CN112093813A - System and method for treating high ammonia nitrogen acidic etching waste liquid - Google Patents
System and method for treating high ammonia nitrogen acidic etching waste liquid Download PDFInfo
- Publication number
- CN112093813A CN112093813A CN202010802733.2A CN202010802733A CN112093813A CN 112093813 A CN112093813 A CN 112093813A CN 202010802733 A CN202010802733 A CN 202010802733A CN 112093813 A CN112093813 A CN 112093813A
- Authority
- CN
- China
- Prior art keywords
- tank
- waste liquid
- ammonia nitrogen
- conveying
- sodium chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a system and a method for treating high ammonia nitrogen acidic etching waste liquid, wherein the system comprises a waste liquid pretreatment device, a copper recovery treatment device, a polyaluminium chloride preparation device and a sodium chloride evaporation drying device; the waste liquid pretreatment device comprises a waste liquid collecting tank, a pump, a metering tank, a pH adjusting tank and a sodium hydroxide adding device, wherein the waste liquid collecting tank is connected with the pH adjusting tank through the pump and the metering tank, and the sodium hydroxide adding device is connected with the pH adjusting tank. The invention relates to a system and a method for treating high ammonia nitrogen acidic etching waste liquid, which aim at comprehensive disposal and utilization of the high ammonia nitrogen acidic etching waste liquid in a circuit board (PCB) production plant.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of wastes, in particular to a system and a method for treating high ammonia nitrogen acidic etching waste liquid.
Background
The PCB circuit etching mainly comprises an acid etching system and an alkaline etching system, wherein the main component in waste liquid generated by the acid etching system is CuCl2Hydrochloric acid, ammonium chloride and the like, which cause the problems of high ammonia nitrogen in the treatment and utilization process of the etching waste liquid, influence on standard discharge or low purity of byproduct sodium chloride.
In the existing method for treating the acidic etching waste liquid, the aluminum displacement recovered acidic etching liquid has the advantages of high purity of recovered copper powder, full recovery of waste liquid copper, high reaction speed and the like; if the recovered waste liquid does not contain ammonia nitrogen, the recovered waste liquid can be directly polymerized and adjusted to produce the polyaluminium chloride water purifying agent, but most etching solutions contain high-concentration ammonia nitrogen to influence the normal utilization of the residual liquid after replacement.
Disclosure of Invention
Therefore, the invention provides a system and a method for treating high ammonia nitrogen acidic etching waste liquid.
In order to achieve the above purpose, the invention provides the following technical scheme:
the system for treating the high ammonia-nitrogen acidic etching waste liquid comprises a waste liquid pretreatment device, a copper recovery treatment device, a polyaluminium chloride preparation device and a sodium chloride evaporation drying device;
the waste liquid pretreatment device comprises a waste liquid collecting tank, a pump, a metering tank, a pH adjusting tank and a sodium hydroxide adding device, wherein the waste liquid collecting tank is connected with the pH adjusting tank through the pump and the metering tank, and the sodium hydroxide adding device is connected with the pH adjusting tank;
the copper recovery processing device comprises a first-stage displacement reaction tank, a second-stage displacement reaction tank, a copper powder centrifuge and a filtrate collecting tank, wherein the first-stage displacement reaction tank is respectively connected with the pH adjusting tank, the copper powder centrifuge and the second-stage displacement reaction tank, and the filtrate collecting tank is connected with the copper powder centrifuge;
the copper recovery processing device is connected with the polyaluminium chloride device, and the sodium chloride evaporation drying device is connected with the polyaluminium chloride preparation device.
Preferably, the polyaluminium chloride preparation device comprises a first intermediate tank, a filter, a waste liquid neutralization reaction tank, a plate-and-frame filter press, a filter cake temporary storage funnel, a metering conveyor belt, a reaction kettle, a heating device and a storage tank;
the first intermediate tank is connected with the waste liquid neutralization reaction tank through the filter, and the waste liquid neutralization reaction tank is connected with the filter cake temporary storage funnel through the plate-and-frame filter press; the filter cake temporary storage funnel through the measurement conveyer belt with reation kettle connects, reation kettle with the hold up tank is connected.
Preferably, the sodium chloride evaporation drying device comprises a second intermediate tank, an ammonia nitrogen electrolytic tank, a pH adjustment control device, a temporary storage tank III, a sodium chloride solution reduced pressure evaporation device, a sodium chloride concentrated solution collecting tank, a concentrated solution drying device and a condensed water temporary storage tank;
the second intermediate tank is connected with the temporary storage tank III through the ammonia nitrogen electrolytic tank, the temporary storage tank III is connected with the sodium chloride concentrated solution collecting tank through a sodium chloride solution reduced pressure evaporation device, the concentrated solution is connected with the concentrated solution drying device, and the condensed water temporary storage tank is connected with the sodium chloride solution reduced pressure evaporation device;
and the second middle tank is connected with the plate-and-frame filter press.
Preferably, the system also comprises a waste gas treatment device, and the waste gas treatment device is respectively connected with the waste liquid pretreatment device, the copper recovery treatment device and the polyaluminium chloride preparation device.
The invention also provides a method for treating the high ammonia nitrogen acidic etching waste liquid by using the system, which comprises the following steps:
collecting high ammonia nitrogen acidic etching waste liquid by using the waste liquid collecting tank, conveying the high ammonia nitrogen acidic etching waste liquid to the pH adjusting tank through the pump, and adjusting the pH value of the waste liquid to be 1.0-2.0 through the sodium hydroxide adding device;
conveying the waste liquid to a first-stage replacement reaction tank, adding 90-100% of aluminum sheets to react for 30-60 minutes, conveying the supernatant of the first-stage replacement reaction tank to a second-stage replacement reaction tank, conveying the precipitate to the copper powder centrifuge, conveying the centrifuged filtrate to the second-stage replacement reaction tank, adding the aluminum sheets to the second-stage replacement reaction tank to react, conveying the precipitate of the second-stage replacement reaction tank to the first-stage replacement reaction tank, and treating the supernatant of the reaction by using the aluminum chloride polymerization device and the sodium chloride evaporation drying device.
Preferably, the supernatant of the second-stage displacement reaction tank is conveyed to a first intermediate tank, the reaction liquid in the first intermediate tank is conveyed to a waste liquid neutralization reaction tank through a filter, a sodium hydroxide adding device adds sodium hydroxide into the waste liquid neutralization reaction tank to adjust the pH value to 6-8 so as to obtain an aluminum hydroxide precipitate, the aluminum hydroxide precipitate is subjected to pressure filtration through a plate-and-frame filter press to obtain an aluminum hydroxide filter cake, the aluminum hydroxide filter cake is conveyed to a filter cake temporary storage hopper, the filtrate is conveyed to a second intermediate tank, the aluminum hydroxide filter cake is conveyed to a reaction kettle through a metering conveyor belt, hydrochloric acid is added into the reaction kettle to obtain a polymeric aluminum chloride liquid product with the basicity of 30-45% and the aluminum trichloride content of 10-14%, water, calcium aluminate powder or sodium aluminate are added into the product, the mixture is heated and pressurized to obtain a reaction product, the reaction product is conveyed to a storage tank, aging for 2-3 days, adding water to adjust to Al2O3The content is not less than 8 percent to obtain the poly chlorineAnd (4) aluminum melting.
Preferably, the filtrate in the second intermediate tank is conveyed to an ammonia nitrogen electrolytic tank, the pH value of the filtrate is adjusted to 6-8 by a pH adjustment control device, the electrolyzed solution is conveyed to a temporary storage tank III, is subjected to reduced pressure evaporation by a sodium chloride solution reduced pressure evaporation device, is concentrated by a sodium chloride concentrated solution collecting tank, and is dried by a concentrated solution drying device to obtain sodium chloride.
Preferably, the method further comprises:
waste gas that waste liquid pretreatment device, copper recovery processing device, poly aluminium chloride preparation facilities and sodium chloride evaporation drying device produced handles through waste gas treatment device.
The main reactions involved in the present invention are as follows:
the first step of displacement and copper recovery stage:
H++OH-→H2o (neutralization reaction pH)
3Cu2++2Al→3Cu↓+2Al3+(recovery of copper by metathesis)
The second step is a stage for separating aluminum salt by precipitation:
Al3++3OH-→Al(OH)3↓ (aluminum separating sediment)
And step three, generating polyaluminium chloride:
Al(OH)3+3HCl→Al(OH)1.05Cl1.95+3H2o (synthetic polyaluminium chloride)
Al(OH)1.95Cl1.05+Al2O3.CaO+H2O→Al(OH)2.25Cl0.75+CaCl2(Synthesis of polyaluminum chloride)
And fourthly, electrolyzing and removing generated ammonia nitrogen:
anode: 2Cl-→Cl2℃ +2e (Cl generation)2Reaction)
Cl2+H2O＝HClO+H++Cl-
NH3+HClO→NH2Cl (monochloramine) + H2O
NH2Cl+HClO→NHCl2(dichloramine) + H2O
NHCl2+HClO→NCl3(Trichloramine) + H2O
NHCl2+H2O→NOH+2HCl
NHCl2+NOH→N2↑+HClO+H2O
The general reaction formula is as follows:
3Cl2+2NH3+H2O→N2↓ +6HCl (producing HCl reaction)
The invention has the following advantages:
the invention relates to a system and a method for treating high ammonia nitrogen acidic etching waste liquid, which aim at comprehensive disposal and utilization of the high ammonia nitrogen acidic etching waste liquid in a circuit board (PCB) production plant. The system and the process can reduce waste discharge and improve the utilization rate of waste liquid.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
FIG. 1 is a schematic structural diagram of an apparatus for treating a high ammonia nitrogen acidic etching waste liquid provided by the invention;
in the figure: a waste liquid collecting tank 1; a pump 101; a metering tank 2; a pH adjusting tank 3; a first-stage displacement reaction tank 4; a second-stage displacement reaction tank 5; a first intermediate tank 6; a filter 61; a copper powder centrifuge 7; a filtrate collection tank 71; a waste liquid neutralization reaction tank 8; a sodium hydroxide adding device 9; a plate and frame filter press 10; a second intermediate tank 11; a filter cake temporary storage hopper 12; a metering conveyor 121; a reaction kettle 13; a storage tank 14; an ammonia nitrogen electrolytic cell 15; a pH adjustment control device 16; a temporary storage tank III 17; a sodium chloride solution decompression evaporation device 18; a sodium chloride concentrate collection tank 181; a concentrate drying device 182; a condensate temporary storage tank 19; an exhaust gas treatment device 20.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. 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.
As shown in figure 1, the invention provides a system for treating high ammonia nitrogen acidic etching waste liquid, which comprises a waste liquid pretreatment device, a copper recovery treatment device, a polyaluminium chloride preparation device and a sodium chloride evaporation drying device; the waste liquid pretreatment device comprises a waste liquid collecting tank 1, a pump 101, a metering tank 2, a pH adjusting tank and a sodium hydroxide adding device 9, wherein the pump 101 is a corrosion-resistant plastic pump 101, the metering tank 2 is used for metering the amount of the high ammonia nitrogen etching waste liquid, the waste liquid collecting tank 1 is connected with the pH adjusting tank through the pump 101 and the metering tank 2, and the sodium hydroxide adding device 9 is connected with the pH adjusting tank; the copper recovery processing device comprises a first-stage replacement reaction tank 4, a second-stage replacement reaction tank 5, a copper powder centrifuge 7 and a filtrate collecting tank 71, wherein the first-stage replacement reaction tank 4 is respectively connected with a pH adjusting tank, the copper powder centrifuge 7 and the second-stage replacement reaction tank 5, and the filtrate collecting tank 71 is connected with the copper powder centrifuge 7; the copper recovery processing device is connected with the polyaluminium chloride device, and the sodium chloride evaporation drying device is connected with the polyaluminium chloride preparation device. The system of the invention is a system for comprehensively treating and utilizing the high ammonia nitrogen acidic etching waste liquid in a circuit board (PCB) production plant.
The polyaluminium chloride preparation device comprises a first intermediate tank 6, a filter 61, a waste liquid neutralization reaction tank 8, a plate-and-frame filter press, a filter cake temporary storage funnel, a metering conveyor belt 121, a reaction kettle 13, a heating device and a storage tank 14; the first intermediate tank 6 is connected with a waste liquid neutralization reaction tank 8 through a filter 61, and the waste liquid neutralization reaction tank 8 is connected with a filter cake temporary storage funnel through a plate-and-frame filter press; the filter cake temporary storage funnel is connected with the reaction kettle 13 through a metering conveyor belt 121, and the reaction kettle 13 is connected with the storage tank 14.
The sodium chloride evaporation drying device comprises a second intermediate tank 11, an ammonia nitrogen electrolytic tank 15, a pH adjustment control device 16, a temporary storage tank III 17, a sodium chloride solution reduced pressure evaporation device 18, a sodium chloride concentrated solution collecting tank 181, a concentrated solution drying device 182 and a condensed water temporary storage tank 19; the second intermediate tank 11 is connected with a temporary storage tank III 17 through an ammonia nitrogen electrolytic tank 15, the temporary storage tank III 17 is connected with a sodium chloride concentrated solution collecting tank 181 through a sodium chloride solution reduced pressure evaporation device 18, the concentrated solution is connected with a concentrated solution drying device 182, and a condensed water temporary storage tank 19 is connected with the sodium chloride solution reduced pressure evaporation device 18; the second intermediate tank 11 is connected with a plate-and-frame filter press.
The system for treating the high ammonia nitrogen acidic etching waste liquid also comprises a waste gas treatment device 20, wherein the waste gas treatment device 20 is respectively connected with the waste liquid pretreatment device, the copper recovery treatment device and the polyaluminium chloride preparation device.
The invention also provides a method for treating the high ammonia nitrogen acidic etching waste liquid, which comprises the following steps:
collecting high ammonia nitrogen acidic etching waste liquid by using a waste liquid collecting tank 1, conveying the high ammonia nitrogen acidic etching waste liquid to a pH adjusting tank 3 through a pump 101, and adjusting the pH value of the waste liquid to 1.0-2.0 through a sodium hydroxide adding device 9;
conveying the waste liquid to a first-stage replacement reaction tank 4, adding 90-100% of aluminum sheets to react for 30-60 minutes, conveying the supernatant of the first-stage replacement reaction tank 4 to a second-stage replacement reaction tank 5, precipitating and conveying the supernatant to a copper powder centrifuge 7, washing the dehydrated copper powder by the centrifuge, bagging and sealing, conveying the centrifuged filtrate to the second-stage replacement reaction tank 5, adding excessive aluminum sheets which are multiple times or more into the second-stage replacement reaction tank 5 to perform replacement reaction for 30-60 minutes, fully reacting the solution with the aluminum sheets, periodically conveying the precipitate reacted in the second-stage replacement reaction tank 5 to the first-stage replacement reaction tank 4, and treating the reacted supernatant by an aluminum chloride polymerization device and a sodium chloride evaporation drying device. The copper powder recovered by the reaction in the first-stage displacement reaction tank 4 and the second-stage displacement reaction tank 5 has high purity, and the residual copper ions in the filtrate are small.
The supernatant of the second-stage replacement reaction tank 5 is conveyed to a first intermediate tank 6, the reaction liquid in the first intermediate tank 6 is filtered by a precision filter 61 and then conveyed to a waste liquid neutralization reaction tank 8 by a pump 101, a sodium hydroxide adding device 9 adds a sodium hydroxide/sodium carbonate solution into the waste liquid neutralization reaction tank 8 to adjust the pH value to 6-8 to obtain an aluminum hydroxide precipitate, the aluminum hydroxide precipitate is subjected to pressure filtration by a plate-and-frame membrane filter press, namely a plate-and-frame filter press 10 to obtain an aluminum hydroxide filter cake, and conveyed to a filter cake temporary storage hopper 12, the filtrate is conveyed to a second intermediate tank 11, the aluminum hydroxide filter cake is conveyed to a reaction kettle 13 by a metering conveyor belt 121, 105-115% hydrochloric acid and water are added into the reaction kettle 13 to be fully stirred and heated to 130-150 ℃, the pressure in the reaction kettle 13 is 0.25-0.4MPa, and a polymerized aluminum chloride liquid product with the basicity of 30-45% and the aluminum trichloride content of 10-14%, adding water, calcium aluminate powder or sodium aluminate into the product, heating and pressurizing, and keeping the temperature and pressure in the kettle; after the reaction is completely carried out and filter-pressed, the product is conveyed to a storage tank 14, cured for 2 to 3 days, and added with water to adjust to Al2O3The content is not less than 8 percent, and the liquid polyaluminium chloride is obtained.
Conveying the filtrate of the second intermediate tank 11 to an ammonia nitrogen electrolytic tank 15, wherein the filtrate contains high-concentration ammonia nitrogen (500-5000 mg/L), and the ammonia nitrogen electrolytic tank 15 adopts a chlorine-separating ruthenium iridium coating titanium mesh as an anode and an uncoated titanium mesh as a cathode; the pH value of the filtrate is adjusted to 6-8 through a pH adjusting and controlling device 16, after the ammonia nitrogen is reduced to be within 10mg/L within a certain time through circulating electrolysis, the electrolyzed solution is conveyed to a temporary storage tank III 17, the sodium chloride solution with the ammonia nitrogen removed is subjected to reduced pressure evaporation through a sodium chloride solution reduced pressure evaporation device 18 and concentrated through a sodium chloride concentrated solution collecting tank 181, finally, the sodium chloride is obtained through drying through a concentrated solution drying device 182, and the sodium chloride is recovered through a scraper dryer. The evaporated moisture is condensed and collected by air and is used for the links of copper powder cleaning, medicament preparation, dilution and the like in the production process.
The method for treating the high ammonia nitrogen acidic etching waste liquid also comprises the following steps: the waste gas that waste liquid pretreatment device, copper recovery processing device, poly aluminium chloride preparation facilities and sodium chloride evaporation drying device produced is handled through exhaust gas treatment device 20. The process method realizes the complete recycling of the high-ammonia nitrogen acidic etching waste liquid and recovers high-purity copper powder, high-purity polyaluminium chloride, sodium chloride and standard-reaching reuse water.
The working principle of the system for treating the high ammonia nitrogen acidic etching waste liquid is as follows:
conveying the high ammonia nitrogen acidic etching waste liquid to a waste liquid collecting tank 1, analyzing indexes such as copper content, acidity and ammonia nitrogen in the waste liquid, and conveying the high ammonia nitrogen acidic etching waste liquid to a metering tank 2 quantitatively by using a corrosion-resistant plastic pump 101; and (3) conveying all the etching solution in the metering tank 2 to a pH adjusting tank, adjusting the acidity of the waste solution to 1.0-2.0 under the control of pH by a sodium hydroxide adding device 9, reducing the danger generated by hydrogen in the replacement process, and adding proper water to dilute the etching waste solution.
Conveying the etching waste liquid with the adjusted pH and copper ion concentration to a first-stage displacement reaction tank 4, adding an aluminum sheet with the stoichiometric proportion of 90-100% to the etching waste liquid to enable the aluminum sheet to completely react for 30-60 minutes, and standing for precipitation; conveying the supernatant to a second-stage replacement reaction tank 5, simultaneously putting the copper powder replaced in the first-stage replacement reaction tank 4 into a copper powder centrifuge 7, centrifugally dewatering the copper powder through the centrifuge, washing with water, bagging and sealing, and merging the filtrate centrifuged by the centrifuge into the second-stage replacement reaction tank 5; adding more than several times of excessive aluminum sheets into the second-stage displacement reaction tank 5 to carry out displacement reaction for 30-60 minutes, standing and precipitating, conveying supernate into a first intermediate tank 66, periodically transferring the precipitate in the second-stage displacement reaction tank 5 into a first-stage displacement reaction tank 4 to fully react the aluminum sheets, and recovering copper powder from the etching solution waste liquid through displacement of the second-stage aluminum sheets, wherein the copper powder is high in purity and the copper ion content of residual liquid is low.
After the reaction in the first intermediate tank 6 is carried out in the first-stage displacement reaction tank 4 and the second-stage displacement reaction tank 5, the obtained supernatant enters the waste liquid neutralization reaction tank 8 through a filter pump 101 of a precision filter 61, the pH is adjusted to 6-8 by using a sodium hydroxide solution, aluminum hydroxide is precipitated and separated, the precipitate is filtered by using a plate-and-frame filter press 10, a filter cake is washed by using a small amount of condensed water in a filter press, the filter cake is placed in a filter cake temporary storage hopper 12 after the salt content is reduced, and the filtrate flows into a second intermediate tank 11; measuring and crushing an aluminum hydroxide filter cake in the filter cake temporary storage hopper 12, putting the crushed aluminum hydroxide filter cake into a polyaluminium chloride closed synthesis reaction kettle 13, adding 105-115% of measured hydrochloric acid and a proper amount of water into the reaction kettle 13, fully stirring, heating to 130-150 ℃, and keeping the pressure in the kettle at 0.25-0.4Mpa to obtain a polyaluminium chloride liquid with the basicity of 30-45% and the aluminum trichloride content of 10-14%; adding water, calcium aluminate powder or sodium aluminate into the polymerized aluminum chloride liquid in a closed reaction kettle 13, and heating and pressurizing; keeping the temperature and pressure in the kettle; discharging the materials to a storage tank 14 after the reaction is completely filter-pressed, adding water to adjust the materials to Al after curing for 2 to 3 days2O3Preserving the product with the content not less than 8 percent to obtain the finished product of the polyaluminium chloride. The reaction vessel 13 is heated and hot steam is supplied by a heating device.
The concentration of ammonia nitrogen contained in the filtrate in the second intermediate tank 11 is 500-5000 mg/L, far exceeds the sewage discharge standard, the ammonia nitrogen is required to be removed through electrolysis, and the ammonia nitrogen electrolysis tank 15 adopts a chlorine-separating ruthenium iridium coating titanium mesh as an anode and an uncoated titanium mesh as a cathode; the pH adjusting and controlling device 16 automatically controls the addition of liquid caustic soda, maintains the pH of the electrolyte at 6-8, reduces the ammonia nitrogen to below 10mg/L for a certain time of circular electrolysis, and the waste liquid flows into a temporary storage tank III 17 with heat preservation measures. The sodium chloride solution in the temporary storage tank III 17 after ammonia nitrogen removal is subjected to reduced pressure evaporation concentration by a sodium chloride solution reduced pressure evaporation device 18, the concentrated solution is pumped into a sodium chloride concentrated solution collecting tank 181 by a pump 101 after reaching a set concentration, evaporated condensate water flows into a condensate water temporary storage tank 19 for constant volume of etching solution of an etching waste liquid recovery system, copper powder cleaning, polyaluminium chloride dilution and other links; and industrial sodium chloride is dried and recovered by a concentrated solution drying device 182 in a sodium chloride concentrated solution collecting tank 181, and evaporated solution flows back to a temporary storage tank III 17. The treatment system process of the invention relates to waste liquid storage, the reaction link may produce acid mist and other waste gases, the waste gases are exhausted through the waste gas treatment device 20, and the waste gases are discharged after washing treatment.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. The system for treating the high ammonia-nitrogen acidic etching waste liquid is characterized by comprising a waste liquid pretreatment device, a copper recovery treatment device, a polyaluminium chloride preparation device and a sodium chloride evaporation drying device;
the waste liquid pretreatment device comprises a waste liquid collecting tank, a pump, a metering tank, a pH adjusting tank and a sodium hydroxide adding device, wherein the waste liquid collecting tank is connected with the pH adjusting tank through the pump and the metering tank, and the sodium hydroxide adding device is connected with the pH adjusting tank;
the copper recovery processing device comprises a first-stage displacement reaction tank, a second-stage displacement reaction tank, a copper powder centrifuge and a filtrate collecting tank, wherein the first-stage displacement reaction tank is respectively connected with the pH adjusting tank, the copper powder centrifuge and the second-stage displacement reaction tank, and the filtrate collecting tank is connected with the copper powder centrifuge;
the copper recovery processing device is connected with the polyaluminium chloride device, and the sodium chloride evaporation drying device is connected with the polyaluminium chloride preparation device.
2. The system for treating high ammonia nitrogen acidic etching waste liquid according to claim 1,
the polyaluminium chloride preparation device comprises a first intermediate tank, a filter, a waste liquid neutralization reaction tank, a plate-and-frame filter press, a filter cake temporary storage funnel, a metering conveyor belt, a reaction kettle, a heating device and a storage tank;
the first intermediate tank is connected with the waste liquid neutralization reaction tank through the filter, and the waste liquid neutralization reaction tank is connected with the filter cake temporary storage funnel through the plate-and-frame filter press; the filter cake temporary storage funnel through the measurement conveyer belt with reation kettle connects, reation kettle with the hold up tank is connected.
3. The system for treating high ammonia nitrogen acidic etching waste liquid according to claim 2,
the sodium chloride evaporation drying device comprises a second intermediate tank, an ammonia nitrogen electrolytic tank, a pH adjustment control device, a temporary storage tank III, a sodium chloride solution decompression evaporation device, a sodium chloride concentrated solution collecting tank, a concentrated solution drying device and a condensed water temporary storage tank;
the second intermediate tank is connected with the temporary storage tank III through the ammonia nitrogen electrolytic tank, the temporary storage tank III is connected with the sodium chloride concentrated solution collecting tank through a sodium chloride solution reduced pressure evaporation device, the concentrated solution is connected with the concentrated solution drying device, and the condensed water temporary storage tank is connected with the sodium chloride solution reduced pressure evaporation device;
and the second middle tank is connected with the plate-and-frame filter press.
4. The system for treating high ammonia nitrogen acidic etching waste liquid according to claim 1,
the system also comprises a waste gas treatment device, wherein the waste gas treatment device is respectively connected with the waste liquid pretreatment device, the copper recovery treatment device and the polyaluminium chloride preparation device.
5. A method for treating high ammonia nitrogen acidic etching waste liquid by using the system of claim 1, which is characterized by comprising the following steps:
collecting high ammonia nitrogen acidic etching waste liquid by using the waste liquid collecting tank, conveying the high ammonia nitrogen acidic etching waste liquid to the pH adjusting tank through the pump, and adjusting the pH value of the waste liquid to be 1.0-2.0 through the sodium hydroxide adding device;
conveying the waste liquid to a first-stage replacement reaction tank, adding 90-100% of aluminum sheets to react for 30-60 minutes, conveying the supernatant of the first-stage replacement reaction tank to a second-stage replacement reaction tank, conveying the precipitate to the copper powder centrifuge, conveying the centrifuged filtrate to the second-stage replacement reaction tank, adding the aluminum sheets to the second-stage replacement reaction tank to react, conveying the precipitate of the second-stage replacement reaction tank to the first-stage replacement reaction tank, and treating the supernatant of the reaction by using the aluminum chloride polymerization device and the sodium chloride evaporation drying device.
6. The method of claim 5,
conveying the supernatant obtained by the reaction in the second-stage displacement reaction tank to a first intermediate tank, conveying the reaction liquid in the first intermediate tank to a waste liquid neutralization reaction tank through a filter, adding sodium hydroxide into the waste liquid neutralization reaction tank by a sodium hydroxide adding device to adjust the pH value to 6-8 so as to obtain an aluminum hydroxide precipitate, carrying out filter pressing on the aluminum hydroxide precipitate by a plate-and-frame filter press to obtain an aluminum hydroxide filter cake, conveying the aluminum hydroxide filter cake to a filter cake temporary storage hopper, conveying the filtrate to a second intermediate tank, conveying the aluminum hydroxide filter cake to a reaction kettle through a metering conveyor belt, adding hydrochloric acid into the reaction kettle, reacting to obtain a polymeric aluminum chloride liquid product with the basicity of 30-45% and the aluminum trichloride content of 10-14%, adding water, calcium aluminate powder or sodium aluminate into the product, heating and pressurizing to obtain a reaction product, conveying the reaction product to a storage tank, curing for 2-3 days, adding water to adjust to Al2O3The content is not less than 8 percent, and the polyaluminium chloride is obtained.
7. The method of claim 6,
and conveying the filtrate in the second intermediate tank to an ammonia nitrogen electrolytic tank, adjusting the pH of the filtrate to 6-8 by using a pH adjustment control device, conveying the electrolyzed solution to a temporary storage tank III, performing reduced pressure evaporation by using a sodium chloride solution reduced pressure evaporation device, concentrating by using a sodium chloride concentrated solution collecting tank, and finally drying by using a concentrated solution drying device to obtain sodium chloride.
8. The method of claim 6,
the method further comprises the following steps:
waste gas that waste liquid pretreatment device, copper recovery processing device, poly aluminium chloride preparation facilities and sodium chloride evaporation drying device produced handles through waste gas treatment device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010802733.2A CN112093813B (en) | 2020-08-11 | 2020-08-11 | System and method for treating high ammonia nitrogen acid etching waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010802733.2A CN112093813B (en) | 2020-08-11 | 2020-08-11 | System and method for treating high ammonia nitrogen acid etching waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112093813A true CN112093813A (en) | 2020-12-18 |
| CN112093813B CN112093813B (en) | 2023-05-02 |
Family
ID=73753636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010802733.2A Active CN112093813B (en) | 2020-08-11 | 2020-08-11 | System and method for treating high ammonia nitrogen acid etching waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112093813B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004096711A1 (en) * | 2003-03-27 | 2004-11-11 | Hsieh Sen Wu | Methods and devices for recycling copper from a discarded circuit board and a discarded fluid containing copper |
| CN103787483A (en) * | 2012-11-05 | 2014-05-14 | 厦门市铜鑫环保科技有限公司 | Method and equipment for treating acidic etching waste liquor |
| CN103864153A (en) * | 2014-03-12 | 2014-06-18 | 红板（江西）有限公司 | Method for extracting copper and preparing polymerization ferric chloride by replacement of acidic etching liquid of PCB (printed circuit board) factory |
| CN103966607A (en) * | 2013-01-31 | 2014-08-06 | 西安瑞凯电力科技有限公司 | Method for recovering copper and hydrochloric acid from acid etching solution |
| CN208517155U (en) * | 2018-04-09 | 2019-02-19 | 深圳市深投环保科技有限公司 | Copper oxide produces discharge of wastewater processing system |
| 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 |
-
2020
- 2020-08-11 CN CN202010802733.2A patent/CN112093813B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004096711A1 (en) * | 2003-03-27 | 2004-11-11 | Hsieh Sen Wu | Methods and devices for recycling copper from a discarded circuit board and a discarded fluid containing copper |
| CN103787483A (en) * | 2012-11-05 | 2014-05-14 | 厦门市铜鑫环保科技有限公司 | Method and equipment for treating acidic etching waste liquor |
| CN103966607A (en) * | 2013-01-31 | 2014-08-06 | 西安瑞凯电力科技有限公司 | Method for recovering copper and hydrochloric acid from acid etching solution |
| CN103864153A (en) * | 2014-03-12 | 2014-06-18 | 红板（江西）有限公司 | Method for extracting copper and preparing polymerization ferric chloride by replacement of acidic etching liquid of PCB (printed circuit board) factory |
| CN208517155U (en) * | 2018-04-09 | 2019-02-19 | 深圳市深投环保科技有限公司 | Copper oxide produces discharge of wastewater processing system |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112093813B (en) | 2023-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102851684B (en) | A kind of perhalogeno water function of mechanical steam recompression method alkali-making process and device | |
| CN109179457B (en) | Method for extracting lithium from electrolytic aluminum waste residues | |
| CN113636576A (en) | System and method for disposing and recycling miscellaneous salt in coal chemical industry | |
| KR19980023972A (en) | Semen Method of Copper Electrolyte | |
| CN104261443A (en) | Process for calcium-method production of magnesium hydrate by using nanofiltration membrane | |
| CN111547922A (en) | Treatment method of manganese-containing ammonia nitrogen wastewater | |
| CN101654275A (en) | Comprehensive utilization method of acidic and alkaline waste etching solution | |
| CN112093813A (en) | System and method for treating high ammonia nitrogen acidic etching waste liquid | |
| CN114409157B (en) | Recycling method for preparing chlor-alkali by waste salt water electrolysis | |
| CN1054234A (en) | The manufacture method of alkaline carbonate | |
| CN104150519B (en) | A kind of method utilizing sodium sulfate waste liquid to prepare barium sulfate and sodium carbonate | |
| CN110386710A (en) | A method of epsom salt is produced using heat-engine plant desulfurized waste water | |
| CN109809582A (en) | A kind of potassium sulfate Sewage treatment utilizes method | |
| CN109748310A (en) | A kind of separation method of barium sulfate and potassium carbonate mixed solution | |
| CN212532613U (en) | Desulfurization waste water zero release processing apparatus | |
| CN113461044B (en) | Method for separating and recovering calcium and magnesium in chlor-alkali byproduct salt mud | |
| CN113620492A (en) | Method for removing TOC in high-salinity water generated by titanium white chloride | |
| JP3778238B2 (en) | Method for producing sodium persulfate | |
| CN112250131A (en) | Ammonia nitrogen wastewater treatment method | |
| CN114605017A (en) | Treatment process of ammonia nitrogen wastewater | |
| CN105905927B (en) | A kind of Galuber's salt type brine removes the bittern purifying device and method of strontium element | |
| CN216039101U (en) | System for removing TOC in high-salinity water generated by titanium white chloride | |
| CN220049412U (en) | Clean production system for preparing white carbon black from coal gangue | |
| CN219637061U (en) | Zero release system of sodium chloride brine in process of producing white carbon black from coal gangue | |
| CN114291955B (en) | Method for jointly utilizing iron pigment wastewater and reduced titanium tail gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |