CN108862755A - A kind of processing method of nickel cyano complex electroplating wastewater - Google Patents
A kind of processing method of nickel cyano complex electroplating wastewater Download PDFInfo
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- CN108862755A CN108862755A CN201810810258.6A CN201810810258A CN108862755A CN 108862755 A CN108862755 A CN 108862755A CN 201810810258 A CN201810810258 A CN 201810810258A CN 108862755 A CN108862755 A CN 108862755A
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- Prior art keywords
- electroplating wastewater
- nickel
- cyano complex
- cyanogen
- processing method
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000002351 wastewater Substances 0.000 title claims abstract description 104
- 238000009713 electroplating Methods 0.000 title claims abstract description 71
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 63
- 238000003672 processing method Methods 0.000 title claims abstract description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 230000036647 reaction Effects 0.000 claims abstract description 18
- 238000007747 plating Methods 0.000 claims abstract description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001453 nickel ion Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- -1 cyanogen compound Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 4
- 239000002253 acid Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 7
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- VXCSPBPIGBJXJR-UHFFFAOYSA-N cyanic acid;sodium Chemical compound [Na].OC#N VXCSPBPIGBJXJR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017435 S2 In Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of processing methods of nickel cyano complex electroplating wastewater, include the following steps：Step S1：Nickel cyano complex is converted into nickel ammonium complex compound, and is separated in the form of carbonate deposition compound, electroplating wastewater cyanogen root exists in the form of free cyanogen；Step S2：Electroplating wastewater is sent to electrolytic cell, adjusting pH value is 11~12；Step S3：It adds sodium chloride progress cell reaction and obtains the cyanide-containing electroplating water of low concentration；Step S4：Adjusting pH value is 7~8, obtains low concentration free cyanogen alkalescent electroplating wastewater；Step S5：Waste water is passed through after filtering to reverse osmosis membrane assembly, and concentrated water is recycled to the electrolytic cell in step S2, and pure water is then used as plating piece rinsing.Nickel in electroplating wastewater of the present invention is precipitated by complex-precipitation and electrolysis realizes secondary reuse, and cyanide ion obtains cyanic acid sodium solution after making its oxidative degradation, Zassol product is obtained after high-efficiency evaporating and crystallizing by electrolysis and reverse osmosis operation.
Description
Technical field
The present invention relates to electroplating wastewater technical fields, more particularly to a kind of processing side of nickel cyano complex electroplating wastewater
Method.
Background technique
The waste water and waste liquid component that electroplating industry generates are complicated, are classified according to element contained in electroplating wastewater, can be with
It is divided into cyanide wastewater, gives up containing chromium (Cr) waste water, nickeliferous (Ni) waste water, containing cadmium (Cd) waste water, cupric (Cu) waste water, containing zinc (Zn)
Water, (Au) waste water containing gold, argentiferous (Ag) waste water etc..
Cyanide wastewater is usually individually handled, and is not mixed before treatment with other waste water, when Cyanide in Waste Water mass of ion concentration
When less than 50mg/L, alkaline chlorination process is preferably used to handle, oxidizer containing chlorine mainly has sodium hypochlorite, chlorine dioxide, liquid chlorine etc.；It is useless
When cryanide ion mass concentration is greater than 50mg/L in water, electrolysis processing technique is preferably used；And ozone treatment cyanide wastewater, to water inlet cyanogen
There is no limit for mass of ion concentration, but the waste water containing complexing cyanide ion, should not use ozone treatment.
In addition, due to the presence of complexing agent, can all be produced during process and chemical nickel plating are plated in the cyaniding of electroplating industry
The raw waste water containing nickel cyano complex, the waste water containing complexing agent is highly stable, is not easy at normal temperature by sodium hydroxide and vulcanized sodium
It is precipitated, it is difficult to the removing operation of nickel ion is realized using traditional chemical precipitation method, it is also difficult to use traditional alkaline chlorination
Method, electrolysis method and Ozonation carry out the processing of cyanide wastewater.Therefore, before handling such waste water, it usually needs carry out contact break
Pretreatment, to improve the treatment effeciency of nickel cyano complex waste water, often result in complex treatment process, it is at high cost the problems such as.
Summary of the invention
In place of the above the deficiencies in the prior art, the main purpose of the present invention is to provide a kind of plating of nickel cyano complex
The processing method of waste water, for solve nickel cyano complex waste water is difficult in the prior art, treatment effeciency is low, complex process, at
The problems such as this is high.
To achieve the above objectives, the technical solution adopted by the present invention is：
A kind of processing method of nickel cyano complex electroplating wastewater, including following processing step:
Step S1 precipitation reaction：Nickel cyano complex electroplating wastewater into knockout drum, by mole of carbonate and nickel element
Than being 1~1.2：1 addition sodium carbonate liquor, adding ammonia spirit and adjusting pH value is 7.5~9.5, is made big in nickel-containing waste water
Part of nickel is formed compound precipitates and is separated with nickel-ammonium complex compound combination, and cyanide ion is most of in the form of free cyanogen
It is present in electroplating wastewater；During process and chemical nickel plating are plated in the cyaniding of electroplating industry, nickel cyano complex electroplating wastewater
It is present among water body in the form of nickel cyano complex, the nickel element in the complex compound is mainly and the carbon in cyanide ion
Existing vacancy is coordinated, and forming stable complex system makes nickel cyano complex electroplating wastewater be difficult to remove.To above-mentioned plating
It is added into certain density ammonium hydroxide in waste water and forms ammonium ion, since its electronegativity of nitrogen is greater than carbon member in ammonium ion
Element, thus it is more stable with the coordinate bond of nickel formation, so that cyanide ion be made to be present in water body with the state of free cyanogen, and it is added
Sodium carbonate and ammonium hydroxide form certain alkaline water body, promote nickel-ammonium complex compound with carbonate in conjunction with, formation compound precipitates obtain
To separation, which can be used as the preparation that precursor compound is used as lithium battery；
Step S2pH value is adjusted：The processed electroplating wastewater of step S1 is sent to electrolytic cell, hydrogen-oxygen is added into electrolytic cell
Change sodium, adjusting pH value is 11~12；
Step S3 cell reaction：Sodium chloride is added into step S2 treated electroplating wastewater, and anodic current density is set
For 0.3~0.5A/dm2, tank voltage is 8~10V, starts cell reaction, after reacting 6~12h, obtains the plating of low concentration free cyanogen
Waste water, the remaining nickel ion in waste water are then precipitated to obtain enriching and recovering in electric tank cathode；Add sodium chloride in electroplating wastewater, one
Aspect can be used as electrolyte, promote the progress of cell reaction, still further aspect, and chloride ion is converted into the anode-side of electrolytic cell
Chlorine re-dissolves into and is converted into sodium hypochlorite in water body, plays the role of aoxidizing free cyanogen；Under above-mentioned pH value condition, trip
Electronics is lost in the anode of electrolytic cell from cyanogen, oxidation reaction occurs, removed so that free cyanogen be made to be converted into cyanic acid ion,
Just beginning free cyanogen concentration is higher, and cell reaction rate is fast, and the reaction time is longer, and electrolytic efficiency is lower, when control is reacted
Between, to take into account the efficiency of cell reaction and the economy of process program to the greatest extent；
Step S4pH value is adjusted：Mass percentage is added into the low concentration free cyanogen electroplating wastewater that step S3 is obtained is
15% hydrochloric acid solution, adjusting pH value is 7~8, obtains low concentration free cyanogen alkalescent electroplating wastewater；
Step S5 concentration operation：The low concentration free cyanogen alkalescent electroplating wastewater that step S4 is obtained is filtered by filter
Afterwards, it is passed through to reverse osmosis membrane assembly, obtained pure water is used as plating piece rinsing, obtained concentrated water in electroplating process and is recycled to step S2
In electrolytic cell, when cyanide ion accounts for all mass percentages containing cyanogen compound less than 1% in concentrated water, concentrated water outlet receive
Collection, further across obtaining Zassol after high-efficiency evaporating and crystallizing.By the concentrated water that reverse osmosis membrane assembly is concentrated to get contain not by
The free cyanogen handled completely returns to electrolytic cell and carries out oxidative degradation processing again；
Preferably, ozone can also be passed through in the step S3 in cell reaction, gas consumption is 0.2~0.4m3/
(min·min3)。
Preferably, the molality of sodium carbonate liquor is 0.5~2mol/L in the step S1.
Preferably, the mass percentage of ammonia spirit is 10~30% in the step S1.
Preferably, the net pole span of electrolytic cell is 35~45cm in the step S2.
Preferably, the dosage of sodium chloride is calculated by 5~10 times of cyanogen concentration in the step S3.
Preferably, the filtering accuracy of filter is 1~5um in the step S5.
Preferably, the anti-seepage membrane membrane module in the step S5 is polyvinylidene fluoride film.
Beneficial effects of the present invention：
The present invention is added by ammonium hydroxide and sodium carbonate, and nickel-cyano complex in nickel cyano complex electroplating wastewater is promoted to turn
Change nickel-ammonium complex compound into, and in conjunction with carbanion, forming compound precipitates effectively removes nickel element, the precipitating
The precursor compound that compound can be used as lithium battery is recycled；The present invention further pass through electrolysis and it is reverse osmosis concentrated
Contracting operation, economical and efficient make free cyanogen effectively be degraded, and pure water reuse carries out plating piece rinsing；Nickel-containing waste water of the present invention passes through
The secondary reuse for realizing heavy metal is precipitated in complex-precipitation and electrolysis, and cyanide wastewater is made by electrolysis and reverse osmosis operation containing cyanogen
Waste water concentrating cyclic electrolysis, pure water recycle, and realize the zero-emission of electroplating wastewater.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Certain known electroplate factory, is respectively adopted cyaniding plating process and chemical nickel plating, and the nickel cyano complex of the two mixing discharge is useless
Water, wherein cyanide ion concentration is 81mg/L, and nickel ion concentration 35mg/L illustrates electroplating wastewater below in conjunction with specific embodiment
Processing.
Embodiment 1
A kind of processing method of nickel cyano complex electroplating wastewater, including following processing step:
Step S1 precipitation reaction：Nickel cyano complex electroplating wastewater into knockout drum, by mole of carbonate and nickel element
Than being 1：The sodium carbonate liquor that 1 addition molality is 0.5mol/L, adds the ammonium hydroxide that mass percentage is 10%
It is 7.5 that solution, which adjusts pH value, combines most of nickel in nickel-containing waste water with nickel-ammonium complex compound and forms carbonate deposition compound
It is separated, and cyanide wastewater is largely present in electroplating wastewater in the form of free cyanogen；Isolated carbonate deposition
The precursor compound that compound can act on lithium battery uses, and nickel resources is made to obtain effective recycling；
Step S2pH value is adjusted：The processed electroplating wastewater of step S1 is sent to electrolytic cell, the net pole span of electrolytic cell is 35~
Sodium hydroxide is added into electrolytic cell by 45cm, and adjusting pH value is 11；
Step S3 cell reaction：Sodium chloride is added into step S2 treated electroplating wastewater, dosage presses the 5 of cyanogen concentration
It calculates again, setting anodic current density is 0.3A/dm2, tank voltage 8V starts cell reaction, is passed through during cell reaction
Ozone, gas consumption 0.2m3/(min·min3), promote water body stirring, free cyanogen made to obtain more fully oxidation reaction,
After reacting 12h, low concentration free cyanogen electroplating wastewater is obtained, the remaining nickel ion in waste water is then precipitated to obtain richness in electric tank cathode
Collection recycling；
Step S4pH value is adjusted：Mass percentage is added into the low concentration free cyanogen electroplating wastewater that step S3 is obtained is
15% hydrochloric acid solution, adjusting pH value is 7, obtains low concentration free cyanogen alkalescent electroplating wastewater；
Step S5 concentration operation：It is by filtering accuracy by the low concentration free cyanogen alkalescent electroplating wastewater that step S4 is obtained
After the filtering of 1um filter, it is passed through the reverse osmosis membrane assembly to material for polyvinylidene fluoride film, obtained pure water is used as plating
Plating piece rinses in the process, and obtained concentrated water is recycled to the electrolytic cell in step S2, when in concentrated water cyanide ion account for it is all containing cyaniding
When closing the mass percentage of object less than 1%, concentrated water outlet is collected, and concentrated water obtains Zassol crystalline substance after high-efficiency evaporating and crystallizing
Body.
The present embodiment heavy metal nickel 85% is recycled in the form of carbonate complex-precipitation compound, and 15% passes through electrolysis
Slot cathode elemental nickel, which is precipitated, to be recycled, and the removal rate of cyanide ion is 99.1%.
Embodiment 2
Step S1 precipitation reaction：Nickel cyano complex electroplating wastewater into knockout drum, by mole of carbonate and nickel element
Than being 1：The sodium carbonate liquor that 1.1 addition molalities are 1mol/L, adds the ammonium hydroxide that mass percentage is 20%
It is 8.5 that solution, which adjusts pH value, combines most of nickel in nickel-containing waste water with nickel-ammonium complex compound and forms carbonate deposition compound
It is separated, and cyanide wastewater is largely present in electroplating wastewater in the form of free cyanogen；Isolated carbonate deposition
The precursor compound that compound can act on lithium battery uses, and nickel resources is made to obtain effective recycling；
Step S2pH value is adjusted：The processed electroplating wastewater of step S1 is sent to electrolytic cell, the net pole span of electrolytic cell is 40cm,
Sodium hydroxide is added into electrolytic cell, adjusting pH value is 11.5；
Step S3 cell reaction：Sodium chloride is added into step S2 treated electroplating wastewater, dosage presses the 7 of cyanogen concentration
It calculates again, setting anodic current density is 0.4A/dm2, tank voltage 9V starts cell reaction, is passed through during cell reaction
Ozone, gas consumption 0.3m3/(min·min3), promote water body stirring, free cyanogen made to obtain more fully oxidation reaction,
After reacting 9h, low concentration free cyanogen electroplating wastewater is obtained, the remaining nickel ion in nickel-containing waste water is then precipitated in electric tank cathode
To enriching and recovering；
Step S4pH value is adjusted：Mass percentage is added into the low concentration free cyanogen electroplating wastewater that step S3 is obtained is
15% hydrochloric acid solution, adjusting pH value is 7.5, obtains low concentration free cyanogen alkalescent electroplating wastewater；
Step S5 concentration operation：It is by filtering accuracy by the low concentration free cyanogen alkalescent electroplating wastewater that step S4 is obtained
After the filtering of 3um filter, it is passed through the reverse osmosis membrane assembly to material for polyvinylidene fluoride film, obtained pure water is used as plating
Plating piece rinses in the process, and obtained concentrated water is recycled to the electrolytic cell in step S2, when in concentrated water cyanide ion account for it is all containing cyaniding
When closing the mass percentage of object less than 1%, concentrated water outlet is collected, and concentrated water obtains Zassol crystalline substance after high-efficiency evaporating and crystallizing
Body.
The present embodiment heavy metal nickel 87% is recycled in the form of carbonate complex-precipitation compound, and 13% passes through electrolysis
Slot cathode elemental nickel, which is precipitated, to be recycled, and the removal rate of cyanide ion is 99.3%.
Embodiment 3
Step S1 precipitation reaction：Nickel cyano complex electroplating wastewater into knockout drum, by mole of carbonate and nickel element
Than being 1：The sodium carbonate liquor that 1.2 addition molalities are 2mol/L, adds the ammonium hydroxide that mass percentage is 30%
It is 9.5 that solution, which adjusts pH value, combines most of nickel in nickel-containing waste water with nickel-ammonium complex compound and forms carbonate deposition compound
It is separated, and cyanide wastewater is largely present in electroplating wastewater in the form of free cyanogen；Isolated carbonate deposition
The precursor compound that compound can act on lithium battery uses, and nickel resources is made to obtain effective recycling；
Step S2pH value is adjusted：The processed electroplating wastewater of step S1 is sent to electrolytic cell, the net pole span of electrolytic cell is 45cm,
Sodium hydroxide is added into electrolytic cell, adjusting pH value is 12；
Step S3 cell reaction：Sodium chloride is added into step S2 treated electroplating wastewater, dosage is by cyanogen concentration
10 times of calculating, setting anodic current density are 0.5A/dm2, tank voltage 10V starts cell reaction, logical during cell reaction
Enter ozone, gas consumption 0.4m3/(min·min3), promote water body stirring, so that free cyanogen is obtained more fully oxidation anti-
It answers, after reacting 6h, obtains low concentration free cyanogen electroplating wastewater, the remaining nickel ion in nickel-containing waste water is then precipitated in electric tank cathode
Obtain enriching and recovering；
Step S4pH value is adjusted：Mass percentage is added into the low concentration free cyanogen electroplating wastewater that step S3 is obtained is
15% hydrochloric acid solution, adjusting pH value is 8, obtains low concentration free cyanogen alkalescent electroplating wastewater；
Step S5 concentration operation：It is by filtering accuracy by the low concentration free cyanogen alkalescent electroplating wastewater that step S4 is obtained
After the filtering of 5um filter, it is passed through the reverse osmosis membrane assembly to material for polyvinylidene fluoride film, obtained pure water is used as plating
Plating piece rinses in the process, and obtained concentrated water is recycled to the electrolytic cell in step S2, when in concentrated water cyanide ion account for it is all containing cyaniding
When closing the mass percentage of object less than 1%, concentrated water outlet is collected, and concentrated water obtains Zassol crystalline substance after high-efficiency evaporating and crystallizing
Body.
The present embodiment heavy metal nickel 90% is recycled in the form of carbonate complex-precipitation compound, and 10% passes through electrolysis
Slot cathode elemental nickel, which is precipitated, to be recycled, and the removal rate of cyanide ion is 99.5%.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (8)
1. a kind of processing method of nickel cyano complex electroplating wastewater, which is characterized in that including following processing step:
Step S1 precipitation reaction：Nickel cyano complex electroplating wastewater into knockout drum is 1 by the molar ratio of carbonate and nickel element
~1.2：1 addition sodium carbonate liquor, adding ammonia spirit and adjusting pH value is 7.5~9.5, makes most of nickel in nickel-containing waste water
It forms compound precipitates with nickel-ammonium complex compound combination and is separated, and cyanide ion is largely present in the form of free cyanogen
In electroplating wastewater；
Step S2pH value is adjusted：The processed electroplating wastewater of step S1 is sent to electrolytic cell, sodium hydroxide is added into electrolytic cell,
Adjusting pH value is 11~12；
Step S3 cell reaction：Sodium chloride is added into step S2 treated electroplating wastewater, setting anodic current density is 0.3
~0.5A/dm2, tank voltage is 8~10V, starts cell reaction, after reacting 6~12h, obtains low concentration free cyanogen electroplating wastewater,
Remaining nickel ion in waste water is then precipitated to obtain enriching and recovering in electric tank cathode；
Step S4pH value is adjusted：It is 15% that mass percentage is added into the low concentration free cyanogen electroplating wastewater that step S3 is obtained
Hydrochloric acid solution, adjusting pH value is 7~8, obtains low concentration free cyanogen alkalescent electroplating wastewater；
Step S5 concentration operation：The low concentration free cyanogen alkalescent electroplating wastewater that step S4 is obtained after filter filters,
It is passed through to reverse osmosis membrane assembly, obtained pure water is used as plating piece rinsing, obtained concentrated water in electroplating process and is recycled in step S2
Electrolytic cell, when cyanide ion accounts for all mass percentages containing cyanogen compound less than 1% in concentrated water, concentrated water outlet receive
Collection, further across obtaining Zassol after high-efficiency evaporating and crystallizing.
2. the processing method of nickel cyano complex electroplating wastewater as described in claim 1, which is characterized in that electric in the step S3
Ozone can also be passed through in solution reaction, gas consumption is 0.2~0.4m3/(min·min3)。
3. the processing method of nickel cyano complex electroplating wastewater as described in claim 1, which is characterized in that carbon in the step S1
The molality of acid sodium solution is 0.5~2mol/L.
4. the processing method of nickel cyano complex electroplating wastewater as described in claim 1, which is characterized in that ammonia in the step S1
The mass percentage of aqueous solution is 10~30%.
5. the processing method of nickel cyano complex electroplating wastewater as described in claim 1, which is characterized in that electric in the step S2
The solution net pole span of slot is 35~45cm.
6. the processing method of nickel cyano complex electroplating wastewater as described in claim 1, which is characterized in that chlorine in the step S3
Change the dosage of sodium by 5~10 times of calculating of cyanogen concentration.
7. the processing method of nickel cyano complex electroplating wastewater as described in claim 1, which is characterized in that mistake in the step S5
The filtering accuracy of filter is 1~5um.
8. the processing method of nickel cyano complex electroplating wastewater as described in claim 1, which is characterized in that in the step S5
Anti-seepage membrane membrane module is polyvinylidene fluoride film.
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| CN109250803A (en) * | 2018-11-29 | 2019-01-22 | 黄河水利职业技术学院 | A kind of electroplating waste processing equipment and processing method |
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| CN101613162A (en) * | 2009-07-30 | 2009-12-30 | 上海京瓷电子有限公司 | The treatment process that a kind of electroplating wastewater utilizes again |
| CN102701339A (en) * | 2012-06-07 | 2012-10-03 | 中国海洋大学 | Recovery processing method of cyanide barren solution |
| CN105565553A (en) * | 2015-12-22 | 2016-05-11 | 解艳超 | Zero-emission purifying and recycling system of cyanide-containing heavy metal wastewater |
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| CN101613162A (en) * | 2009-07-30 | 2009-12-30 | 上海京瓷电子有限公司 | The treatment process that a kind of electroplating wastewater utilizes again |
| CN102701339A (en) * | 2012-06-07 | 2012-10-03 | 中国海洋大学 | Recovery processing method of cyanide barren solution |
| CN105565553A (en) * | 2015-12-22 | 2016-05-11 | 解艳超 | Zero-emission purifying and recycling system of cyanide-containing heavy metal wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109250803A (en) * | 2018-11-29 | 2019-01-22 | 黄河水利职业技术学院 | A kind of electroplating waste processing equipment and processing method |
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