CN107746953A - The method that high purity copper and nickel nitrate are prepared with electroplating sludge - Google Patents
The method that high purity copper and nickel nitrate are prepared with electroplating sludge Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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Abstract
The present invention relates to scrap metal to handle recovery technology field, more particularly to the method for high purity copper and nickel nitrate is prepared with electroplating sludge, including dissolving is leached, and electroplating sludge aoxidizes with acid solution mixed aeration, obtains leachate；Iron removaling is complexed, oxidizing reaction is added, obtains removing ferrous solution；Resin adsorption, except ferrous solution is passed through ion exchange resin column ionic adsorption, desorption obtains stripping liquid；Electrodeposition sinks copper, using Ti/SnO2‑Sb2O3/PbO2Stripping liquid is carried out electrodeposition reaction, obtains fine copper and low copper solution by CNTs PDDA as anode；Abstraction impurity removal, obtain nickeliferous strip liquor D and organic phase D；Ultrasonic oil removing, segmentation oil removing is carried out to strip liquor D, through supersonic gas vibrating and secondary air-floatation oil removing, obtain nickel nitrate solution；It is concentrated and dried, nickel nitrate solution is concentrated by evaporation, cooling and drying, obtains nickel nitrate crystal.The method technique of the present invention is simple, and energy consumption is relatively low, is capable of the metallic copper of regenerating high purity.
Description
Technical field
High purity copper and nitric acid are prepared the present invention relates to scrap metal processing recovery technology field, more particularly to electroplating sludge
The method of nickel.
Background technology
With expanding economy and the continuous improvement of industrialized level, plating industry has obtained fast development, but electroplates production
Industry easily causes the heavy metal pollution in place in evolution, and its pollution is concentrated mainly on sewage treatment plant, raw material stockyard
Near, if without direct landfill of being prudent in dealing with, larger ecological threat can be brought to surrounding environment, how it is repaired
Have become the focus of research with improvement.
Electroplating sludge is product of the electroplating wastewater after acid-base neutralization, flocculation sediment, and moisture, content of ashes are very high, category
In meta-alkalescence material.The elements such as the Cr in electroplating wastewater, Fe, Ni, Cu, Zn, Pb, Cd are transferred in sludge, and content is much super
National Environmental discharge standard is crossed, is banked up for a long time, harmful element will be lost in and cause more serious secondary pollution, electroplating sludge
Thus it is put into China's danger wastes register the HW17th.China's electroplating enterprise small scale, product are more, and caused sludge is basic
On be the composition containing various metals mixing sludge, some of which tenor is even above common metal ore deposit.According to statistics, China's electricity
Plate enterprise and produce about 10,000,000 t electroplating sludges every year, wherein there is substantial amounts of valuable metal to reclaim.It is big in native metal resource
Under the present situation for measuring consumption, by valuable metal in electroplated mud recycling, the fundamental requirement of environmental protection, Ye Shike are not only
Sustainable development and the important means of recycling economy.Electroplating technology mainly includes the plating of the monometallics such as copper facing, nickel plating and binary is closed
Metallic element species and content are different in the electroplating sludge that gold, multicomponent alloy plating, therefore different electroplating technologies obtain.By right
The field research of electroplating wastewater treatment technique and analysis to separate sources electroplating sludge physicochemical property understand, electroplating sludge group
Point mainly comprising heavy metal compound and the solubility salt such as copper, nickel, pH value is meta-alkalescence material between 7.5~8.0, moisture
And content of ashes is high.The metal recovery processes of electroplating sludge still have complex process at present, and energy consumption is higher, the gold of reclaiming
Belong to the problem of purity is relatively low.
The content of the invention
In view of this, it is an object of the invention to provide the method that high purity copper and nickel nitrate are prepared with electroplating sludge, this method
Technique is simple, and energy consumption is relatively low, being capable of regenerating high purity metallic copper.
The present invention solves above-mentioned technical problem by following technological means：
The method that high purity copper and nickel nitrate are prepared with electroplating sludge, comprises the following steps：
Dissolving is leached, and electroplating sludge is mixed with acid solution, 3~5h of aerating oxidation, is filtrated to get filter residue A and leachate；
Iron removaling is complexed, behind pH=2.5~3.0 for adjusting leachate, adds oxidizing reaction 1.5h, then adjust pH=
3.5~3.8, it is filtrated to get filter residue B and except ferrous solution；
Resin adsorption, 35~45 DEG C will be heated to except ferrous solution, be passed through strong-acid cation-exchange resin post carry out copper ion,
Nickel ion adsorbs, and after resin adsorption saturation, carries out backwash desorption to resin column with 3mol/L sulfuric acid solution, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, and the moon is used as using pure copper starting sheet
Pole, stripping liquid is subjected to electrodeposition reaction under DC current effect, obtains fine copper and low copper solution；
Abstraction impurity removal, P204 extractants are added into low copper solution and sodium carbonate liquor carries out one-level saponifiable extraction, are obtained
Nickeliferous raffinate A and organic phase A, P204 extractants are continuously added in raffinate A and sodium carbonate liquor carries out two level saponifiable extraction
Processing, obtains raffinate C and nickeliferous organic phase C, and the salpeter solution that 3mol/L is added in organic phase C is stripped, contained
Nickel strip liquor D and organic phase D；
Ultrasonic oil removing, segmentation oil removing is carried out to strip liquor D, after supersonic gas vibrating and secondary air-floatation oil removing, then use fiber
Ball or filament absorption oil removing, press filtration obtain nickel nitrate solution；
It is concentrated and dried, nickel nitrate solution is evaporated concentration, and adjust concentrate pH=2.0, decrease temperature crystalline, filters dry
It is dry, obtain nickel nitrate crystal.
Further, the strong-acid cation-exchange resin is NDA-36 resins.
Further, tree is exchanged except ferrous solution is passed through strong-acid cation with 1~4BV/h flow velocity in the resin adsorption step
Fat post carries out copper ion, nickel ion absorption, and the liquids recovery after absorption, which is used to dissolve, leaches process, and sulfuric acid solution is with 2~4BV/h
Flow velocity to resin column carry out backwash desorption.
Further, the Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is in Ti/SnO using pulse electrodeposition method2-
Sb2O3Upper deposition β-PbO2It is made with CNTs/PDDA.
CNT is to stack the thing with tubular structure formed two-by-two in the form of hexatomic ring by substantial amounts of carbon atom
Matter, there is the premium properties such as larger surface area, electric conductivity are high and chemical stability is good；PDDA is a kind of safe and nontoxic, readily soluble
In the conductive polyelectrolyte of water；Negatively charged CNT and positively charged PDDA are incorporated in one by electrostatic attraction
Rise, and be entrained in PbO2In layer, electrode surface is set to generate more free OH, it is possible to increase O2Deposition potential, enhancing electricity
The electrocatalysis characteristic of pole, electrolytic efficiency is improved, reduces power consumption to a certain extent.
Further, the CNT is the CNT with sharp end nose cone shape prepared using hydrogen arc process.
Further, the Ti/SnO2-Sb2O3/PbO2In-CNTs-PDDA preparation, by Ti/SnO2-Sb2O3It is placed in plating
In liquid, using three-electrode system, Ti/SnO2-Sb2O3It is that reference electrode is implemented to electrode, Ag/AgCl to be for working electrode, platinized platinum
Pulse electrodeposition 15min, obtains Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA combination electrodes.
Further, the key component of the electroplate liquid is 0.5mol/LPb (NO3)2、0.15mol/LHNO3、0.05mol/
LKF2·H2O、50g/LCNTs/PDDA。
Further, it is 55~65 DEG C, 2.0~2.5V of tank voltage of temperature that the electrodeposition, which sinks the parameter of copper step, current density
230A/m2。
Further, the parameter of the ultrasonic oil removing is 15~25 DEG C, 25~30kHz of frequency, power 350W of temperature.
Beneficial effects of the present invention：The present invention is neutralized electroplating sludge and acid solution, and metal is carried out into dissolving leaching
Go out to obtain the leachate of metal ion, metal is converted into metal ion as much as possible is present in leachate；The present invention is to leaching
Go out liquid and iron ion is removed by the way of oxidation complexation, technique is simple, and de-ferrous effect is preferable；The present invention is to except ferrous solution is using tree
Fat adsorption treatment, extract except the cupro-nickel ion in ferrous solution, other ion isolations are gone out；Used in the heavy copper of electrode of the present invention
Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA electrode surfaces can give birth to
Into more free OH, it is possible to increase O2Deposition potential, strengthen the catalytic performance of electrode.The method technique of the present invention is simple,
Energy consumption is relatively low, can regenerate purity higher metallic copper and nickel nitrate.
Brief description of the drawings
Fig. 1 is the schematic flow sheet for the method that the present invention prepares high purity copper and nickel nitrate with electroplating sludge.
Embodiment
Below with reference to the drawings and specific embodiments, the present invention is described in detail：
As shown in figure 1, in the method that high purity copper and nickel nitrate are prepared with electroplating sludge of the present invention, comprise the following steps：
Dissolving is leached, and electroplating sludge is mixed with acid solution, 3~5h of aerating oxidation, is filtrated to get filter residue A and leachate；
Iron removaling is complexed, behind pH=2.5~3.0 for adjusting leachate, adds oxidizing reaction 1.5h, then adjust pH=
3.5~3.8, it is filtrated to get filter residue B and except ferrous solution；
Resin adsorption, 35~45 DEG C will be heated to except ferrous solution, be passed through strong-acid cation-exchange resin post carry out copper ion,
Nickel ion adsorbs, and after resin adsorption saturation, carries out backwash desorption to resin column with 3mol/L sulfuric acid solution, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, and the moon is used as using pure copper starting sheet
Pole, stripping liquid is subjected to electrodeposition reaction under DC current effect, obtains fine copper and low copper solution；
Abstraction impurity removal, P204 extractants are added into low copper solution and sodium carbonate liquor carries out one-level saponifiable extraction, are obtained
Nickeliferous raffinate A and organic phase A, P204 extractants are continuously added in raffinate A and sodium carbonate liquor carries out two level saponifiable extraction
Processing, obtains raffinate C and nickeliferous organic phase C, and the salpeter solution that 3mol/L is added in organic phase C is stripped, contained
Nickel strip liquor D and organic phase D；
Ultrasonic oil removing, segmentation oil removing is carried out to strip liquor D, after supersonic gas vibrating and secondary air-floatation oil removing, then use fiber
Ball or filament absorption oil removing, press filtration obtain nickel nitrate solution；
It is concentrated and dried, nickel nitrate solution is evaporated concentration, and adjust concentrate pH=2.0, decrease temperature crystalline, filters dry
It is dry, obtain nickel nitrate crystal.
Ti/SnO is used in the heavy copper step of the electrodeposition of the present invention2-Sb2O3/PbO2- CNTs-PDDA carries out copper as anode and sunk
Product, the Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is by Ti/SnO2-Sb2O3It is placed in electroplate liquid, using three-electrode system,
Ti/SnO2-Sb2O3It is that reference electrode implementation pulse electrodeposition 15min obtains to electrode, Ag/AgCl to be for working electrode, platinized platinum
, it is prepared as follows：
Embodiment one：Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA preparation
CNTs/PDDA preparation, the CNT with sharp end nose cone shape is prepared using hydrogen arc process, uses mass concentration
The concentrated nitric acid that the concentrated sulfuric acid and mass concentration for 98% are 65% is mixed to get acidic mixed solution, and the CNT is placed in into acid
Property mixed solution in be heated to reflux 10h, the CNT that centrifuge washing is acidified to neutrality, the CNT of acidifying is added
Stirred in hydrogen peroxide, while be to slowly warm up to 100 DEG C, centrifuge washing to neutrality, be dried to obtain the CNT of pretreatment, take poly-
The alkyl dimethyl ammonium chloride of dialkylene third, which is added in sodium-chloride water solution, to be stirred and evenly mixed, and the PDDA that PDDA mass concentrations are 40% is made
The aqueous solution, the addition pretreated CNTs of 5g in every 100mLPDDA aqueous solution, stirring 20h, filtration washing, dry
To CNTs/PDDA.
Titanium base pre-processes, and takes 0.5mm titanium plate successively to be polished with the sand paper of 1000 mesh numbers and 2000 mesh numbers, to titanium
Titanium base is rinsed in surface similar to smooth as minute surface, then with distilled water, then clean 20min with distilled water ultrasonic wave, and acetone is ultrasonic
The greasy dirt that 20min removes matrix surface is cleaned, after distilled water rinses Titanium base, is corroded with 20wt% hydrochloric acid solution at 80 DEG C
1h makes Titanium base surface form frosting, is cleaned by ultrasonic 15min with distilled water, obtains pretreated Titanium base, be stored in second
In alcohol.
Ti/SnO2-Sb2O3Preparation, under conditions of 130 DEG C, into ethylene glycol add citric acid reactions obtain ethylene glycol
Citrate polymeric precursor solvent, it is 8 that mass ratio is added into citrate polymeric precursor solvent：1 SnCl4·4H2O
And SbCl3·3H2O stirs and evenly mixs to obtain intermediate layer presoma, by the titanium-based of intermediate layer presoma even application after the pre-treatment
On body, and 8min is kept in 150 DEG C of baking oven, after keeping 8min, taking-up to be cooled to normal temperature in 450 DEG C of Muffle furnace,
The even application intermediate layer presoma on titanium sheet matrix again, equally keeps 8min in 150 DEG C of baking oven, then at 450 DEG C of horse
8min is not kept in stove, is so repeated 5 times, after keeping 1.5h in 500 DEG C of Muffle furnace for the last time, obtains having SnO2-
Sb2O3The Titanium base in intermediate layer.
Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA preparation, configures electroplate liquid, and the main component of the electroplate liquid is
0.5mol/LPb(NO3)2、0.15mol/LHNO3、0.05mol/LKF2·H2O, 50g/LCNTs/PDDA, by Ti/SnO2-Sb2O3
It is placed in 60 DEG C of electroplate liquid, sets pulse mode as cathode pulse -30mA, time 2ms, anodic pulse+30mA, time 8ms,
1s, 0mA are spaced, temperature is 70 DEG C, using three-electrode system, Ti/SnO2-Sb2O3It is to electrode, Ag/ for working electrode, platinized platinum
AgCl is that reference electrode implements pulse electrodeposition 15min, obtains Ti/SnO2-Sb2O3/PbO2-CNTs-PDDA。
Embodiment two：The method that high purity copper and nickel nitrate are prepared with electroplating sludge
The method that high purity copper and nickel nitrate are prepared with electroplating sludge of the present embodiment, comprises the following steps：
Dissolving is leached, and electroplating sludge is mixed with the sulfuric acid solution that mass concentration is 28%, 0.5h is stirred, is passed through air exposure
Gas aoxidizes 3h, is filtrated to get filter residue A1 and leachate, detects the pH=1.1 of leachate；
Iron removaling is complexed, after the pH=2.5 that leachate is adjusted with the sodium carbonate liquor that mass concentration is 14%, adds hydrogen peroxide
Oxidation reaction 1.5h, then pH=3.5 is adjusted with the sodium carbonate liquor that mass concentration is 14%, it is filtrated to get filter residue B1 and iron removaling is molten
Liquid；
Resin adsorption, except ferrous solution is heated to 35 DEG C, by except ferrous solution is with 1BV/h flow velocity, it is passed through strong-acid cation friendship
Change in resin column and carry out copper ion, nickel ion absorption, what is filled in strong-acid cation-exchange resin post is NDA-36 resins, absorption
Liquids recovery afterwards leaches process for dissolving, after resin adsorption saturation, with 3mol/L sulfuric acid solution with 2BV/h flow velocity pair
Resin column carries out backwash desorption, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, and the moon is used as using pure copper starting sheet
Pole, in 55 DEG C of temperature, 2.0~2.5V of tank voltage, current density 230A/m2Under conditions of, stripping liquid is acted in DC current
Lower progress electrodeposition reaction, obtains fine copper and low copper solution；
Abstraction impurity removal, P204 extractants are added into low copper solution and sodium carbonate liquor carries out one-level saponifiable extraction processing,
It is 75% to control saponification rate, and nickeliferous raffinate A1 and organic phase A1 is obtained by extraction, and adding sulfuric acid solution in organic phase A1 is carried out instead
Extraction, obtains strip liquor B1 and organic phase B1, contains copper ion in strip liquor B1, will be reclaimed after strip liquor B1 oil removings for electrodeposition
Heavy copper step, organic phase B1 are reclaimed for one-level continuous saponification process, counter-current extraction step；P204 extractions are continuously added in raffinate A1
Agent and sodium carbonate liquor carry out two level saponifiable extraction processing, controls saponification rate as 75%, and raffinate C1 is obtained by extraction and nickeliferous has
Machine phase C1, the salpeter solution that 3mol/L is added in organic phase C 1 are stripped, obtain nickeliferous strip liquor D1 and organic phase D 1, have
Machine phase D1 is reclaimed for two level saponifiable extraction step；
Ultrasonic oil removing, segmentation oil removing is carried out to strip liquor D1, first remove suspension of the particle diameter more than 60 μm through sloping plate oil separation tank
Elaioleucite, then scattered elaioleucite of the particle diameter less than 60 μm is removed through one-level air supporting, with after 15 DEG C of temperature, frequency 25kHz, power 350W
Under the conditions of carry out supersonic gas vibrating oil removing, then carry out secondary air-floatation remove solution in oil emulsion, finally with fibrous nodules or fiber
Silk removes remaining oil emulsion in solution and is partly dissolved oil, accurate press filtration remove the fibrous nodules brought into solution, filament and
Solid suspension, obtain nickel nitrate solution；
It is concentrated and dried, nickel nitrate solution is evaporated concentration, when the density for being evaporated to nickel nitrate solution is 1.62g/L,
And concentrate pH=2.0 is adjusted, 20 DEG C of crystallizations are cooled to, drying is filtered, obtains nickel nitrate crystal.
Embodiment three：The method that high purity copper and nickel nitrate are prepared with electroplating sludge
The method that high purity copper and nickel nitrate are prepared with electroplating sludge of the present embodiment, comprises the following steps：
Dissolving is leached, and electroplating sludge is mixed with the sulfuric acid solution that mass concentration is 28%, 0.5h is stirred, is passed through air exposure
Gas aoxidizes 4h, is filtrated to get filter residue A2 and leachate, detects the pH=1.1 of leachate；
Iron removaling is complexed, after the pH=2.5 that leachate is adjusted with the sodium carbonate liquor that mass concentration is 14%, adds hydrogen peroxide
Oxidation reaction 1.5h, then pH=3.5 is adjusted with the sodium carbonate liquor that mass concentration is 14%, it is filtrated to get filter residue B2 and iron removaling is molten
Liquid；
Resin adsorption, except ferrous solution is heated to 40 DEG C, by except ferrous solution is with 3BV/h flow velocity, it is passed through strong-acid cation friendship
Change in resin column and carry out copper ion, nickel ion absorption, what is filled in strong-acid cation-exchange resin post is NDA-36 resins, absorption
Liquids recovery afterwards leaches process for dissolving, after resin adsorption saturation, with 3mol/L sulfuric acid solution with 3BV/h flow velocity pair
Resin column carries out backwash desorption, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, and the moon is used as using pure copper starting sheet
Pole, in temperature 60 C, 2.0~2.5V of tank voltage, current density 230A/m2Under conditions of, stripping liquid is acted in DC current
Lower progress electrodeposition reaction, obtains fine copper and low copper solution；
Abstraction impurity removal, P204 extractants are added into low copper solution and sodium carbonate liquor carries out one-level saponifiable extraction processing,
It is 75% to control saponification rate, and nickeliferous raffinate A2 and organic phase A2 is obtained by extraction, and adding sulfuric acid solution in organic phase A2 is carried out instead
Extraction, obtains strip liquor B2 and organic phase B2, contains copper ion in strip liquor B2, will be reclaimed after strip liquor B2 oil removings for electrodeposition
Heavy copper step, organic phase B2 are reclaimed for one-level continuous saponification process, counter-current extraction step；P204 extractions are continuously added in raffinate A2
Agent and sodium carbonate liquor carry out two level saponifiable extraction processing, controls saponification rate as 75%, and raffinate C2 is obtained by extraction and nickeliferous has
Machine phase C2, the salpeter solution that 3mol/L is added in organic phase C 2 are stripped, obtain nickeliferous strip liquor D2 and organic phase D 2, have
Machine phase D2 is reclaimed for two level saponifiable extraction step；
Ultrasonic oil removing, segmentation oil removing is carried out to strip liquor D2, first remove suspension of the particle diameter more than 60 μm through sloping plate oil separation tank
Elaioleucite, then scattered elaioleucite of the particle diameter less than 60 μm is removed through one-level air supporting, with after 20 DEG C of temperature, frequency 28kHz, power 350W
Under the conditions of carry out supersonic gas vibrating oil removing, then carry out secondary air-floatation remove solution in oil emulsion, finally with fibrous nodules or fiber
Silk removes remaining oil emulsion in solution and is partly dissolved oil, accurate press filtration remove the fibrous nodules brought into solution, filament and
Solid suspension, obtain nickel nitrate solution；
It is concentrated and dried, nickel nitrate solution is evaporated concentration, when the density for being evaporated to nickel nitrate solution is 1.62g/L,
And concentrate pH=2.0 is adjusted, 20 DEG C of crystallizations are cooled to, drying is filtered, obtains nickel nitrate crystal.
Example IV：The method that high purity copper and nickel nitrate are prepared with electroplating sludge
The method that high purity copper and nickel nitrate are prepared with electroplating sludge of the present embodiment, comprises the following steps：
Dissolving is leached, and electroplating sludge is mixed with the sulfuric acid solution that mass concentration is 28%, 0.5h is stirred, is passed through air exposure
Gas aoxidizes 4h, is filtrated to get filter residue A3 and leachate, detects the pH=1.1 of leachate；
Iron removaling is complexed, after the pH=2.6 that leachate is adjusted with the sodium carbonate liquor that mass concentration is 14%, adds hydrogen peroxide
Oxidation reaction 1.5h, then pH=3.6 is adjusted with the sodium carbonate liquor that mass concentration is 14%, it is filtrated to get filter residue B3 and iron removaling is molten
Liquid；
Resin adsorption, except ferrous solution is heated to 40 DEG C, by except ferrous solution is with 4BV/h flow velocity, it is passed through strong-acid cation friendship
Change in resin column and carry out copper ion, nickel ion absorption, what is filled in strong-acid cation-exchange resin post is NDA-36 resins, absorption
Liquids recovery afterwards leaches process for dissolving, after resin adsorption saturation, with 3mol/L sulfuric acid solution with 4BV/h flow velocity pair
Resin column carries out backwash desorption, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, and the moon is used as using pure copper starting sheet
Pole, in temperature 60 C, 2.0~2.5V of tank voltage, current density 230A/m2Under conditions of, stripping liquid is acted in DC current
Lower progress electrodeposition reaction, obtains fine copper and low copper solution；
Abstraction impurity removal, P204 extractants are added into low copper solution and sodium carbonate liquor carries out one-level saponifiable extraction processing,
It is 75% to control saponification rate, and nickeliferous raffinate A3 and organic phase A3 is obtained by extraction, and adding sulfuric acid solution in organic phase A3 is carried out instead
Extraction, obtains strip liquor B3 and organic phase B3, contains copper ion in strip liquor B3, will be reclaimed after strip liquor B3 oil removings for electrodeposition
Heavy copper step, organic phase B3 are reclaimed for one-level continuous saponification process, counter-current extraction step；P204 extractions are continuously added in raffinate A3
Agent and sodium carbonate liquor carry out two level saponifiable extraction processing, controls saponification rate as 75%, and raffinate C3 is obtained by extraction and nickeliferous has
Machine phase C3, the salpeter solution that 3mol/L is added in organic phase C 3 are stripped, obtain nickeliferous strip liquor D3 and organic phase D 3, have
Machine phase D3 is reclaimed for two level saponifiable extraction step；
Ultrasonic oil removing, segmentation oil removing is carried out to strip liquor D3, first remove suspension of the particle diameter more than 60 μm through sloping plate oil separation tank
Elaioleucite, then scattered elaioleucite of the particle diameter less than 60 μm is removed through one-level air supporting, with after 25 DEG C of temperature, frequency 30kHz, power 350W
Under the conditions of carry out supersonic gas vibrating oil removing, then carry out secondary air-floatation remove solution in oil emulsion, finally with fibrous nodules or fiber
Silk removes remaining oil emulsion in solution and is partly dissolved oil, accurate press filtration remove the fibrous nodules brought into solution, filament and
Solid suspension, obtain nickel nitrate solution；
It is concentrated and dried, nickel nitrate solution is evaporated concentration, when the density for being evaporated to nickel nitrate solution is 1.62g/L,
And concentrate pH=2.0 is adjusted, 20 DEG C of crystallizations are cooled to, drying is filtered, obtains nickel nitrate crystal.
Embodiment five：The method that high purity copper and nickel nitrate are prepared with electroplating sludge
The method that high purity copper and nickel nitrate are prepared with electroplating sludge of the present embodiment, comprises the following steps：
Dissolving is leached, and electroplating sludge is mixed with the sulfuric acid solution that mass concentration is 28%, 0.5h is stirred, is passed through air exposure
Gas aoxidizes 5h, is filtrated to get filter residue A4 and leachate, detects the pH=1.1 of leachate；
Iron removaling is complexed, after the pH=3.0 that leachate is adjusted with the sodium carbonate liquor that mass concentration is 14%, adds hydrogen peroxide
Oxidation reaction 1.5h, then pH=3.8 is adjusted with the sodium carbonate liquor that mass concentration is 14%, it is filtrated to get filter residue B4 and iron removaling is molten
Liquid；
Resin adsorption, except ferrous solution is heated to 45 DEG C, by except ferrous solution is with 4BV/h flow velocity, it is passed through strong-acid cation friendship
Change in resin column and carry out copper ion, nickel ion absorption, what is filled in strong-acid cation-exchange resin post is NDA-36 resins, absorption
Liquids recovery afterwards leaches process for dissolving, after resin adsorption saturation, with 3mol/L sulfuric acid solution with 4BV/h flow velocity pair
Resin column carries out backwash desorption, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, and the moon is used as using pure copper starting sheet
Pole, in 65 DEG C of temperature, 2.0~2.5V of tank voltage, current density 230A/m2Under conditions of, stripping liquid is acted in DC current
Lower progress electrodeposition reaction, obtains fine copper and low copper solution；
Abstraction impurity removal, P204 extractants are added into low copper solution and sodium carbonate liquor carries out one-level saponifiable extraction processing,
It is 75% to control saponification rate, and nickeliferous raffinate A4 and organic phase A4 is obtained by extraction, and adding sulfuric acid solution in organic phase A4 is carried out instead
Extraction, obtains strip liquor B4 and organic phase B4, contains copper ion in strip liquor B4, will be reclaimed after strip liquor B4 oil removings for electrodeposition
Heavy copper step, organic phase B4 are reclaimed for one-level continuous saponification process, counter-current extraction step；P204 extractions are continuously added in raffinate A4
Agent and sodium carbonate liquor carry out two level saponifiable extraction processing, controls saponification rate as 75%, and raffinate C4 is obtained by extraction and nickeliferous has
Machine phase C4, the salpeter solution that 3mol/L is added in organic phase C 4 are stripped, obtain nickeliferous strip liquor D4 and organic phase D 4, have
Machine phase D4 is reclaimed for two level saponifiable extraction step；
Ultrasonic oil removing, segmentation oil removing is carried out to strip liquor D4, first remove suspension of the particle diameter more than 60 μm through sloping plate oil separation tank
Elaioleucite, then scattered elaioleucite of the particle diameter less than 60 μm is removed through one-level air supporting, with after 25 DEG C of temperature, frequency 30kHz, power 350W
Under the conditions of carry out supersonic gas vibrating oil removing, then carry out secondary air-floatation remove solution in oil emulsion, finally with fibrous nodules or fiber
Silk removes remaining oil emulsion in solution and is partly dissolved oil, accurate press filtration remove the fibrous nodules brought into solution, filament and
Solid suspension, obtain nickel nitrate solution；
It is concentrated and dried, nickel nitrate solution is evaporated concentration, when the density for being evaporated to nickel nitrate solution is 1.62g/L,
And concentrate pH=2.0 is adjusted, 20 DEG C of crystallizations are cooled to, drying is filtered, obtains nickel nitrate crystal.
After testing, the purity for the copper that the electrodeposition of embodiment two to five obtains is more than 99.99%.
The above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferred embodiment to this hair
It is bright to be described in detail, it will be understood by those within the art that, technical scheme can be modified
Or equivalent substitution, without departing from the objective and scope of technical solution of the present invention, it all should cover the claim in the present invention
Among scope.The present invention be not described in detail technology, shape, construction part be known technology.
Claims (9)
1. the method for high purity copper and nickel nitrate is prepared with electroplating sludge, it is characterised in that comprise the following steps：
Dissolving is leached, and electroplating sludge is mixed with acid solution, 3~5h of aerating oxidation, is filtrated to get filter residue A and leachate；
Iron removaling is complexed, behind pH=2.5~3.0 for adjusting leachate, adds oxidizing reaction 1.5h, then adjust pH=3.5
~3.8, it is filtrated to get filter residue B and except ferrous solution；
Resin adsorption, 35~45 DEG C will be heated to except ferrous solution, be passed through strong-acid cation-exchange resin post carry out copper ion, nickel from
Son adsorbs, and after resin adsorption saturation, carries out backwash desorption to resin column with 3mol/L sulfuric acid solution, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, using pure copper starting sheet as negative electrode, will solve
Imbibition carries out electrodeposition reaction under DC current effect, obtains fine copper and low copper solution；
Abstraction impurity removal, P204 extractants are added into low copper solution and sodium carbonate liquor carries out one-level saponifiable extraction, are obtained nickeliferous
P204 extractants are continuously added in raffinate A and organic phase A, raffinate A and sodium carbonate liquor carries out two level saponifiable extraction processing,
Raffinate C and nickeliferous organic phase C are obtained, the salpeter solution that 3mol/L is added in organic phase C is stripped, and obtains nickeliferous back extraction
Liquid D and organic phase D；
Ultrasonic oil removing, segmentation oil removing is carried out to strip liquor D, after supersonic gas vibrating and secondary air-floatation oil removing, then with fibrous nodules or
Filament adsorbs oil removing, and press filtration obtains nickel nitrate solution；
It is concentrated and dried, nickel nitrate solution is evaporated concentration, and adjust concentrate pH=2.0, decrease temperature crystalline, filters drying,
Obtain nickel nitrate crystal.
2. the method according to claim 1 that high purity copper and nickel nitrate are prepared with electroplating sludge, it is characterised in that described strong
Weak acid cation exchange resin is NDA-36 resins.
3. the method according to claim 2 that high purity copper and nickel nitrate are prepared with electroplating sludge, it is characterised in that the tree
In fat adsorption step copper ion, nickel ion are carried out except ferrous solution is passed through strong-acid cation-exchange resin post with 1~4BV/h flow velocity
Absorption, sulfuric acid solution carry out backwash desorption with 2~4BV/h flow velocity to resin column.
4. the method according to claim 3 that high purity copper and nickel nitrate are prepared with electroplating sludge, it is characterised in that described
Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is in Ti/SnO using pulse electrodeposition method2-Sb2O3Upper deposition β-PbO2And CNTs/
PDDA is made.
5. the method according to claim 4 that high purity copper and nickel nitrate are prepared with electroplating sludge, it is characterised in that the carbon
Nanotube is the CNT with sharp end nose cone shape prepared using hydrogen arc process.
6. the method according to claim 5 that high purity copper and nickel nitrate are prepared with electroplating sludge, it is characterised in that described
Ti/SnO2-Sb2O3/PbO2In-CNTs-PDDA preparation, by Ti/SnO2-Sb2O3It is placed in electroplate liquid, using three electrode bodies
System, Ti/SnO2-Sb2O3It is that reference electrode implements pulse electrodeposition 15min to electrode, Ag/AgCl to be for working electrode, platinized platinum,
Obtain Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA combination electrodes.
7. the method according to claim 6 that high purity copper and nickel nitrate are prepared with electroplating sludge, it is characterised in that the electricity
The key component of plating solution is 0.5mol/LPb (NO3)2、0.15mol/LHNO3、0.05mol/LKF2·H2O、50g/LCNTs/
PDDA。
8. the method according to claim 7 that high purity copper and nickel nitrate are prepared with electroplating sludge, it is characterised in that the electricity
The parameter of deposition copper step is 55~65 DEG C, 2.0~2.5V of tank voltage, current density 230A/m of temperature2。
9. the method according to claim 8 that high purity copper and nickel nitrate are prepared with electroplating sludge, it is characterised in that described super
The parameter of sound oil removing is 15~25 DEG C, 25~30kHz of frequency, power 350W of temperature.
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| CN109628953A (en) * | 2018-12-26 | 2019-04-16 | 浙江工业大学 | The method of arsenic removal antimony bismuth is gone in a kind of copper electrolyte |
| CN114988499A (en) * | 2022-05-30 | 2022-09-02 | 金川镍钴研究设计院有限责任公司 | Method for treating copper-nickel alloy under high-acid condition |
| CN117222765A (en) * | 2023-07-31 | 2023-12-12 | 青美邦新能源材料有限公司 | Method for extracting nickel and cobalt from laterite-nickel ore in green and low cost manner |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336194A (en) * | 2018-12-13 | 2019-02-15 | 怀化恒安石化有限公司 | A kind of process of the waste nitric acid nickel solution through removing chloride production nickel nitrate product |
| CN109628953A (en) * | 2018-12-26 | 2019-04-16 | 浙江工业大学 | The method of arsenic removal antimony bismuth is gone in a kind of copper electrolyte |
| CN109628953B (en) * | 2018-12-26 | 2020-10-23 | 浙江工业大学 | Method for removing arsenic, antimony and bismuth in copper electrolyte |
| CN114988499A (en) * | 2022-05-30 | 2022-09-02 | 金川镍钴研究设计院有限责任公司 | Method for treating copper-nickel alloy under high-acid condition |
| CN117222765A (en) * | 2023-07-31 | 2023-12-12 | 青美邦新能源材料有限公司 | Method for extracting nickel and cobalt from laterite-nickel ore in green and low cost manner |
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