CN107746953B - The method for preparing high purity copper and nickel nitrate with electroplating sludge - Google Patents
The method for preparing high purity copper and nickel nitrate with electroplating sludge Download PDFInfo
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- CN107746953B CN107746953B CN201710899456.XA CN201710899456A CN107746953B CN 107746953 B CN107746953 B CN 107746953B CN 201710899456 A CN201710899456 A CN 201710899456A CN 107746953 B CN107746953 B CN 107746953B
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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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
- 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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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- 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 present invention relates to scrap metals to handle recovery technology field, more particularly to the method for preparing high purity copper and nickel nitrate with electroplating sludge, including dissolution is leached, and electroplating sludge and acid solution mixed aeration aoxidize, and obtain leachate；Complexing removes iron, and oxidizing reaction is added, and obtains except 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/PbO2- CNTs-PDDA is used as anode, and stripping liquid is carried out electrodeposition reaction, obtains fine copper and low copper solution；Abstraction impurity removal obtains nickeliferous strip liquor D and organic phase D；Ultrasonic oil removing carries out segmentation oil removing, through supersonic gas vibrating and secondary air-floatation oil removing to strip liquor D, obtains nickel nitrate solution；It is concentrated and dried, nickel nitrate solution is concentrated by evaporation, cooling and drying, obtains nickel nitrate crystal.Method and process of the invention is simple, and energy consumption is lower, is capable of the metallic copper of regenerating high purity.
Description
Technical field
The present invention relates to scrap metals to handle recovery technology field, more particularly to prepares high purity copper and nitric acid with electroplating sludge
The method of nickel.
Background technique
With the development of economy with the continuous improvement of industrialized level, plating industry is grown rapidly, but is electroplated and is produced
Industry easily causes the heavy metal pollution in place in development process, and pollution is concentrated mainly on sewage treatment plant, raw material stockyard
Near, if can bring biggish ecological threat to ambient enviroment without direct landfill of being prudent in dealing with, how to be repaired to it
Have become the hot spot of research with improvement.
Electroplating sludge is product of the electroplating wastewater after acid-base neutralization, flocculation sedimentation, and moisture, content of ashes are very high, is belonged to
In meta-alkalescence substance.Cr in electroplating wastewater, Fe, Ni, Cu, Zn, Pb, the elements such as 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 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 the sludge of generation is basic
On be the ingredient containing various metals mixing sludge, some of them tenor is even higher than common metal mine.According to statistics, China's electricity
Plating enterprise generates about 10,000,000 t electroplating sludges every year, wherein there is a large amount of valuable metal that can recycle.It is big in native metal resource
Under the status for measuring consumption, by valuable metal in electroplated mud resource utilization, it is not only the fundamental requirement of protection environment, and can
The important means of sustainable development and circular economy.Electroplating technology mainly includes that the plating of the monometallics such as copper facing, nickel plating and binary are closed
Gold, multicomponent alloy plating, therefore metallic element type and content is different in the obtained electroplating sludge of different electroplating technology.By right
The field research of electroplating wastewater treatment technique and to the analysis of separate sources electroplating sludge physicochemical property it is found that electroplating sludge group
Divide mainly comprising heavy metal compounds and solubility salts such as copper, nickel, pH value is meta-alkalescence substance, moisture between 7.5~8.0
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 lower problem of purity.
Summary of the invention
In view of this, the object of the present invention is to provide the method for preparing high purity copper and nickel nitrate with electroplating sludge, this method
Simple process, energy consumption is lower, being capable of regenerating high purity metallic copper.
The present invention solves above-mentioned technical problem by following technological means:
The method for preparing high purity copper and nickel nitrate with electroplating sludge, comprising the following steps:
Dissolution is leached, and electroplating sludge is mixed with acid solution, filter residue A and leachate is obtained by filtration in 3~5h of aerating oxidation；
Except iron behind pH=2.5~3.0 for adjusting leachate, oxidizing reaction 1.5h is added, then adjust pH=in complexing
3.5~3.8, filter residue B is obtained by filtration and except ferrous solution；
Resin adsorption will be heated to 35~45 DEG C except ferrous solution, be passed through strong-acid cation-exchange resin column carry out copper ion,
Nickel ion absorption carries out backwash desorption to resin column with the sulfuric acid solution of 3mol/L, obtains stripping liquid after resin adsorption is saturated；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, using pure copper starting sheet as yin
Stripping liquid is carried out electrodeposition reaction under DC current effect, obtains fine copper and low copper solution by pole；
Abstraction impurity removal, P204 extractant is added into low copper solution and sodium carbonate liquor carries out level-one saponifiable extraction, obtains
P204 extractant is continuously added in nickeliferous raffinate A and organic phase A, raffinate A and sodium carbonate liquor carries out second level saponifiable extraction
Processing, obtains raffinate C and nickeliferous organic phase C, and the nitric acid solution that 3mol/L is added in organic phase C is stripped, is contained
Nickel strip liquor D and organic phase D；
Ultrasonic oil removing carries out segmentation oil removing, after supersonic gas vibrating and secondary air-floatation oil removing to strip liquor D, then uses fiber
Ball or fiber filament adsorb oil removing, and filters pressing 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 dry
It is dry, obtain nickel nitrate crystal.
Further, the strong-acid cation-exchange resin is NDA-36 resin.
Further, strong-acid cation exchange tree is passed through with the flow velocity of 1~4BV/h except ferrous solution in the resin adsorption step
Rouge column carries out copper ion, nickel ion absorption, and the liquids recovery after absorption leaches process for dissolving, 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 using pulse electrodeposition method in Ti/SnO2-
Sb2O3Upper deposition β-PbO2It is made with CNTs/PDDA.
Carbon nanotube is to stack the object with tubular structure formed two-by-two in the form of hexatomic ring by a large amount of carbon atom
Matter has the excellent performances such as biggish 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 carbon nanotube and positively charged PDDA are incorporated in one by electrostatic attraction
It rises, and is entrained in PbO2In layer, so that electrode surface is generated more free OH, can be improved O2Deposition potential, enhancing electricity
The electrocatalysis characteristic of pole improves electrolytic efficiency, reduces power consumption to a certain extent.
Further, the carbon nanotube is the carbon nanotube with sharp end nose cone shape using the preparation of hydrogen arc process.
Further, the Ti/SnO2-Sb2O3/PbO2In the preparation of-CNTs-PDDA, by Ti/SnO2-Sb2O3It is placed in plating
In liquid, using three-electrode system, Ti/SnO2-Sb2O3For working electrode, platinized platinum, to be to electrode, Ag/AgCl be that reference electrode is implemented
Pulse electrodeposition 15min, obtains Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA combination electrode.
Further, the main component of the electroplate liquid is 0.5mol/LPb (NO3)2、0.15mol/LHNO3、0.05mol/
LKF2·H2O、50g/LCNTs/PDDA。
Further, the parameter of the heavy copper step of the electrodeposition is 55~65 DEG C of temperature, 2.0~2.5V of tank voltage, current density
230A/m2。
Further, the parameter of the ultrasonic oil removing is 15~25 DEG C of temperature, 25~30kHz of frequency, power 350W.
Beneficial effects of the present invention: the present invention neutralizes electroplating sludge and acid solution, and metal is carried out dissolution leaching
The leachate of metal ion is obtained out, and converting metal ion for metal as much as possible, there are in leachate；The present invention is to leaching
Liquid removes iron ion by the way of oxidation complexation out, simple process, and de-ferrous effect is preferable；The present invention is to except ferrous solution is using tree
Rouge adsorption treatment extracts except the cupro-nickel ion in ferrous solution, other ion isolations is gone out；It is 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 surface can give birth to
At more free OH, O can be improved2Deposition potential enhances the catalytic performance of electrode.Method and process of the invention is simple,
Energy consumption is lower, can regenerate the higher metallic copper of purity and nickel nitrate.
Detailed description of the invention
Fig. 1 is the flow diagram for the method that the present invention prepares high purity copper and nickel nitrate with electroplating sludge.
Specific 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 for the invention for preparing high purity copper and nickel nitrate with electroplating sludge, comprising the following steps:
Dissolution is leached, and electroplating sludge is mixed with acid solution, filter residue A and leachate is obtained by filtration in 3~5h of aerating oxidation；
Except iron behind pH=2.5~3.0 for adjusting leachate, oxidizing reaction 1.5h is added, then adjust pH=in complexing
3.5~3.8, filter residue B is obtained by filtration and except ferrous solution；
Resin adsorption will be heated to 35~45 DEG C except ferrous solution, be passed through strong-acid cation-exchange resin column carry out copper ion,
Nickel ion absorption carries out backwash desorption to resin column with the sulfuric acid solution of 3mol/L, obtains stripping liquid after resin adsorption is saturated；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, using pure copper starting sheet as yin
Stripping liquid is carried out electrodeposition reaction under DC current effect, obtains fine copper and low copper solution by pole；
Abstraction impurity removal, P204 extractant is added into low copper solution and sodium carbonate liquor carries out level-one saponifiable extraction, obtains
P204 extractant is continuously added in nickeliferous raffinate A and organic phase A, raffinate A and sodium carbonate liquor carries out second level saponifiable extraction
Processing, obtains raffinate C and nickeliferous organic phase C, and the nitric acid solution that 3mol/L is added in organic phase C is stripped, is contained
Nickel strip liquor D and organic phase D；
Ultrasonic oil removing carries out segmentation oil removing, after supersonic gas vibrating and secondary air-floatation oil removing to strip liquor D, then uses fiber
Ball or fiber filament adsorb oil removing, and filters pressing 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 dry
It is dry, obtain nickel nitrate crystal.
Ti/SnO is used in the heavy copper step of electrodeposition of the invention2-Sb2O3/PbO2- CNTs-PDDA carries out copper as anode and sinks
Product, the Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is by Ti/SnO2-Sb2O3It is placed in electroplate liquid, using three-electrode system,
Ti/SnO2-Sb2O3For working electrode, platinized platinum, to be to electrode, Ag/AgCl be that reference electrode implements pulse electrodeposition 15min obtains
, it is prepared as follows:
Embodiment one: Ti/SnO2-Sb2O3/PbO2The preparation of-CNTs-PDDA
The preparation of CNTs/PDDA is had the carbon nanotube of sharp end nose cone shape using the preparation of 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, which is placed in acid
Property mixed solution in be heated to reflux 10h, the carbon nanotube of acidification is added the carbon nanotube that centrifuge washing is acidified to neutrality
It is stirred in hydrogen peroxide, while being to slowly warm up to 100 DEG C, centrifuge washing to neutrality is dried to obtain pretreated carbon nanotube, takes poly-
The third alkyl dimethyl ammonium chloride of dialkylene, which is added in sodium-chloride water solution, to be stirred and evenly mixed, and the PDDA that PDDA mass concentration is 40% is made
Aqueous solution, the addition pretreated carbon nanotube of 5g in every 100mLPDDA aqueous solution, stirring 20h, filtration washing, dry
To CNTs/PDDA.
Titanium base pretreatment, takes the titanium plate of 0.5mm successively to be polished with the sand paper of 1000 mesh numbers and 2000 mesh numbers, until titanium
Titanium base is then rinsed with distilled water similar to smooth as mirror surface in surface, then uses distilled water ultrasonic cleaning 20min, and acetone is ultrasonic
The greasy dirt for cleaning 20min removal matrix surface is corroded at 80 DEG C after distilled water rinses Titanium base with the hydrochloric acid solution of 20wt%
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 be added citric acid reactions obtain ethylene glycol
The SnCl that mass ratio is 8:1 is added into citrate polymeric precursor solvent for citrate polymeric precursor solvent4·4H2O
And SbCl3·3H2O stirs and evenly mixs to obtain middle layer presoma, by the titanium-based of middle 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 room temperature in 450 DEG C of Muffle furnace,
The even application middle 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 furnace, is so repeated 5 times, and after keeping 1.5h in 500 DEG C of Muffle furnace for the last time, is obtained with SnO2-
Sb2O3The Titanium base of middle layer.
Ti/SnO2-Sb2O3/PbO2The preparation of-CNTs-PDDA, 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,
It is spaced 1s, 0mA, 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 for preparing high purity copper and nickel nitrate with electroplating sludge
The method for preparing high purity copper and nickel nitrate with electroplating sludge of the present embodiment, comprising the following steps:
Dissolution is leached, and electroplating sludge is mixed with the sulfuric acid solution that mass concentration is 28%, stirs 0.5h, is passed through air exposure
Gas aoxidizes 3h, and filter residue A1 and leachate is obtained by filtration, detects the pH=1.1 of leachate；
Complexing removes iron, and after the pH=2.5 that leachate is adjusted with the sodium carbonate liquor that mass concentration is 14%, hydrogen peroxide is added
Oxidation reaction 1.5h, then the sodium carbonate liquor for being 14% with mass concentration adjust pH=3.5, filter residue B1 are obtained by filtration and except iron is molten
Liquid；
Resin adsorption, by except ferrous solution is with the flow velocity of 1BV/h, is passed through strong-acid cation friendship except ferrous solution is heated to 35 DEG C
It changes in resin column and carries out copper ion, nickel ion absorption, what is filled in strong-acid cation-exchange resin column is NDA-36 resin, absorption
Liquids recovery afterwards leaches process for dissolving, after resin adsorption saturation, with the sulfuric acid solution of 3mol/L with the flow velocity pair of 2BV/h
Resin column carries out backwash desorption, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, using pure copper starting sheet as yin
Pole, 55 DEG C of Yu Wendu, 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 extractant is added into low copper solution and sodium carbonate liquor carries out the processing of level-one saponifiable extraction,
Controlling saponification rate is 75%, and nickeliferous raffinate A1 and organic phase A1 is obtained by extraction, sulfuric acid solution is added in organic phase A1 and carries out instead
Extraction, obtains strip liquor B1 and organic phase B1, contains copper ion in strip liquor B1, and recycling after strip liquor B1 oil removing is used for electrodeposition
Heavy copper step, organic phase B1 recycling are used for level-one continuous saponification process, counter-current extraction step；P204 extraction is continuously added in raffinate A1
Agent and sodium carbonate liquor carry out the processing of second level saponifiable extraction, and control saponification rate is 75%, and raffinate C1 is obtained by extraction and nickeliferous has
Machine phase C1, the nitric acid 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 recycling is used for second level saponifiable extraction step；
Ultrasonic oil removing carries out segmentation oil removing to strip liquor D1, first removes the suspension that partial size is greater than 60 μm through sloping plate oil separation tank
Elaioleucite, then dispersion elaioleucite of the partial size less than 60 μm is removed through level-one air bearing, then in 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 use fibrous nodules or fiber
Silk removes remaining oil emulsion in solution and is partly dissolved oil, accurate filters pressing remove the fibrous nodules brought into solution, fiber filament and
Solid suspension obtains 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 for preparing high purity copper and nickel nitrate with electroplating sludge
The method for preparing high purity copper and nickel nitrate with electroplating sludge of the present embodiment, comprising the following steps:
Dissolution is leached, and electroplating sludge is mixed with the sulfuric acid solution that mass concentration is 28%, stirs 0.5h, is passed through air exposure
Gas aoxidizes 4h, and filter residue A2 and leachate is obtained by filtration, detects the pH=1.1 of leachate；
Complexing removes iron, and after the pH=2.5 that leachate is adjusted with the sodium carbonate liquor that mass concentration is 14%, hydrogen peroxide is added
Oxidation reaction 1.5h, then the sodium carbonate liquor for being 14% with mass concentration adjust pH=3.5, filter residue B2 are obtained by filtration and except iron is molten
Liquid；
Resin adsorption, by except ferrous solution is with the flow velocity of 3BV/h, is passed through strong-acid cation friendship except ferrous solution is heated to 40 DEG C
It changes in resin column and carries out copper ion, nickel ion absorption, what is filled in strong-acid cation-exchange resin column is NDA-36 resin, absorption
Liquids recovery afterwards leaches process for dissolving, after resin adsorption saturation, with the sulfuric acid solution of 3mol/L with the flow velocity pair of 3BV/h
Resin column carries out backwash desorption, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, using pure copper starting sheet as yin
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 extractant is added into low copper solution and sodium carbonate liquor carries out the processing of level-one saponifiable extraction,
Controlling saponification rate is 75%, and nickeliferous raffinate A2 and organic phase A2 is obtained by extraction, sulfuric acid solution is added in organic phase A2 and carries out instead
Extraction, obtains strip liquor B2 and organic phase B2, contains copper ion in strip liquor B2, and recycling after strip liquor B2 oil removing is used for electrodeposition
Heavy copper step, organic phase B2 recycling are used for level-one continuous saponification process, counter-current extraction step；P204 extraction is continuously added in raffinate A2
Agent and sodium carbonate liquor carry out the processing of second level saponifiable extraction, and control saponification rate is 75%, and raffinate C2 is obtained by extraction and nickeliferous has
Machine phase C2, the nitric acid 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 recycling is used for second level saponifiable extraction step；
Ultrasonic oil removing carries out segmentation oil removing to strip liquor D2, first removes the suspension that partial size is greater than 60 μm through sloping plate oil separation tank
Elaioleucite, then dispersion elaioleucite of the partial size less than 60 μm is removed through level-one air bearing, then in 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 use fibrous nodules or fiber
Silk removes remaining oil emulsion in solution and is partly dissolved oil, accurate filters pressing remove the fibrous nodules brought into solution, fiber filament and
Solid suspension obtains 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 for preparing high purity copper and nickel nitrate with electroplating sludge
The method for preparing high purity copper and nickel nitrate with electroplating sludge of the present embodiment, comprising the following steps:
Dissolution is leached, and electroplating sludge is mixed with the sulfuric acid solution that mass concentration is 28%, stirs 0.5h, is passed through air exposure
Gas aoxidizes 4h, and filter residue A3 and leachate is obtained by filtration, detects the pH=1.1 of leachate；
Complexing removes iron, and after the pH=2.6 that leachate is adjusted with the sodium carbonate liquor that mass concentration is 14%, hydrogen peroxide is added
Oxidation reaction 1.5h, then the sodium carbonate liquor for being 14% with mass concentration adjust pH=3.6, filter residue B3 are obtained by filtration and except iron is molten
Liquid；
Resin adsorption, by except ferrous solution is with the flow velocity of 4BV/h, is passed through strong-acid cation friendship except ferrous solution is heated to 40 DEG C
It changes in resin column and carries out copper ion, nickel ion absorption, what is filled in strong-acid cation-exchange resin column is NDA-36 resin, absorption
Liquids recovery afterwards leaches process for dissolving, after resin adsorption saturation, with the sulfuric acid solution of 3mol/L with the flow velocity pair of 4BV/h
Resin column carries out backwash desorption, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, using pure copper starting sheet as yin
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 extractant is added into low copper solution and sodium carbonate liquor carries out the processing of level-one saponifiable extraction,
Controlling saponification rate is 75%, and nickeliferous raffinate A3 and organic phase A3 is obtained by extraction, sulfuric acid solution is added in organic phase A3 and carries out instead
Extraction, obtains strip liquor B3 and organic phase B3, contains copper ion in strip liquor B3, and recycling after strip liquor B3 oil removing is used for electrodeposition
Heavy copper step, organic phase B3 recycling are used for level-one continuous saponification process, counter-current extraction step；P204 extraction is continuously added in raffinate A3
Agent and sodium carbonate liquor carry out the processing of second level saponifiable extraction, and control saponification rate is 75%, and raffinate C3 is obtained by extraction and nickeliferous has
Machine phase C3, the nitric acid 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 recycling is used for second level saponifiable extraction step；
Ultrasonic oil removing carries out segmentation oil removing to strip liquor D3, first removes the suspension that partial size is greater than 60 μm through sloping plate oil separation tank
Elaioleucite, then dispersion elaioleucite of the partial size less than 60 μm is removed through level-one air bearing, then in 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 use fibrous nodules or fiber
Silk removes remaining oil emulsion in solution and is partly dissolved oil, accurate filters pressing remove the fibrous nodules brought into solution, fiber filament and
Solid suspension obtains 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 for preparing high purity copper and nickel nitrate with electroplating sludge
The method for preparing high purity copper and nickel nitrate with electroplating sludge of the present embodiment, comprising the following steps:
Dissolution is leached, and electroplating sludge is mixed with the sulfuric acid solution that mass concentration is 28%, stirs 0.5h, is passed through air exposure
Gas aoxidizes 5h, and filter residue A4 and leachate is obtained by filtration, detects the pH=1.1 of leachate；
Complexing removes iron, and after the pH=3.0 that leachate is adjusted with the sodium carbonate liquor that mass concentration is 14%, hydrogen peroxide is added
Oxidation reaction 1.5h, then the sodium carbonate liquor for being 14% with mass concentration adjust pH=3.8, filter residue B4 are obtained by filtration and except iron is molten
Liquid；
Resin adsorption, by except ferrous solution is with the flow velocity of 4BV/h, is passed through strong-acid cation friendship except ferrous solution is heated to 45 DEG C
It changes in resin column and carries out copper ion, nickel ion absorption, what is filled in strong-acid cation-exchange resin column is NDA-36 resin, absorption
Liquids recovery afterwards leaches process for dissolving, after resin adsorption saturation, with the sulfuric acid solution of 3mol/L with the flow velocity pair of 4BV/h
Resin column carries out backwash desorption, obtains stripping liquid；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is used as anode, using pure copper starting sheet as yin
Pole, 65 DEG C of Yu Wendu, 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 extractant is added into low copper solution and sodium carbonate liquor carries out the processing of level-one saponifiable extraction,
Controlling saponification rate is 75%, and nickeliferous raffinate A4 and organic phase A4 is obtained by extraction, sulfuric acid solution is added in organic phase A4 and carries out instead
Extraction, obtains strip liquor B4 and organic phase B4, contains copper ion in strip liquor B4, and recycling after strip liquor B4 oil removing is used for electrodeposition
Heavy copper step, organic phase B4 recycling are used for level-one continuous saponification process, counter-current extraction step；P204 extraction is continuously added in raffinate A4
Agent and sodium carbonate liquor carry out the processing of second level saponifiable extraction, and control saponification rate is 75%, and raffinate C4 is obtained by extraction and nickeliferous has
Machine phase C4, the nitric acid 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 recycling is used for second level saponifiable extraction step；
Ultrasonic oil removing carries out segmentation oil removing to strip liquor D4, first removes the suspension that partial size is greater than 60 μm through sloping plate oil separation tank
Elaioleucite, then dispersion elaioleucite of the partial size less than 60 μm is removed through level-one air bearing, then in 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 use fibrous nodules or fiber
Silk removes remaining oil emulsion in solution and is partly dissolved oil, accurate filters pressing remove the fibrous nodules brought into solution, fiber filament and
Solid suspension obtains 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.
Through detecting, the purity for the copper that two to five electrodeposition of embodiment obtains is 99.99% or more.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferred embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present invention
Or equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in claim of the invention
In range.Technology not described in detail in the present invention, shape, construction portion are well-known technique.
Claims (5)
1. the method for preparing high purity copper and nickel nitrate with electroplating sludge, which comprises the following steps:
Dissolution is leached, and electroplating sludge is mixed with acid solution, filter residue A and leachate is obtained by filtration in 3~5h of aerating oxidation；
Except iron behind pH=2.5~3.0 for adjusting leachate, oxidizing reaction 1.5h is added, then adjust pH=3.5 in complexing
~3.8, filter residue B is obtained by filtration and except ferrous solution；
Resin adsorption will be heated to 35~45 DEG C except ferrous solution, be passed through strong-acid cation-exchange resin column carry out copper ion, nickel from
Son absorption carries out backwash desorption to resin column with the sulfuric acid solution of 3mol/L, obtains stripping liquid after resin adsorption is saturated；
Electrodeposition sinks copper, using Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA will be solved as anode using pure copper starting sheet as cathode
Imbibition carries out electrodeposition reaction under DC current effect, obtains fine copper and low copper solution；
Abstraction impurity removal, P204 extractant is added into low copper solution and sodium carbonate liquor carries out level-one saponifiable extraction, obtains nickeliferous
P204 extractant is continuously added in raffinate A and organic phase A, raffinate A and sodium carbonate liquor carries out the processing of second level saponifiable extraction,
Raffinate C and nickeliferous organic phase C are obtained, the nitric acid solution that 3mol/L is added in organic phase C is stripped, and nickeliferous back extraction is obtained
Liquid D and organic phase D；
Ultrasonic oil removing carries out segmentation oil removing, after supersonic gas vibrating and secondary air-floatation oil removing to strip liquor D, then with fibrous nodules or
Fiber filament adsorbs oil removing, and filters pressing obtains nickel nitrate solution；
It being concentrated and dried, nickel nitrate solution is evaporated concentration, and adjust concentrate pH=2.0, decrease temperature crystalline filters drying,
Obtain nickel nitrate crystal；
The Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA is using pulse electrodeposition method in Ti/SnO2-Sb2O3Upper deposition β-
PbO2It is made with CNTs/PDDA, the carbon nanotube is the carbon nanometer with sharp end nose cone shape using the preparation of hydrogen arc process
Pipe, the Ti/SnO2-Sb2O3/PbO2In the preparation of-CNTs-PDDA, by Ti/SnO2-Sb2O3Being placed in main component is
0.5mol/LPb(NO3)2、0.15mol/LHNO3、0.05mol/LKF2·H2O, it in the electroplate liquid of 50g/LCNTs/PDDA, uses
Three-electrode system, Ti/SnO2-Sb2O3For working electrode, platinized platinum, to be to electrode, Ag/AgCl be that reference electrode implements pulse electricity is heavy
Product 15min, obtains Ti/SnO2-Sb2O3/PbO2- CNTs-PDDA combination electrode.
2. the method according to claim 1 for preparing high purity copper and nickel nitrate with electroplating sludge, which is characterized in that described strong
Weak acid cation exchange resin is NDA-36 resin.
3. the method according to claim 2 for preparing high purity copper and nickel nitrate with electroplating sludge, which is characterized in that the tree
Copper ion, nickel ion are carried out except ferrous solution is passed through strong-acid cation-exchange resin column with the flow velocity of 1~4BV/h in rouge adsorption step
Absorption, sulfuric acid solution carry out backwash desorption to resin column with the flow velocity of 2~4BV/h.
4. the method according to claim 3 for preparing high purity copper and nickel nitrate with electroplating sludge, which is characterized in that the electricity
The parameter of deposition copper step is 55~65 DEG C of temperature, 2.0~2.5V of tank voltage, current density 230A/m2。
5. the method according to claim 4 for preparing high purity copper and nickel nitrate with electroplating sludge, which is characterized in that described super
The parameter of sound oil removing is 15~25 DEG C of temperature, 25~30kHz of frequency, power 350W.
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