CN110921950A - Electroplating wastewater recycling treatment method - Google Patents
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Abstract
The invention provides a method for recycling electroplating wastewater, which comprises the following steps: cyanogen breaking treatment, namely adding a cyanogen breaker into the electroplating wastewater under an alkaline condition to remove cyanides in the electroplating wastewater; breaking the complex, namely adding a breaking agent into the electroplating wastewater subjected to the cyanide breaking treatment, or performing catalytic oxidation treatment on the electroplating wastewater subjected to the cyanide breaking treatment to remove a complex in the electroplating wastewater; performing precipitation filtration treatment, namely performing precipitation filtration on the electroplating wastewater subjected to the vein breaking treatment to obtain filtered sludge and clear liquid; filtering the sludge into precipitates and suspended matters containing recoverable heavy metals; and (2) post-treatment, namely performing membrane concentration treatment and evaporative crystallization treatment on the clear liquid to obtain a first concentrated solution, crystallized salt and first produced water, mixing the first concentrated solution and the clear liquid for retreatment, feeding the first produced water into a first produced water recycling pool for recycling, and recycling the filtered sludge in a recycling workshop after filter pressing.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for recycling electroplating wastewater.
Background
In the electroplating industry, because the production process and the finished product are different, the water quality of the wastewater is very complex, the wastewater contains various heavy metals, and particularly the production wastewater in the electroplating park can be divided into electroplating wastewater and electroplating waste liquid according to different production processes and water quality characteristics. Wherein the electroplating wastewater usually comprises electroplating nickel wastewater, chemical nickel wastewater, chromium-containing wastewater, copper-containing cyanide wastewater, zinc-containing wastewater, acid copper wastewater, pyrocopper wastewater, comprehensive wastewater, anodic oxidation wastewater, pretreatment wastewater and the like; the electroplating waste liquid comprises bath liquid with high organic matter and complex, various electroplating work seed bath liquid without organic matter and complex, waste acid liquid, removed hanging piece, removed product waste liquid and the like. When the electroplating wastewater is treated, the production wastewater is generally required to be subjected to sewage disposal, flow division, classified collection and quality division treatment. At present, the standard discharge process for treating the electroplating wastewater is commonly realized by adopting a physicochemical and biochemical process or a physicochemical and biochemical membrane process, the two processes are mature and stable, the operation cost is low, and the discharge standard can be reached. But the finally discharged water still contains partial heavy metals, and the discharged water can cause secondary pollution to the environment; in addition, under the condition that the current environment has no environmental wastewater capacity, the discharge standard of the electroplating wastewater is more and more strict, so that the more and more strict wastewater discharge standard is difficult to meet.
Aiming at the situation, a process method of materialization, biochemistry, membrane method and evaporation is provided in the related technology to recycle the water resource in the electroplating wastewater.
However, the waste water is concentrated and evaporated, heavy metals in the waste water finally exist in evaporation residues, the residues belong to dangerous waste, enterprises cannot recycle the residues, the residues need to be treated by an organization with dangerous waste treatment qualification, the treatment cost is high, and the electroplating waste water cannot effectively realize zero emission.
Disclosure of Invention
The invention provides a method for recycling electroplating wastewater, which aims to solve the problem that in the related technology, when the electroplating wastewater is treated, heavy metals in the wastewater finally exist in evaporation residues, enterprises cannot recycle the heavy metals, the heavy metals need to be treated by a mechanism with dangerous wastewater treatment qualification, and the treatment cost is high, so that the electroplating wastewater cannot be effectively subjected to zero emission.
In order to realize the aim, the invention provides a method for recycling electroplating wastewater, which comprises the following steps:
cyanogen breaking treatment, namely adding a cyanogen breaker into the electroplating wastewater under an alkaline condition to remove cyanides in the electroplating wastewater;
carrying out cyanogen breaking treatment, namely adding a cyanogen breaking agent into the electroplating wastewater subjected to cyanogen breaking treatment, or carrying out catalytic oxidation treatment on the electroplating wastewater subjected to cyanogen breaking treatment to remove a complex in the electroplating wastewater;
performing precipitation filtration treatment, namely performing precipitation filtration on the electroplating wastewater subjected to the vein breaking treatment to obtain filtered sludge and clear liquid; the filtered sludge is sediment and suspended matters containing recoverable heavy metals;
and post-treatment, namely performing membrane concentration treatment and evaporative crystallization treatment on the clear liquid to obtain first concentrated solution, crystallized salt and first produced water, mixing the first concentrated solution with the clear liquid for retreatment, feeding the first produced water into a first produced water recycling pool for recycling, and recycling the filtered sludge in a recycling workshop after filter pressing.
In an alternative mode, the cyanogen breaking treatment comprises:
first-stage cyanogen breaking, namely adding the cyanogen breaking agent into the electroplating wastewater under the condition that the pH value is 10.5-11, and breaking cyanogen in the electroplating wastewater under the condition that the oxidation reduction potential is 300-350;
and (2) secondary cyanogen breaking, namely adding the cyanogen breaking agent into the electroplating wastewater under the condition that the pH value is 8-9, and breaking cyanogen in the electroplating wastewater under the condition that the oxidation reduction potential is 600-650.
In an optional manner, the decomplexing process includes:
adding an oxidant into the electroplating wastewater subjected to the cyanogen breaking treatment to remove a complex in the electroplating wastewater;
or, carrying out electrocatalytic oxidation on the electroplating wastewater subjected to the cyanogen breaking treatment to remove the complex in the electroplating wastewater.
In an alternative form, the precipitation filtration process includes:
precipitating, namely adjusting the pH value of the electroplating wastewater subjected to the complex breaking treatment until heavy metal ions in the electroplating wastewater are precipitated;
and (3) filtering, namely filtering the electroplating wastewater subjected to the precipitation treatment to remove particulate matters and suspended matters in the electroplating wastewater.
In an alternative, the precipitation process includes:
and when the heavy metal ions in the electroplating wastewater are precipitated, adding a coagulant and a flocculant into the electroplating wastewater in sequence.
In an alternative form, the membrane concentration process includes:
performing primary membrane concentration treatment, wherein the electroplating wastewater subjected to the precipitation filtration treatment enters primary reverse osmosis membrane treatment equipment to obtain second produced water and second concentrated solution; wherein the second produced water enters a produced water mixing pool;
and evaporating and crystallizing the second membrane concentrated solution to obtain the crystallized salt and a condensate, and mixing the condensate with the second produced water.
In an alternative mode, the membrane concentration process further includes:
and performing secondary membrane concentration treatment, wherein the second produced water and the condensate enter secondary reverse osmosis membrane concentration treatment equipment to obtain first produced water and first concentrated solution.
In an alternative form, the primary membrane concentration process includes:
the pretreated electroplating wastewater is sequentially subjected to first reverse osmosis membrane treatment, second reverse osmosis membrane treatment and third reverse osmosis membrane treatment; and respectively feeding the produced water obtained by the first reverse osmosis membrane treatment, the second reverse osmosis membrane treatment and the third reverse osmosis membrane treatment into a produced water mixing pool to obtain second produced water.
In an alternative mode, the operating pressure of the second reverse osmosis membrane treatment is 40 bar-60 bar.
In an alternative mode, the operating pressure of the third reverse osmosis membrane treatment is 100bar to 160 bar.
The invention provides a method for recycling electroplating wastewater, which comprises the following steps: cyanogen breaking treatment, namely adding a cyanogen breaker into the electroplating wastewater under an alkaline condition to remove cyanides in the electroplating wastewater; breaking the complex, namely adding a breaking agent into the electroplating wastewater subjected to the cyanide breaking treatment, or performing catalytic oxidation treatment on the electroplating wastewater subjected to the cyanide breaking treatment to remove a complex in the electroplating wastewater; performing precipitation filtration treatment, namely performing precipitation filtration on the electroplating wastewater subjected to the vein breaking treatment to obtain filtered sludge and clear liquid; filtering the sludge into precipitates and suspended matters containing recoverable heavy metals; and (2) post-treatment, namely performing membrane concentration treatment and evaporative crystallization treatment on the clear liquid to obtain a first concentrated solution, crystallized salt and first produced water, mixing the first concentrated solution and the clear liquid for retreatment, feeding the first produced water into a first produced water recycling pool for recycling, and recycling the filtered sludge in a recycling workshop after filter pressing. Therefore, cyanide and complex in the electroplating wastewater can be effectively removed by carrying out cyanide breaking and complex breaking treatment on the electroplating wastewater, so that the subsequent recovery and utilization of heavy metal ions in the electroplating wastewater are ensured, and the recovery utilization rate of the heavy metal ions in the electroplating wastewater is improved; after membrane concentration treatment, evaporation crystallization is carried out on the concentrated solution, so that the amount of evaporated and crystallized water can be reduced to the maximum extent, the investment and operation cost is saved, and the quality of the intermediate product water is ensured to reach the standard. The recycling of the heavy metal ions in the electroplating wastewater is improved, the problem of secondary pollution of the heavy metal ions to the environment is avoided, meanwhile, the produced water subjected to membrane concentration treatment is recycled, the recycling of water resources is ensured, the utilization efficiency of the water resources is improved, and the zero emission of the electroplating wastewater is ensured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart of an implementation of a recycling method for electroplating wastewater according to an embodiment of the present application;
fig. 2 is a process flow chart of the treatment of the zinc-containing cyanide-containing wastewater and the zinc-containing wastewater by the electroplating wastewater recycling treatment method provided in an embodiment of the present application;
FIG. 3 is a process flow chart of the method for recycling electroplating wastewater according to an embodiment of the present application for treating cyanide-containing wastewater, acid copper wastewater and pyrocopper wastewater;
fig. 4 is a process flow chart of the treatment of the comprehensive electroplating wastewater by the electroplating wastewater recycling treatment method according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. 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 embodiments described below and the features of the embodiments can be combined with each other without conflict.
In the description of the embodiments of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
FIG. 1 is a flow chart of an embodiment of the present application for recycling electroplating wastewater.
Referring to fig. 1, an electroplating wastewater recycling method provided in an embodiment of the present application includes the following steps:
and step 10, cyanogen breaking treatment, namely adding a cyanogen breaker into the electroplating wastewater under an alkaline condition to remove cyanides in the electroplating wastewater.
Specifically, the electroplating wastewater recycling treatment method provided by the embodiment of the application is mainly applied to treatment of cyanide-containing zinc-containing copper-containing cyanide and comprehensive wastewater. In the specific application, the zinc-containing cyanide-containing wastewater, the copper-containing cyanide-containing wastewater and the comprehensive wastewater in each workshop are collected through pipelines and automatically flow into a water collecting well, and then are pumped into a regulating reservoir through a lifting pump for homogeneous and uniform treatment, so that stable and continuous water inlet is provided for the subsequent treatment of the electroplating wastewater. In some optional embodiments, a pH value regulator such as acidity (for example, hydrochloric acid or sulfuric acid) or alkalinity (for example, sodium hydroxide or sodium carbonate) is added into the regulating reservoir to regulate the pH value of the electroplating wastewater to an alkaline condition, and then a cyanide breaking agent is added into the alkaline electroplating wastewater to ensure the oxidation-reduction potential of the electroplating wastewater, so that cyanide in the electroplating wastewater undergoes oxidation-reduction reaction under the alkaline condition, and cyanide breaking treatment is realized.
And step 12, carrying out complex breaking treatment, namely adding a complex breaking agent into the electroplating wastewater subjected to the cyanide breaking treatment, or carrying out catalytic oxidation treatment on the electroplating wastewater subjected to the cyanide breaking treatment to remove a complex in the electroplating wastewater.
Specifically, in the embodiment of the present application, the complex breaking treatment and the cyanogen breaking treatment may be performed simultaneously, and in some optional manners, the complex breaking treatment and the cyanogen breaking treatment may also be performed separately, which is not specifically limited in this embodiment.
Specifically, in the embodiment of the application, the pH value of the electroplating wastewater after the cyanide breaking and complex breaking treatment is adjusted by adjusting the pH value of the wastewater, for example, adding an acidic regulator (such as hydrochloric acid or sulfuric acid) or an alkaline regulator (such as sodium hydroxide or sodium carbonate) and the like, until the heavy metal ions in the electroplating wastewater are completely precipitated.
In some alternative embodiments, when the pH regulator is added to the electroplating wastewater, a coagulant and a flocculant may also be added to the electroplating wastewater; in specific application, the coagulant can be polyaluminium chloride (PAC), and specifically, the adding amount of the PAC can be 500-5000 ppm; the flocculating agent can be Polyacrylamide (PAM), and the adding amount of the flocculating agent PAM can be 1-20 PPM.
And step 16, post-treatment, namely performing membrane concentration treatment and evaporative crystallization treatment on the clear liquid to obtain a first concentrated solution, crystallized salt and first produced water, mixing the first concentrated solution and the clear liquid for retreatment, feeding the first produced water into a first produced water recycling pool for recycling, and recycling the filtered sludge in a recycling workshop after filter pressing.
The electroplating wastewater recycling treatment method provided by the embodiment of the application comprises the following steps: cyanogen breaking treatment, namely adding a cyanogen breaker into the electroplating wastewater under an alkaline condition to remove cyanides in the electroplating wastewater; breaking the complex, namely adding a breaking agent into the electroplating wastewater subjected to the cyanide breaking treatment, or performing catalytic oxidation treatment on the electroplating wastewater subjected to the cyanide breaking treatment to remove a complex in the electroplating wastewater; performing precipitation filtration treatment, namely performing precipitation filtration on the electroplating wastewater subjected to the vein breaking treatment to obtain filtered sludge and clear liquid; filtering the sludge into precipitates and suspended matters containing recoverable heavy metals; and (2) post-treatment, namely performing membrane concentration treatment and evaporative crystallization treatment on the clear liquid to obtain a first concentrated solution, crystallized salt and first produced water, mixing the first concentrated solution and the clear liquid for retreatment, feeding the first produced water into a first produced water recycling pool for recycling, and recycling the filtered sludge in a recycling workshop after filter pressing. Therefore, cyanide and complex in the electroplating wastewater can be effectively removed by carrying out cyanide breaking and complex breaking treatment on the electroplating wastewater, so that the subsequent recovery and utilization of heavy metal ions in the electroplating wastewater are ensured, and the recovery utilization rate of the heavy metal ions in the electroplating wastewater is improved; after membrane concentration treatment, evaporation crystallization is carried out on the concentrated solution, so that the amount of evaporated and crystallized water can be reduced to the maximum extent, the investment and operation cost is saved, and the quality of the intermediate product water is ensured to reach the standard. The recycling of the heavy metal ions in the electroplating wastewater is improved, the problem of secondary pollution of the heavy metal ions to the environment is avoided, meanwhile, the produced water subjected to membrane concentration treatment is recycled, the recycling of water resources is ensured, the utilization efficiency of the water resources is improved, and the zero emission of the electroplating wastewater is ensured.
In some specific examples, the electroplating wastewater recycling treatment method provided by the embodiment of the application mainly comprises treatment of zinc containing cyanide, copper containing cyanide and comprehensive wastewater; for the purpose of clarity of the present application, the following description will be made with respect to the treatment of wastewater containing cyanogen and zinc, containing copper and cyanogen, and the treatment of integrated wastewater.
Fig. 2 is a process flow chart of the treatment of the zinc-containing cyanide-containing wastewater and the zinc-containing wastewater by the electroplating wastewater recycling treatment method provided in an embodiment of the present application.
Based on the foregoing embodiment, referring to fig. 2, the method for recycling electroplating wastewater provided in an embodiment of the present application specifically includes the following steps when treating zinc-containing cyanide-containing wastewater:
and step 10, cyanogen breaking treatment, namely adding a cyanogen breaker into the electroplating wastewater under an alkaline condition to remove cyanides in the electroplating wastewater.
Specifically, in this embodiment, the cyanogen-breaking treatment includes:
and (3) primary cyanogen breaking, namely adding a cyanogen breaking agent into the electroplating wastewater under the condition that the pH value is 10.5-11, and breaking cyanogen of the electroplating wastewater under the condition that the oxidation reduction potential is 300-350.
And (2) secondary cyanogen breaking, namely adding a cyanogen breaking agent into the electroplating wastewater under the condition that the pH value is 8-9, and breaking cyanogen of the electroplating wastewater under the condition that the oxidation-reduction potential is 600-650.
Specifically, in the present embodiment, the cyanide breaking agent may be sodium hypochlorite (NaClO).
Specifically, in this embodiment, the precipitation filtration process includes:
and (4) precipitation treatment, namely adjusting the pH value of the electroplating wastewater subjected to the complex breaking treatment until heavy metal ions in the electroplating wastewater are precipitated.
Specifically, in this embodiment, the wastewater containing cyanogen and containing cyanogen is subjected to the above cyanogen breaking treatment, and then enters a pH adjusting tank together with the wastewater containing cyanogen and is added with an acid (HCl/H)2SO4) Or adjusting the pH value of the wastewater to 5.4-6.4 by alkali (NaOH), enabling zinc ions in the wastewater to generate zinc hydroxide precipitate under the condition, and adding coagulants PAC and PAM to accelerate the precipitation.
And (4) filtering, namely filtering the electroplating wastewater subjected to the precipitation treatment to remove particulate matters and suspended matters in the electroplating wastewater.
Specifically, in the embodiment, the electroplating wastewater after reaction automatically flows into the concentration tank from the pH adjustment tank to be subjected to mud-water separation, sludge at the bottom of the concentration tank is discharged and then is pressed by a plate frame, a sludge cake is transported to a recycling workshop, a press filtrate is returned to the pH adjustment tank, and zinc hydroxide in the sludge cake has economic value; the supernatant of the concentration tank enters a TMF (tubular microfiltration) system, and impurities such as residual fine particles, suspended matters and the like in the wastewater are thoroughly removed by utilizing the physical interception function of a tubular microfiltration membrane.
And step 16, post-treatment, namely performing membrane concentration treatment and evaporative crystallization treatment on the clear liquid to obtain a first concentrated solution, crystallized salt and first produced water, mixing the first concentrated solution and the clear liquid for retreatment, feeding the first produced water into a first produced water recycling pool for recycling, and recycling the filtered sludge in a recycling workshop after filter pressing.
Specifically, in this embodiment, the membrane concentration process includes:
performing primary membrane concentration treatment, wherein the electroplating wastewater subjected to the precipitation filtration treatment enters primary reverse osmosis membrane treatment equipment to remove soluble pollutants in the electroplating wastewater to obtain primary produced water and primary concentrated solution; wherein, the primary produced water enters a produced water mixing pool, and the primary concentrated solution enters a membrane concentrated solution storage pool.
Specifically, in the embodiment, the treatment membrane concentration treatment can adopt a reverse osmosis membrane to treat the electroplating wastewater subjected to the precipitation filtration treatment, and the reverse osmosis membrane can intercept pollutants such as soluble salts, organic matters and heavy metal ions in the electroplating wastewater to form a membrane concentrated solution, so that the separation of the pollutants such as the soluble salts, the organic matters and the heavy metal ions in the electroplating wastewater is realized. And after separation, soluble salt, organic matters, heavy metal ions and other pollutants exist in the membrane concentrated solution, and the produced water of the reverse osmosis membrane is used as primary produced water and enters a produced water mixing pool for subsequent treatment.
Performing resource treatment, namely performing solid-liquid separation on the primary concentrated solution to obtain second sludge, crystallized salt and condensate, wherein the second sludge is sludge containing recoverable heavy metals, and the condensate is mixed with the primary produced water and then subjected to secondary membrane concentration treatment to obtain secondary concentrated solution and secondary produced water; mixing the secondary concentrated solution with the pretreated wastewater for secondary treatment, and allowing secondary produced water to enter a produced water recycling pool; and recovering the first sludge after filter pressing.
In some embodiments, the primary membrane concentration process comprises:
the pretreated electroplating wastewater is sequentially subjected to first reverse osmosis membrane treatment, second reverse osmosis membrane treatment and third reverse osmosis membrane treatment; and the produced water obtained by the first reverse osmosis membrane treatment, the second reverse osmosis membrane treatment and the third reverse osmosis membrane treatment respectively enters a produced water mixing pool to obtain second produced water.
In some optional modes, the first reverse osmosis membrane can be a first-stage roll type RO membrane, substances such as soluble salt, organic matters and heavy metals in sewage are concentrated and separated through the RO membrane element, and water produced by the membrane system enters a water production mixing pool.
In some optional modes, referring to fig. 2, the concentrated solution obtained after the first roll-type RO treatment enters a second reverse osmosis membrane for treatment, specifically, the second reverse osmosis membrane may be a high-pressure wide-flow-channel reverse osmosis membrane (SRO-OGF membrane) system, the concentrated solution after the first roll-type RO treatment is further concentrated again, and the produced water of the SRO-OGF membrane system enters a produced water mixing tank.
In some embodiments, the operating pressure of the SRO-OGF membrane system is between 40bar and 60 bar.
Referring to fig. 2, the concentrated solution obtained after the treatment of the SRO-OGF membrane treatment system enters a third reverse osmosis membrane for treatment, specifically, the third reverse osmosis membrane may be a high-pressure special reverse osmosis membrane SUPER RO (SRO-160 membrane treatment system) which continuously performs reduction concentration on the concentrated water of the SRO-OGF membrane system by using the high-power concentration and ultrahigh pressure resistance characteristics of a special reverse osmosis membrane element, the produced water of the SRO-160 membrane system enters a produced water mixing tank, and the concentrated water of the SRO-160 membrane system enters a membrane concentrated solution storage tank. In some embodiments, the SRO-160 membrane system is operated at a pressure of 100bar to 160 bar.
In some alternatives, the solid-liquid separation may be evaporative crystallization using an MVR system. In some optional modes, the conditions of evaporation crystallization are controlled at 60-100 ℃ and under the negative pressure condition of 0.1-0.9 bar, and salt (sodium chloride, sodium sulfate, ammonium salt and phosphonium salt) and organic matters in the electroplating wastewater form crystallized salt. Referring to fig. 2, evaporation condensate enters a produced water mixing pool, and crystallized salt is subjected to ex-situ treatment for solid waste.
In some optional modes, the condensed water is mixed with the primary produced water and then is subjected to secondary membrane concentration treatment to obtain secondary concentrated solution and secondary produced water; and mixing the secondary concentrated solution with the pretreated wastewater for secondary treatment, and allowing secondary produced water to enter a produced water recycling pool.
Specifically, the concentration of second grade membrane can be formula RO system is rolled up to the second grade, produces the mixed liquid in the water mixing tank and gets into formula RO system is rolled up to the second grade, further intercepts remaining soluble salinity and organic matter etc. in producing the water and filters, reduces the impurity content of producing water.
For further explanation, the following specific examples are provided to illustrate the technical effects achieved by the embodiments of the present application using the above technical solutions.
Referring to table 1, table 1 shows a water quality analysis table of zinc-containing, cyanide-containing, zinc-containing electroplating wastewater. As can be seen from table 1, the zinc-containing cyanide wastewater and the zinc-containing wastewater are alkaline and contain a large amount of zinc ions; the zinc-containing cyanide wastewater also contains partial cyanide.
TABLE 1 Water quality analysis chart for zinc-containing, cyanide-containing and zinc-containing electroplating wastewater
By the method for recycling electroplating wastewater provided by the embodiment of the application, after the zinc-containing cyanide-containing electroplating wastewater in the table 1 is subjected to recycling treatment, referring to the table 2, the table 2 refers to 100m3And d, treating the zinc-containing cyanide-containing and zinc-containing electroplating wastewater according to the water quality indexes of each process stage.
TABLE 2 Water quality index of zinc-containing cyanide-containing and zinc-containing electroplating wastewater in each process stage
As can be seen from table 2, after the electroplating wastewater resource treatment method provided by the embodiment of the present application is used for treating the electroplating wastewater containing zinc and cyanogen, the electroplating wastewater containing zinc has the following technical advantages:
1) mixing the zinc-containing cyanide-containing wastewater after oxidation reduction with the zinc-containing wastewater, and generating heavy metal zinc ions into zinc hydroxide with economic value by adjusting the pH value;
2) the wastewater after the physicochemical treatment is completely mixed and enters a multi-stage multi-section reverse osmosis system, so that the wastewater can be concentrated to the maximum extent, the later-stage evaporation water amount is reduced, the investment and the operating cost are saved, and the stable standard reaching of the reclaimed water can be ensured;
3) the crystallized salt obtained by MVR evaporation of the final concentrated solution is common industrial solid waste, and the treatment cost is low.
Fig. 3 is a process flow chart of the electroplating wastewater recycling method for treating cyanide-containing wastewater, copper-containing wastewater and copper-scorching wastewater.
Based on the foregoing embodiment, referring to fig. 3, an electroplating wastewater recycling method provided in an embodiment of the present application, wherein the step 12 of breaking the complex specifically includes:
and (3) carrying out electrocatalytic oxidation on the electroplating wastewater subjected to the cyanogen breaking treatment to remove the complex in the electroplating wastewater.
after two-stage cyanogen breaking treatment, the electroplating wastewater automatically flows into a reduction pool, and the ORP value of the wastewater is controlled below 200 by adding a reducing agent (sodium bisulfite).
the copper cyanide-containing wastewater treated by the method enters a pH adjusting tank together with acid copper wastewater, and acid (HCl/H) is added2SO4) Or adjusting the pH value of the wastewater to 4.4-6.4 by alkali (NaOH), generating copper hydroxide precipitate by copper ions in the wastewater under the condition, and simultaneously adding a coagulant PAC and a flocculant PAM; PAC dosage is 500-5000 ppm, and PAM dosage is 1-20 ppm to accelerate precipitation.
For further explanation, the following specific examples are provided to illustrate the technical effects achieved by the embodiments of the present application using the above technical solutions.
Referring to Table 3, Table 3 shows water quality analysis tables of the copper-containing cyanide-containing wastewater, the copper-containing wastewater and the copper-coke wastewater. As can be seen from Table 3, the cyanide-containing wastewater containing copper is alkaline and contains a large amount of copper ions and part of cyanide; the copper coke wastewater is acidic and contains a large amount of copper ions; the coke copper wastewater is alkaline and contains a large amount of copper ions, partial organic matters and complex compounds.
TABLE 3 Water quality analysis Table for copper-containing cyanide-containing wastewater, copper-containing wastewater and copper-coke wastewater
By the method for recycling electroplating wastewater provided by the embodiment of the application, after the copper-containing cyanide-containing wastewater, the copper-containing wastewater and the pyrocopper wastewater in the table 3 are subjected to recycling treatment, referring to table 4, table 4 shows that 100m of electroplating wastewater is treated3And d, treating the copper-containing cyanide-containing wastewater, the copper-containing wastewater and the copper-scorching wastewater according to the water quality indexes of each process stage.
TABLE 4 Water quality index of copper-containing cyanide-containing wastewater, copper-containing wastewater and copper-coke wastewater at each process stage
As can be seen from table 4, after the electroplating wastewater recycling treatment method provided by the embodiment of the present application is used to treat cyanide-containing wastewater containing copper, copper-containing wastewater and copper-scorched wastewater, the following technical advantages are obtained:
1) firstly carrying out electrocatalytic oxidation on the pyrocopper wastewater and the like, and then adjusting the pH value to finally generate copper hydroxide with economic value;
2) the wastewater after the physicochemical treatment is completely mixed and enters a multi-stage multi-section reverse osmosis system, so that the wastewater can be concentrated to the maximum extent, the later-stage evaporation water amount is reduced, the investment and the operating cost are saved, and the stable standard reaching of the reclaimed water can be ensured;
3) the crystallized salt obtained by evaporating the final concentrated solution through MVR is common industrial solid waste, and the treatment cost is low.
Fig. 4 is a process flow chart of the treatment of the comprehensive electroplating wastewater by the electroplating wastewater recycling treatment method according to an embodiment of the present application.
Based on the foregoing embodiment, referring to fig. 4, an electroplating wastewater recycling treatment method provided in an embodiment of the present application, wherein the step 12 of breaking the complex specifically includes:
adding an oxidant into the electroplating wastewater subjected to cyanogen breaking treatment to remove a complex in the electroplating wastewater.
Specifically, in this example, the electroplating wastewater after the cyanogen breaking treatment was adjusted to a pH of 2 to 3, and hydrogen peroxide (H) was added2O2) Removing the complex in the electroplating wastewater.
For further explanation, the following specific examples are provided to illustrate the technical effects achieved by the embodiments of the present application using the above technical solutions.
Referring to Table 5, Table 5 shows the water quality analysis table of the comprehensive electroplating wastewater. From table 5, it can be seen that the comprehensive wastewater contains various heavy metal ions and contains a certain amount of cyanide and complex, so that the comprehensive wastewater is only subjected to water resource recycling. Heavy metal ions in the wastewater are too miscellaneous, the recovery difficulty is high, the cost is too high, and the recovery is abandoned. The miscellaneous salt in the waste water appears in the mode of general solid waste rather than dangerous waste, and the aim of reducing the operation cost is fulfilled.
TABLE 5 comprehensive water quality analysis meter for electroplating wastewater
By the method for recycling electroplating wastewater provided by the embodiment of the application, after the comprehensive electroplating wastewater in the table 5 is recycled, referring to the table 6, the table 6 refers to 100m3And d, treating the water quality indexes of each process stage by comprehensively electroplating wastewater.
TABLE 6 Water quality index of the electroplating wastewater in each process stage
The electroplating wastewater recycling treatment method provided by the embodiment of the application comprises the following steps: cyanogen breaking treatment, namely adding a cyanogen breaker into the electroplating wastewater under an alkaline condition to remove cyanides in the electroplating wastewater; breaking the complex, namely adding a breaking agent into the electroplating wastewater subjected to the cyanide breaking treatment, or performing catalytic oxidation treatment on the electroplating wastewater subjected to the cyanide breaking treatment to remove a complex in the electroplating wastewater; performing precipitation filtration treatment, namely performing precipitation filtration on the electroplating wastewater subjected to the vein breaking treatment to obtain filtered sludge and clear liquid; filtering the sludge into precipitates and suspended matters containing recoverable heavy metals; and (2) post-treatment, namely performing membrane concentration treatment and evaporative crystallization treatment on the clear liquid to obtain a first concentrated solution, crystallized salt and first produced water, mixing the first concentrated solution and the clear liquid for retreatment, feeding the first produced water into a first produced water recycling pool for recycling, and recycling the filtered sludge in a recycling workshop after filter pressing. Therefore, cyanide and complex in the electroplating wastewater can be effectively removed by carrying out cyanide breaking and complex breaking treatment on the electroplating wastewater, so that the subsequent recovery and utilization of heavy metal ions in the electroplating wastewater are ensured, and the recovery utilization rate of the heavy metal ions in the electroplating wastewater is improved; after membrane concentration treatment, evaporation crystallization is carried out on the concentrated solution, so that the amount of evaporated and crystallized water can be reduced to the maximum extent, the investment and operation cost is saved, and the quality of the intermediate product water is ensured to reach the standard. The recycling of the heavy metal ions in the electroplating wastewater is improved, the problem of secondary pollution of the heavy metal ions to the environment is avoided, meanwhile, the produced water subjected to membrane concentration treatment is recycled, the recycling of water resources is ensured, the utilization efficiency of the water resources is improved, and the zero emission of the electroplating wastewater is ensured.
The implementation case is as follows:
the total amount of wastewater treatment is 22000 tons per day, and the wastewater comprises main wastewater of the electroplating industry. The water quality parameters of the inlet water are as follows:
the effluent quality requirement is as follows:
| detecting items | PH | Color intensity | Turbidity of water | Electrical conductivity of |
| Unit of measurement | Dimensionless | Multiple times | NTU | us/cm |
| Detection value | 6～8 | ≤3 | ≤1 | ≤300 |
Final hazardous waste generation amount:
| item | Sludge amount (tpd) |
| Nickel electroplating wastewater sludge | 0.75 |
| Chemical nickel wastewater sludge | 0.08 |
| Chromium-containing wastewater sludge | 2.63 |
| Zinc-containing cyanide-containing wastewater and zinc-containing wastewater sludge | 0.04 |
| Copper-containing cyanide-containing wastewater, acid copper wastewater and pyrocopper wastewater sludge | 0.85 |
| Anodic oxidation of wastewater sludge | 0.08 |
| Comprehensive waste water sludge | 0.05 |
| Total up to | 4.47 |
Final general industrial solid waste production:
resource workshop product amount:
the overall process has the advantages that:
the heavy metal is classified and recycled, so that the high treatment cost of hazardous waste generated by the heavy metal and needing to be paid is reduced, the resource products can be recycled, and the income is obtained.
The full-membrane process not only realizes zero discharge of wastewater and resource recycling, but also reduces the addition of chemicals, reduces the treatment cost and greatly reduces the solid waste.
The conventional physicochemical technology, biochemical technology, membrane treatment and evaporation technology needs to add a large amount of medicament, the amount of the residual sludge is 0.6-0.8 percent of the amount of the wastewater, the residual sludge belongs to hazardous wastes, and the hazardous wastes need to be treated by a hazardous waste treatment mechanism to pay huge treatment cost. The final sludge amount of the embodiment of the application only accounts for one third of that of the traditional process, and only less than 8 percent of the residual sludge belongs to dangerous waste.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for recycling electroplating wastewater is characterized by comprising the following steps:
cyanogen breaking treatment, namely adding a cyanogen breaker into the electroplating wastewater under an alkaline condition to remove cyanides in the electroplating wastewater;
carrying out cyanogen breaking treatment, namely adding a cyanogen breaking agent into the electroplating wastewater subjected to cyanogen breaking treatment, or carrying out catalytic oxidation treatment on the electroplating wastewater subjected to cyanogen breaking treatment to remove a complex in the electroplating wastewater;
performing precipitation filtration treatment, namely performing precipitation filtration on the electroplating wastewater subjected to the vein breaking treatment to obtain filtered sludge and clear liquid; the filtered sludge is sediment and suspended matters containing recoverable heavy metals;
and post-treatment, namely performing membrane concentration treatment and evaporative crystallization treatment on the clear liquid to obtain first concentrated solution, crystallized salt and first produced water, mixing the first concentrated solution with the clear liquid for retreatment, feeding the first produced water into a first produced water recycling pool for recycling, and recycling the filtered sludge in a recycling workshop after filter pressing.
2. The method of claim 1, wherein the cyanogen-breaking treatment comprises:
first-stage cyanogen breaking, namely adding the cyanogen breaking agent into the electroplating wastewater under the condition that the pH value is 10.5-11, and breaking cyanogen in the electroplating wastewater under the condition that the oxidation reduction potential is 300-350;
and (2) secondary cyanogen breaking, namely adding the cyanogen breaking agent into the electroplating wastewater under the condition that the pH value is 8-9, and breaking cyanogen in the electroplating wastewater under the condition that the oxidation reduction potential is 600-650.
3. The method of claim 1, wherein the decomplexing process comprises:
adding an oxidant into the electroplating wastewater subjected to the cyanogen breaking treatment to remove a complex in the electroplating wastewater;
or, carrying out electrocatalytic oxidation on the electroplating wastewater subjected to the cyanogen breaking treatment to remove the complex in the electroplating wastewater.
4. The method of claim 1, wherein the precipitation filtration process comprises:
precipitating, namely adjusting the pH value of the electroplating wastewater subjected to the complex breaking treatment until heavy metal ions in the electroplating wastewater are precipitated;
and (3) filtering, namely filtering the electroplating wastewater subjected to the precipitation treatment to remove particulate matters and suspended matters in the electroplating wastewater.
5. The method of claim 4, wherein the precipitation treatment comprises:
and when the heavy metal ions in the electroplating wastewater are precipitated, adding a coagulant and a flocculant into the electroplating wastewater in sequence.
6. The method of claim 1, wherein the membrane concentration process comprises:
performing primary membrane concentration treatment, wherein the electroplating wastewater subjected to the precipitation filtration treatment enters primary reverse osmosis membrane treatment equipment to obtain second produced water and second concentrated solution; wherein the second produced water enters a produced water mixing pool;
and evaporating and crystallizing the second membrane concentrated solution to obtain the crystallized salt and a condensate, and mixing the condensate with the second produced water.
7. The method of claim 6, wherein the membrane concentration process further comprises:
and performing secondary membrane concentration treatment, wherein the second produced water and the condensate enter secondary reverse osmosis membrane concentration treatment equipment to obtain first produced water and first concentrated solution.
8. The method according to claim 6, wherein the primary membrane concentration treatment comprises:
the pretreated electroplating wastewater is sequentially subjected to first reverse osmosis membrane treatment, second reverse osmosis membrane treatment and third reverse osmosis membrane treatment; and respectively feeding the produced water obtained by the first reverse osmosis membrane treatment, the second reverse osmosis membrane treatment and the third reverse osmosis membrane treatment into a produced water mixing pool to obtain second produced water.
9. The method of claim 8 wherein the operating pressure of the second reverse osmosis membrane treatment is in the range of 40bar to 60 bar.
10. The method of claim 8 wherein said third reverse osmosis membrane treatment is performed at an operating pressure of 100bar to 160 bar.
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