CN115140865B - Cyanide-containing wastewater treatment method and cyanide-containing wastewater treatment system - Google Patents
Cyanide-containing wastewater treatment method and cyanide-containing wastewater treatment system Download PDFInfo
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 98
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000009713 electroplating Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000000571 coke Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- CIPAYOUGKKKEEN-UHFFFAOYSA-L copper carboxylato carbonate Chemical compound [Cu+2].[O-]C(=O)OC([O-])=O CIPAYOUGKKKEEN-UHFFFAOYSA-L 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- -1 pyrophosphate copper-tin alloy Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- 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
Abstract
The application discloses a cyanide-containing wastewater treatment method and a cyanide-containing wastewater treatment system, and relates to the technical field of electroplating wastewater treatment, wherein the method comprises the steps of continuously injecting pyrocopper wastewater into cyanide-containing wastewater to be treated for mixing until the PH of mixed liquid is within a preset first range and the copper ion content of the mixed liquid is within a preset second range; performing cyanide breaking treatment on the mixed liquid to obtain cyanide breaking mixed liquid, wherein the cyanide content of the cyanide breaking mixed liquid meets a preset emission standard; and carrying out copper removal treatment on the cyanide-breaking mixed solution and filtering the cyanide-breaking mixed solution subjected to copper removal treatment. The application is beneficial to improving the treatment efficiency of cyanide-containing wastewater.
Description
Technical Field
The application relates to the technical field of electroplating wastewater treatment, in particular to a cyanide-containing wastewater treatment method and a cyanide-containing wastewater treatment system.
Background
The cyanide-containing wastewater mainly comes from water washing after silver and gold precipitation in electroplating engineering, belongs to one of electroplating wastewater, and the pollutants comprise total COD, total CN, heavy metals and the like, and belong to cancerogenic, teratogenic and mutagenic highly toxic substances. Most of the existing electroplating wastewater treatment stations use a chlorine oxidation method and a hydrogen peroxide oxidation method to treat cyanide-containing wastewater, and the treatment efficiency of the cyanide-containing wastewater is always low due to the problems of complex process, slower reaction rate, limited area of a reaction tank and the like.
Disclosure of Invention
The present application aims to solve at least one of the technical problems existing in the prior art. Therefore, the application provides a cyanide-containing wastewater treatment method and a cyanide-containing wastewater treatment system, which are beneficial to improving the cyanide-containing wastewater treatment efficiency.
An embodiment of the first aspect of the present application provides a method for treating cyanide-containing wastewater, the method comprising:
continuously injecting the pyrocopper wastewater into cyanide-containing wastewater to be treated and mixing until the PH of the mixed liquid is within a preset first range and the copper ion content of the mixed liquid is within a preset second range;
performing cyanide breaking treatment on the mixed liquid to obtain cyanide breaking mixed liquid, wherein the cyanide content of the cyanide breaking mixed liquid meets a preset emission standard;
and carrying out copper removal treatment on the cyanide-breaking mixed solution and filtering the cyanide-breaking mixed solution subjected to copper removal treatment.
The embodiment of the first aspect of the application provides a method for treating cyanide-containing wastewater, which has at least the following beneficial effects: according to the application, the copper pyrocarbonate wastewater is added into the cyanide wastewater, the acidity of the copper pyrocarbonate wastewater can neutralize the alkalinity of the cyanide wastewater so that the cyanide wastewater is in a state with good cyanide breaking effect, and meanwhile, copper ions of the copper pyrocarbonate wastewater play a role of a catalyst, so that the cyanide breaking reaction rate can be accelerated.
According to some embodiments of the first aspect of the application, the first range is within 7-11.
According to some embodiments of the first aspect of the application, the second range is 50-150mg/L.
According to some embodiments of the first aspect of the present application, the step of performing a cyanide breaking treatment on the mixed liquid to obtain a cyanide breaking mixed liquid includes:
and adding hydrogen peroxide into the mixed liquid for reaction, and waiting for preset time until cyanide content in the mixed liquid is less than 0.5mg/L to obtain cyanide breaking mixed liquid.
According to some embodiments of the first aspect of the present application, the decoppering the cyanogen-breaking mixed solution includes: and continuously injecting a sulfuric acid solution into the cyanide-breaking mixed solution until the pH value of the cyanide-breaking mixed solution meets a preset pH value.
According to some embodiments of the first aspect of the application, the sulfuric acid solution is H with a concentration of 30% 2 SO 4 。
According to some embodiments of the first aspect of the application, the PH is 6.
According to some embodiments of the first aspect of the application, before the continuously injecting the pyrocopper wastewater into the cyanide-containing wastewater to be treated for mixing, the method further comprises: and (3) carrying out water separation treatment on the electroplating wastewater to obtain pyrocopper wastewater and cyanide-containing wastewater to be treated.
According to some embodiments of the first aspect of the present application, the filtering treatment of the cyanide-broken mixed solution after the copper removal treatment includes:
filtering the cyanide-broken mixed solution after copper removal treatment to obtain concentrated solution and filtered water;
and (3) carrying out mud pressing treatment on the concentrated solution and mud generated when the cyanide breaking mixed solution is subjected to copper removal treatment.
An embodiment of the second aspect of the present application provides a cyanide-containing wastewater treatment system, using a method according to any of the embodiments of the first aspect of the present application, the system comprising:
the PH adjusting tank is used for adjusting the PH of cyanide-containing wastewater to be treated;
the cyanide breaking reaction tank is used for breaking cyanide of the cyanide-containing wastewater to be treated after the PH is adjusted;
and the precipitation filter tank is used for carrying out copper removal treatment on the cyanide-containing wastewater to be treated after the cyanide breaking treatment.
Drawings
Additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a flow chart of a method for treating cyanide-containing wastewater provided by some embodiments of the present application;
fig. 2 is a schematic structural diagram of a cyanide-containing wastewater treatment system according to some embodiments of the present application.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
It should be noted that although a logical order is illustrated in the flowchart, in some cases, the steps illustrated or described may be performed in an order different from that in the flowchart. The terms and the like in the description and in the claims, and in the above-described drawings, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
In the description of the present application, the description of the first and second is only for the purpose of distinguishing technical features, and should not be construed as indicating or implying relative importance or implying the number of technical features indicated or the precedence of the technical features indicated.
In the description of the present application, unless explicitly defined otherwise, terms such as arrangement, installation, connection, etc. should be construed broadly and the specific meaning of the terms in the present application can be reasonably determined by a person skilled in the art in combination with the specific contents of the technical scheme.
The flow diagrams depicted in the figures are exemplary only, and do not necessarily include all of the elements and operations/steps, nor must they be performed in the order described. For example, some operations/steps may be decomposed, and some operations/steps may be combined or partially combined, so that the order of actual execution may be changed according to actual situations.
The principle of some chemicals used in the examples of the present application will be briefly described as follows:
the principle of breaking cyanogen by the chloridizing method is as follows: the oxidizing property of hypochlorite is utilized to oxidize cyanide into low-toxic cyanate, which is further oxidized into non-toxic carbonate and nitrogen. When using the oxychlorination method: although the chemical agents (such as bleaching water, bleaching powder and sodium hypochlorite) added in the water treatment device are relatively easy to obtain, so that the ton water treatment cost is relatively low. However, when the secondary chlorine is used, residual chlorine in the water is extremely harmful to a reverse osmosis membrane in reclaimed water, so that the RO membrane is damaged in a short time. So that the chlorine oxidation method is obviously unsuitable for breaking cyanide when the reclaimed water is reused in the electroplating sewage station instead of being directly discharged.
The principle of breaking cyanogen by hydrogen peroxide is as follows: under the reaction condition of PH > 7, hydrogen peroxide is used as oxidant to oxidize cyanide in the wastewater into cyanate, and the cyanate is hydrolyzed into carbonate and ammonia. When a hydrogen peroxide oxidation process is used: the reaction rate of hydrogen peroxide with cyanide generally requires about 1-2 hours of reaction time to treat the cyanide to < 0.5mg/L. The too high reaction time leads to excessively long occupation time of the cyanide breaking tank, and the cyanide breaking tank has limited use area, thereby affecting the treatment efficiency of cyanide-containing wastewater.
The cyanide-containing wastewater mainly comes from water washing after silver and gold precipitation in electroplating engineering, and pollutants of the cyanide-containing wastewater comprise total COD, total CN and heavy metals. And the heavy metals with higher recovery value are recovered by using a recovery process at the front end of the cyanide-containing wastewater discharged to a sewage station. Therefore, only total cyanide and total COD generally remain in cyanide-containing wastewater. The pyrophosphate copper wastewater mainly comes from the electroplating processes of pyrophosphate copper plating, pyrophosphate copper-tin alloy plating and the like, and the main pollutants in the wastewater are copper ions, phosphate, ammonia nitrogen, organic matters and the like. The existing electroplating wastewater treatment stations are used for separately treating the pyrocopper wastewater and the cyanide-containing wastewater, wherein the treatment method of the pyrocopper wastewater is usually that copper ions in the pyrocopper wastewater are acidified to generate copper sulfate precipitate, and then supernatant fluid is taken and combined into the comprehensive wastewater for treatment. The treatment method of cyanide-containing wastewater generally includes a chlorine oxidation method and a hydrogen peroxide oxidation method. Therefore, the existing method for separately treating the copper coke wastewater and the cyanide-containing wastewater has the defects of complex process, slower reaction rate, excessively long occupation time of a reaction tank caused by the slower reaction rate and the like, and further causes the problems of lower wastewater treatment efficiency and higher cost. Based on the method, the application provides a cyanide-containing wastewater treatment method and a cyanide-containing wastewater treatment system, and the cyanide-containing wastewater treatment efficiency can be improved and the cost can be saved by using the method of treating waste with waste.
Embodiments of the present application will be further described below with reference to the accompanying drawings.
Referring to fig. 1, an embodiment of the first aspect of the present application provides a method for treating cyanide-containing wastewater, including:
step 110, continuously injecting the pyrocopper wastewater into the cyanide-containing wastewater to be treated for mixing until the PH of the mixed liquid is within a preset first range and the copper ion content of the mixed liquid is within a preset second range.
In some embodiments, after the cyanide-containing wastewater is extracted by noble metals, the PH of the cyanide-containing wastewater is greater than or equal to 11, and the cyanide-containing wastewater is in an excessively high alkaline state, and if the cyanide is removed by directly using a hydrogen peroxide oxidation method, the problem of low removal rate exists. Because the waste water of the copper coke is acidic, the waste water of the copper coke is injected into the waste water containing cyanide, and the neutralization reaction can occur, so that the PH value of the waste water containing cyanide is reduced. At the moment, no additional chemical agent is needed for neutralization, waste is used for preparing waste, and the cost is lower. In addition, copper ions in the pyrocopper wastewater can form complexes (Cu (CN)) with cyanide ions under alkaline conditions 4 ) 3- Not only can the improvement of the cyanide breaking rate be quickened, but also the removal rate of cyanide can be improved, so that copper ions in the coke copper wastewater can play a role of a catalyst, and further the cyanide breaking process is quickened.
Specifically, the pH of the mixed liquid may be 10, and the copper ion content of the mixed liquid may be 50-150mg/L.
And 120, carrying out cyanide breaking treatment on the mixed liquid to obtain a cyanide breaking mixed liquid, wherein the cyanide content of the cyanide breaking mixed liquid meets the preset emission standard.
In some embodiments, the mixed liquid is injected into the cyanide breaking tank by using a lifting pump, a dosing pump is used for dosing hydrogen peroxide into the cyanide breaking tank, then circulation stirring is started, after 0.5-1h of reaction, the cyanide content of the cyanide breaking mixed liquid is detected, when the cyanide content is less than 0.5mg/L, the preset discharge standard is met, and then the cyanide breaking mixed liquid is overflowed to the inclined plate sedimentation tank by using a gravity mode.
And 130, carrying out copper removal treatment on the cyanide-breaking mixed solution and filtering the cyanide-breaking mixed solution subjected to the copper removal treatment.
In some embodiments, H is used at a concentration of 30% 2 SO 4 Copper removal treatment is carried out on the cyanogen breaking mixed solution, H 2 SO 4 Copper ions in the cyanide breaking mixed solution can be made to generate copper sulfate precipitation, after standing for a period of time, the copper sulfate precipitation is separated from supernatant, and the supernatant can enter a subsequent reclaimed water recycling working section.
Specifically, H with concentration of 30% is continuously injected into the cyanide-breaking mixed solution 2 SO 4 Until the PH value of the cyanogen breaking mixed solution is 6.
Therefore, the application adds the pyrocopper wastewater into the cyanide-containing wastewater, the acidity of the pyrocopper wastewater can neutralize the alkalinity of the cyanide-containing wastewater so that the cyanide-containing wastewater is in a state with better cyanide breaking effect, and simultaneously, copper ions of the pyrocopper wastewater play a role of a catalyst, so that the cyanide breaking reaction rate can be accelerated.
It will be appreciated that the first range is in the range 7 to 11.
It will be appreciated that the second range is 50-150mg/L.
Illustratively, the pyrocopper wastewater is continuously injected into the cyanide-containing wastewater to be treated and mixed until the ph=10 of the mixed liquid, and the copper ion content of the mixed liquid is 89mg/L.
It can be understood that, in step 120, the step of performing a cyanogen breaking treatment on the mixed liquid to obtain a cyanogen breaking mixed liquid includes: and adding hydrogen peroxide into the mixed liquid for reaction, and waiting for a preset time until cyanide content in the mixed liquid is less than 0.5mg/L to obtain cyanide breaking mixed liquid.
It can be understood that the step 130 of performing the copper removal treatment on the cyanide-breaking mixed solution includes: and continuously injecting sulfuric acid solution into the cyanide breaking mixed solution until the pH value of the cyanide breaking mixed solution meets the preset pH value.
It will be appreciated that the sulfuric acid solution is 30% H 2 SO 4 。
It will be appreciated that the method further comprises, prior to mixing, step 110, the continuous injection of the copper-coke wastewater into the cyanide-containing wastewater to be treated: and (3) carrying out water separation treatment on the electroplating wastewater to obtain pyrocopper wastewater and cyanide-containing wastewater to be treated.
It can be understood that the step 130 of filtering the cyanide-broken mixed solution after the copper removal treatment includes: and filtering the cyanide-broken mixed solution after copper removal treatment to obtain concentrated solution and filtered water, and performing mud pressing treatment on the concentrated solution and mud generated when the cyanide-broken mixed solution is subjected to copper removal treatment.
In some embodiments, the RO reverse osmosis membrane set is used for filtration, and the filtered water after filtration can be reused.
In some embodiments, a sterilizing device such as ultraviolet light may be provided, and a multi-stage filter may be provided.
In a second aspect, embodiments of the present application provide a cyanide-containing wastewater treatment system, comprising:
the PH adjusting tank is used for adjusting the PH of cyanide-containing wastewater to be treated;
the cyanide breaking reaction tank is used for breaking cyanide of cyanide-containing wastewater to be treated after PH adjustment;
and the precipitation filter tank is used for carrying out copper removal treatment on cyanide-containing wastewater to be treated after the cyanide breaking treatment.
It should be noted that, referring to fig. 2, in some embodiments, the treatment system further includes a cyanide-containing wastewater collection tank and an RO reverse osmosis system, and the specific operation process is as follows: injecting cyanide-containing wastewater to be treated into a PH adjusting tank from a cyanide-containing wastewater collecting tank, adding pyrocopper wastewater into the PH adjusting tank for mixing so as to adjust the PH of the cyanide-containing wastewater to be treated to 10 and the copper ion content to 50-150mg/L; injecting the mixed liquid into a cyanide breaking reaction tank by using a lifting pump, and adding hydrogen peroxide into the cyanide breaking reaction tank for cyanide breaking treatment; overflowing the cyanide-broken liquid into a precipitation filter tank, adding sulfuric acid into the precipitation filter tank to adjust the pH to 6, reacting sulfate radical with copper ions in the liquid to generate copper sulfate precipitate, standing to separate supernatant and precipitate, filtering the supernatant by an RO reverse osmosis system to obtain concentrated solution and filtered water, recycling the filtered water, and performing mud pressing treatment on the concentrated solution and sludge generated during copper removal treatment on the cyanide-broken mixed solution.
Illustratively, the precipitation filtration tank may be an inclined plate precipitation tank.
The following describes the implementation of the cyanide-containing wastewater treatment method in a specific example.
After the electroplating wastewater is subjected to water diversion treatment, 500ml of pyrocopper wastewater and 500ml of cyanide-containing wastewater to be treated are obtained, the pyrocopper wastewater is injected into the cyanide-containing wastewater to be treated in batches, stirring is started until the PH=10 of the mixed liquid is measured, and at the moment, the total injection amount of the pyrocopper wastewater is 223ml; adding hydrogen peroxide with the mass concentration of 1.5g/L into the mixed liquid for reaction, stirring for 40min, standing for 10min, and detecting cyanide breaking mixed liquid with the cyanide content of 0.1mg/L by adopting a silver nitrate titration method; continuously injecting 30% H into the cyanogen-breaking mixed solution 2 SO 4 And (3) until the PH of the cyanide breaking mixed solution is 6, filtering and precipitating to obtain supernatant and copper sulfate precipitate, filtering the supernatant by an RO reverse osmosis system to obtain concentrated solution and filtered water, recycling the filtered water, and pressing mud together with sludge generated when the cyanide breaking mixed solution is subjected to copper removal treatment.
Compared with the prior art, the method for separating the wastewater containing the cyanide from the copper wastewater has the advantages that when copper ions are used as catalysts after the copper wastewater is added, the cyanide breaking reaction rate is improved by 1 time, and the volume of a corresponding cyanide breaking reaction tank is reduced by 1 time. In the first step, the PH of the cyanide-containing wastewater is adjusted from 11 to 10, no sulfuric acid is used, and the wastewater is neutralized only by the acidity of the copper coke wastewater, so that the consumption of sulfuric acid is reduced, and the cost is saved.
The embodiments of the present application have been described in detail with reference to the accompanying drawings, but the present application is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present application.
Claims (6)
1. A method for treating cyanide-containing wastewater, comprising the steps of:
continuously injecting the pyrocopper wastewater into cyanide-containing wastewater to be treated and mixing until the pH value of the mixed liquid is within a preset first range and the copper ion content of the mixed liquid is within a preset second range;
performing cyanide breaking treatment on the mixed liquid to obtain cyanide breaking mixed liquid, wherein the cyanide content of the cyanide breaking mixed liquid meets a preset emission standard;
copper removal treatment is carried out on the cyanide-breaking mixed solution, and the cyanide-breaking mixed solution after copper removal treatment is subjected to filtration treatment;
the copper removing treatment for the cyanide breaking mixed solution comprises the following steps:
continuously injecting a sulfuric acid solution into the cyanide-breaking mixed solution until the pH value of the cyanide-breaking mixed solution meets a preset pH value;
the first range is 7-11;
the second range is 50-150mg/L;
the step of carrying out cyanogen breaking treatment on the mixed liquid to obtain cyanogen breaking mixed liquid comprises the following steps:
and adding hydrogen peroxide into the mixed liquid for reaction, and waiting for preset time until cyanide content in the mixed liquid is less than 0.5mg/L to obtain cyanide breaking mixed liquid.
2. The method of claim 1, wherein the sulfuric acid solution is 30% h 2 SO 4 。
3. The method of claim 1, wherein the pH is 6.
4. A method according to any one of claims 1 to 3, wherein prior to said continuously injecting the copper coke wastewater into the cyanide-containing wastewater to be treated for mixing, the method further comprises:
and (3) carrying out water separation treatment on the electroplating wastewater to obtain pyrocopper wastewater and cyanide-containing wastewater to be treated.
5. A method according to any one of claims 1 to 3, wherein said subjecting the decoppered cyanogen-broken mixed solution to a filtration treatment comprises:
filtering the cyanide-broken mixed solution after copper removal treatment to obtain concentrated solution and filtered water;
and (3) carrying out mud pressing treatment on the concentrated solution and mud generated when the cyanide breaking mixed solution is subjected to copper removal treatment.
6. A cyanide-containing wastewater treatment system employing the method of any one of claims 1 to 5, the system comprising:
the pH adjusting tank is used for adjusting the pH of cyanide-containing wastewater to be treated;
the cyanide breaking reaction tank is used for breaking cyanide of the cyanide-containing wastewater to be treated after the pH is adjusted;
and the precipitation filter tank is used for carrying out copper removal treatment on the cyanide-containing wastewater to be treated after the cyanide breaking treatment.
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