effect evaporator is connected with a condenser, a filter pump and the like, the condenser is provided with a vacuum system, and uncondensed gas generated in the triple-effect evaporator is pumped out by the vacuum system, so that the condenser and the triple-effect evaporator are kept in a negative pressure state, and the evaporation efficiency of an evaporation system is improved; the other side of the triple-effect evaporator is connected with a discharge pump, a crystallizing tank and the like, so that the final separation of water and salt is realized, the obtained crystals are recovered, waste can be changed into valuable, and the triple-effect evaporator has extremely high economic benefit and environmental benefit.
Further, in the above wastewater treatment process for etching cleaning wastewater, the coagulant in step (1) is one or a mixture of more of aluminum sulfate, ferric chloride and ferrous sulfate.
When the coagulant is added in the coagulation process, metal ion hydrolysis and polymerization reactions occur, and hydrolysis and polymerization products and water body particles are subjected to the effects of neutralization and destabilization, double electric layers compression, adsorption bridging or adhesion sweeping, sediment net catching and the like to generate coarse floccules, so that the coagulation process is completed.
Further, in the above wastewater treatment process for etching cleaning wastewater, the flocculant in step (1) is one or a mixture of more of polyaluminium chloride, polyferric sulfate and polyacrylamide.
The flocculant is a substance which can make suspended particles which are not easy to settle in liquid agglomerate and settle, can effectively remove suspended matters in water, reduce CODcr and remove harmful bacteria, and has good effects on water eutrophication, wastewater decoloration and the like. The flocculant is one or a mixture of more of polyaluminium chloride, polyferric sulfate and polyacrylamide, has the advantages of strong adaptability, high efficiency, low price and the like compared with the traditional ferric salt flocculant and aluminum salt flocculant, and is a coagulant aid for improving the flocculation effect and water quality.
Further, in the above wastewater treatment process for etching cleaning wastewater, the defoaming agent in the step (2) is a polyether modified silicone defoaming agent.
Because the process of flocculation precipitation, a large amount of foam can be generated in the wastewater, and the subsequent evaporation desalting process can be influenced.
Further, in the above wastewater treatment process for etching cleaning wastewater, in the step (2), the three-effect evaporator includes a one-effect forced circulation crystallization evaporator, a two-effect forced circulation evaporator, and a three-effect forced circulation evaporator, and the one-effect forced circulation crystallization evaporator, the two-effect forced circulation evaporator, and the three-effect forced circulation evaporator are connected in series and are communicated with each other through a balance pipe.
The waste water in the clean water tank firstly enters the one-effect forced circulation crystallization evaporator which is provided with a circulating pump, the one-effect forced circulation crystallization evaporator comprises an evaporation heat exchange chamber and a crystallization evaporation chamber, a salt collection chamber is arranged below the evaporation crystallization chamber, and the salt collection chamber is connected with a salt suction pump, a vortex salt separator and a salt storage pool.
In the evaporation heat exchange chamber, the external steam is liquefied to generate latent heat of vaporization, and the waste water is heated. Due to the high pressure in the evaporation heat exchange chamber, the waste water is heated to be overheated in the evaporation heat exchange chamber at the pressure higher than the boiling point of normal liquid. After the heated liquid enters the crystallization evaporation chamber, the pressure of the waste water is rapidly reduced to cause flash evaporation or rapid boiling of part of the waste water.
Under the action of negative pressure, the wastewater flows from the one-effect forced circulation crystallization evaporator to the two-effect forced circulation evaporator and the three-effect forced circulation crystallization evaporator in sequence, the wastewater is continuously evaporated, the concentration of salt in the wastewater is higher and higher, and when the salt in the wastewater is in a super-supersaturated state, the salt in the water can be continuously separated out and enters the salt collecting chamber below the evaporation crystallization chamber. The salt absorption pump continuously sends the waste water containing salt to the vortex salt separator, and solid salt is separated in the vortex salt separator and enters the salt storage pool.
And then, the separated wastewater enters the two-effect forced circulation evaporator for heating, and the whole process is repeated in cycles to realize the final separation of water and salt.
Wherein, the condenser is connected with a vacuum system, and the vacuum system pumps out uncondensed gas generated in the triple-effect evaporator, so that the condenser and the triple-effect evaporator are kept in a negative pressure state, and the evaporation efficiency of the evaporation system is improved. Under the action of negative pressure, secondary steam generated by the wastewater in the triple-effect forced circulation evaporator automatically enters the condenser, and under the cooling of circulating cooling water, the secondary steam generated by the wastewater is quickly converted into condensed water.
Further, in the above wastewater treatment process for etching cleaning wastewater, in the step (3), the process further includes the following steps: and (5) recovering filter residues.
Further, in the above wastewater treatment process for etching and cleaning wastewater, the treatment of the filter residue includes the following steps: and washing the filter residue for multiple times, putting the filter residue into an enamel reactor, reacting the filter residue with sulfuric acid to generate a concentrated copper sulfate solution, cooling and crystallizing to obtain crystal copper sulfate.
In the flocculation precipitation process, a coagulant and a flocculant are added to perform chemical reaction with copper ions in the etching solution to generate precipitation, so that the separation of copper in the waste liquid is realized, the main components of the filter residue are precipitated copper hydroxide and other impurities, the impurities such as chloride ions and the like adsorbed by the filter residue are washed by water and react with sulfuric acid to generate a concentrated copper sulfate solution, and the concentrated copper sulfate solution is cooled and crystallized to obtain crystal copper sulfate, so that the copper in the filter residue is recovered and reused in a new etching solution, thereby changing waste into valuable and having extremely high economic benefit and environmental benefit.
Compared with the prior art, the invention has the following beneficial effects:
(1) the wastewater treatment process for the etching cleaning wastewater has the advantages of reasonable step arrangement, simple process, realization of zero discharge of sewage, no generation of toxic and harmful byproducts in treatment engineering, no pollution, extremely high economic benefit and environmental benefit, clear water quality, no obvious suspended matters, conductivity less than or equal to 700us/cm and wide application prospect;
(2) the wastewater treatment process for the etching cleaning wastewater adopts the triple-effect evaporator to remove evaporation, crystallization and salt, has good effect, low operation cost and high efficiency, and can recycle the obtained crystals and change waste into valuable;
(3) according to the wastewater treatment process for etching cleaning wastewater, the coagulant and the flocculant are added to perform chemical reaction with copper ions in the etching solution to generate precipitation, so that the separation of copper in the waste liquid is realized, the precipitation effect is good, the copper removal rate reaches over 99%, copper in filter residues is recovered and is reused in a new etching solution, waste can be changed into valuables, and the wastewater treatment process for etching cleaning wastewater has extremely high economic benefit and environmental benefit.
Drawings
FIG. 1 is a schematic view showing the connection of an evaporative desalination system for wastewater treatment process of etching and cleaning wastewater according to the present invention;
FIG. 2 is a schematic diagram of the connection of a triple-effect evaporator in an evaporative desalination system for wastewater treatment process of etching cleaning wastewater according to the present invention;
in the figure: the system comprises an evaporation desalination system 1, a three-effect evaporator 11, a one-effect forced circulation crystallization evaporator 111, a two-effect forced circulation evaporator 112, a three-effect forced circulation evaporator 113, a balance pipe 114, a discharge pump 12, a crystallization tank 13, a centrifuge 14, a filtrate tank 15, a condenser 16, a condensate water tank 17, a filter pump 18, a multi-medium filter tank 19, a clear water tank 20, a conveying pump 21 and a crystal.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to fig. 1 and 2 and specific experimental data, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following embodiments provide a wastewater treatment process for etching cleaning wastewater, as shown in fig. 1, the evaporation desalination system 1 includes a three-effect evaporator 11, a discharge pump 12, a crystallization tank 13, a centrifuge 14, a filtrate tank 15, a condensate water tank 16, a filter pump 17, a multi-media filter tank 18, a clean water tank 19, and a delivery pump 20; the wastewater is evaporated and crystallized through the triple-effect evaporator 11; the triple-effect evaporator 11 is respectively connected with the discharge pump 12 and the condensate water tank 16; the discharge pump 12, the crystallizing tank 13 and the centrifuge 14 are sequentially connected, crystals and filtrate are obtained after treatment by the centrifuge 14, and the filtrate flows to the filtrate barrel 15 and enters the three-effect evaporator 11 through the filtrate barrel 15 for treatment again; the condensed water tank 16, the filter pump 17, the multi-medium filter tank 18, the clear water barrel 19 and the delivery pump 20 are connected in sequence.
Further, as shown in fig. 2, the three-effect evaporator 11 includes a single-effect forced circulation crystallization evaporator 111, a two-effect forced circulation evaporator 112, and a three-effect forced circulation evaporator 113, and the single-effect forced circulation crystallization evaporator 111, the two-effect forced circulation evaporator 112, and the three-effect forced circulation evaporator 113 are connected in series and communicated with each other through a balance pipe 114.
Further, the coagulant in the step (1) is one or a mixture of aluminum sulfate, ferric chloride and ferrous sulfate.
Further, the flocculating agent in the step (1) is one or more of polyaluminium chloride, polyferric sulfate and polyacrylamide.
Further, the defoaming agent in the step (2) is a polyether modified organic silicon defoaming agent.
Examples
(1) Flocculation and precipitation: collecting etching cleaning wastewater in a wastewater collection tank, conveying the etching cleaning wastewater to a reaction tank through a wastewater lifting pump, adding alkali into the reaction tank, adjusting the pH value to be neutral, adding a coagulant, and adding a flocculant; the sediment in the reaction tank is sunk into a sludge hopper below in the sedimentation tank under the action of gravity, and the wastewater in the reaction tank flows to a clear water tank through an upper overflow weir;
(2) evaporation and desalination: adding a defoaming agent into the wastewater in the clean water tank, then feeding the wastewater into an evaporation desalination system 1 for evaporation desalination, wherein the water obtained by evaporation is recycled and utilized through a condenser 16, a condensate water tank 17, a filter pump 18, a multi-medium filter tank 19, a clean water tank 20 and a conveying pump 21, the crystals obtained by evaporation pass through a discharge pump 12, a crystallizing tank 13 and a centrifuge 14, the crystals contain water, the crystals are thoroughly separated from salt through the centrifuge 14, the obtained crystals a are recycled, certain salt and impurities in the filtered water need to flow back to the evaporation desalination system 1 for secondary treatment, and zero discharge of the wastewater is realized;
(3) sludge treatment: and (2) treating the precipitate in the sludge hopper through a plate-and-frame filter press to obtain filter residue and filtrate, refluxing the filtrate to the wastewater collection tank for treatment again, washing the filter residue for multiple times, putting the filter residue into an enamel reactor, reacting the filter residue with sulfuric acid to generate a concentrated copper sulfate solution, cooling and crystallizing to obtain crystal copper sulfate.
The wastewater treatment process for the etching cleaning wastewater can achieve the effect of removing more than 99% of copper in the wastewater, has clear water quality and wide application range, has the advantages of conductivity of less than or equal to 700us/cm, low operation cost, and can realize zero discharge of sewage by repeatedly refluxing the separated filtrate, recycle the obtained filter residue and crystals, change waste into valuables, and have extremely high economic benefit and environmental benefit.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination between the embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the idea of the present invention.
Claims (7)
1. A wastewater treatment process for etching cleaning wastewater is characterized by comprising the following steps:
(1) flocculation and precipitation: collecting etching cleaning wastewater in a wastewater collection tank, conveying the etching cleaning wastewater to a reaction tank through a wastewater lifting pump, adding alkali into the reaction tank, adjusting the pH value to be neutral, adding a coagulant, and adding a flocculant; the sediment in the reaction tank is sunk into a sludge hopper below in the sedimentation tank under the action of gravity, and the wastewater in the reaction tank flows to a clear water tank through an upper overflow weir;
(2) evaporation and desalination: adding a defoaming agent into the wastewater in the clear water tank, and then entering an evaporation desalting system (1); the evaporation desalination system (1) comprises a triple-effect evaporator (11), a discharge pump (12), a crystallizing tank (13), a centrifuge (14), a filtrate tank (15), a condenser (16), a condensate water tank (17), a filter pump (18), a multi-medium filter tank (19), a clear water tank (20) and a delivery pump (21); the wastewater is evaporated and crystallized through the triple-effect evaporator (11); the triple-effect evaporator (11) is respectively connected with the discharge pump (12) and the condenser (16); the discharge pump (12), the crystallizing tank (13) and the centrifuge (14) are sequentially connected, crystals and filtrate are obtained after the treatment of the centrifuge (14), and the filtrate flows to the filtrate barrel (15) and enters the triple-effect evaporator (11) through the filtrate barrel (15) for treatment again; the condenser (16), the condensation water tank (17), the filter pump (18), the multi-medium filter tank (19), the clear water barrel (20) and the delivery pump (21) are connected in sequence;
(3) sludge treatment: and (3) treating the precipitate in the sludge hopper through a plate-and-frame filter press to obtain filter residue and filtrate, and refluxing the filtrate to the wastewater collection tank for treatment again.
2. The wastewater treatment process for etching and cleaning wastewater according to claim 1, wherein the coagulant in step (1) is one or more of aluminum sulfate, ferric chloride and ferrous sulfate.
3. The wastewater treatment process for etching and cleaning wastewater according to claim 1, wherein the flocculating agent in the step (1) is one or more of polyaluminium chloride, polyferric sulfate and polyacrylamide.
4. The wastewater treatment process for etching cleaning wastewater according to claim 1, wherein the defoaming agent in the step (2) is a polyether modified silicone defoaming agent.
5. The wastewater treatment process for etching cleaning wastewater according to claim 4, wherein in the step (2), the three-effect evaporator (11) comprises a one-effect forced circulation crystallization evaporator (111), a two-effect forced circulation evaporator (112) and a three-effect forced circulation evaporator (113), and the one-effect forced circulation crystallization evaporator (111), the two-effect forced circulation evaporator (112) and the three-effect forced circulation evaporator (113) are connected in series and communicated through a balance pipe (114).
6. The wastewater treatment process for etching cleaning wastewater according to claim 1, characterized in that the step (3) further comprises the steps of: and (5) recovering filter residues.
7. The wastewater treatment process for etching and cleaning wastewater according to claim 6, wherein the treatment of the filter residue comprises the following steps: and washing the filter residue for multiple times, putting the filter residue into an enamel reactor, reacting the filter residue with sulfuric acid to generate a concentrated copper sulfate solution, cooling and crystallizing to obtain crystal copper sulfate.
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