CN107164785A - A kind of copper electrolyte precipitation to remove impurities and precipitating reagent chlorination regeneration method - Google Patents
A kind of copper electrolyte precipitation to remove impurities and precipitating reagent chlorination regeneration method Download PDFInfo
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- CN107164785A CN107164785A CN201710372522.8A CN201710372522A CN107164785A CN 107164785 A CN107164785 A CN 107164785A CN 201710372522 A CN201710372522 A CN 201710372522A CN 107164785 A CN107164785 A CN 107164785A
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- antimony
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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
- C25C7/06—Operating or servicing
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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
- C22B15/0089—Treating solutions by chemical methods
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
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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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- 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
A kind of copper electrolyte precipitation to remove impurities and precipitating reagent chlorination regeneration method, it is to add antimonial into copper electrolyte to remove arsenic, antimony, bismuth co-precipitation, copper electrolyte directly returns to electrolysis system after removing impurities, and carbon thermal chlorination and gradient temperature control condensation method synthetical recovery are used containing arsenic, antimony, bismuth precipitation.Under coke and chlorinating agent effect, precipitation, which carries out carbon thermal chlorination, must contain arsenic, antimony, the mixed gas of bismuth chloride；Mixed gas condenses to obtain bismuth chloride and high temperature condensation tail gas through high temperature；High temperature condenses tail gas and condenses to obtain antimony chloride and middle temperature condensation tail gas through middle temperature；Middle temperature condensation tail gas obtains arsenic chloride and ammonia-containing exhaust through cryogenic condensation；Antimony chloride and ammonia-containing exhaust are slowly added in water, and hydrolysis transition obtains antimonial, and precipitation to remove impurities process is returned as precipitating reagent.The present invention have technological process is short, simple to operate, removal efficiency is high, without " three wastes " discharge, precipitating reagent it is reusable, it is with low cost the features such as, be adapted to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of purification method of electrolyte in non-ferrous metal hydrometallurgy process, particularly in copper electrolyte
Arsenic, antimony, the method for bismuth impurity removal and synthetical recovery.
Background technology
With developing rapidly for copper metallurgy industry, high-quality copper concentrate is fewer and fewer, the impurity such as arsenic, antimony, bismuth in mineral products anode copper
Content is in continuous ascendant trend, causes arsenic in copper electrolyte, antimony, bi content high.Due to arsenic, antimony, the deposition potential of bismuth and copper
Deposition potential is close, after the arsenic in electrolyte, antimony, bi content reach finite concentration, is easily separated out together with copper in negative electrode, separately
Outside, in electrolyte arsenic, antimony, bismuth easily forms " the floating earth of positive pole " adhesion or mechanical entrainment on tough cathode, so as to influence the moon
The quality of pole copper.
To ensure that copper electrolytic process is normally carried out, current cupric electrolysis industry is often purified using revulsion to electrolyte
Processing, to remove the impurity such as the arsenic in electrolyte, antimony, bismuth, but for high antimony, the copper electrolyte of high bismuth, the technique removing impurities efficiency
Low, net liquid measure is big, cost is high, it is big to produce toxic gas environmental pollution.In recent years, domestic and foreign scholars are seeking new copper always
Electrolyte purification technique, and many effective arsenic removals, antimony, bismuth method are developed, purified including stannic acid and charcoal absorption,
Barium carbonate, strontium carbonate co-precipitation bismuth, polymeric adsorbent absorption antimony, bismuth, the method such as solvent extraction arsenic, antimony, bismuth, but these methods are different
Degree has that removing impurities efficiency is low, fixed investment big, produce the defects such as certain side effect to electrolyte.Patent application
201410333413.1,201510422489.6 and 201610775577.9, the method for disclosing copper electrolyte removing impurity by means of precipitation, with
The oxide and its hydrate of antimony or/and bismuth are adsorbent or precipitating reagent, remove arsenic, antimony, bismuth in electrolyte, but these methods
Common ground is all to carry out alkali leaching to gained solid sediment, so as to regenerate precipitating reagent, is handed over accordingly, there exist technological process length, soda acid
Replace, reagent consumes the defect such as big, while arsenic, antimony, bismuth can not individually open a way, and can also produce various wastewater, it is necessary to further
Recycling.
The content of the invention
Can be by arsenic in copper electrolyte, antimony, bismuth efficient removal and individually open circuit is reclaimed, simultaneously it is an object of the present invention to provide one kind
The method of the renewable reuse of precipitating reagent, with technological process is short, simple to operate, removal efficiency is high, nothing " three wastes " is discharged, precipitation
Agent is reusable, it is with low cost the features such as, be adapted to large-scale industrial production.
To reach above-mentioned purpose, the present invention is adopted the technical scheme that：Antimonial is added into copper electrolyte as heavy
Shallow lake agent, the arsenic in copper electrolyte, antimony, bismuth co-precipitation are removed, filter after removing impurities copper electrolyte and containing arsenic, antimony, bismuth precipitation；
Copper electrolyte directly returns to copper electrolysis system after removing impurities, and precipitation reclaims arsenic, antimony using carbon thermal chlorination and gradient temperature control condensation method
And bismuth；In the presence of coke and chlorinating agent, precipitation carry out carbon thermal chlorination obtain containing arsenic, antimony, bismuth chloride mixed gas；It is mixed
Close gas and obtain bismuth chloride and high temperature condensation tail gas through high temperature condensation；High temperature condenses tail gas and obtains antimony chloride through the condensation of middle temperature
Tail gas is condensed with middle temperature；Middle temperature condensation tail gas obtains arsenic chloride and ammonia-containing exhaust through cryogenic condensation；The antimony that middle temperature condensation is obtained
Chloride and cryogenic condensation ammonia-containing exhaust are slowly added in water, are occurred hydrolysis transition and are obtained antimonial, are used as precipitating reagent
Return to copper electrolyte precipitation to remove impurities process.
Specific technical process and technological parameter are as follows.
1. precipitation to remove impurities.Copper electrolyte is put into tank diameter, antimony oxide, antimony tetroxide, five oxidations two are added
One or more of mixtures in antimony carry out precipitation to remove impurities as precipitating reagent, through filter after removing impurities copper electrolyte and containing arsenic,
Copper electrolyte directly returns to copper electrolysis system after the precipitation of antimony, bismuth, removing impurities.Precipitation to remove impurities process conditions are：Copper in copper electrolyte
Concentration be that 20.0-70.0 g/L, the concentration of sulfuric acid are that 100.0-500.0 g/L, the concentration of arsenic are 2.0-40.0 g/L, antimony
Concentration is that 0.01-5.0 g/L, the concentration of bismuth are 0.01-5.0 g/L, and precipitating reagent addition is 5.0-30.0 g/L, and temperature is
25-95 DEG C, the time is 0.5-5.0 hours.
2. carbon thermal chlorination.By containing arsenic, antimony, the precipitation of bismuth and chlorinating agent and coke value 10 in mass ratio:5:0.5-10:25:
5 are mixed, being 500-1000 DEG C in temperature carries out carbon thermal chlorination 0.5-5.0 hour, obtain mixing containing arsenic, antimony, bismuth chloride
Close gas.Chlorinating agent is NH4Cl, or NH4Cl and FeCl2、MgCl2、AlCl3、Cl2Middle one or more of mixture.
3. high temperature is condensed.Mixed gas passes through 300-400 DEG C of warm condenser, condenses 0.5-5.0 hours, obtains bismuth
Chloride and high temperature condensation tail gas.High temperature condensation tail gas send middle temperature to condense.
4. middle temperature condensation.High temperature condensation tail gas passes through 150-220 DEG C of middle temperature condenser, condenses 0.5-5.0 hours, obtains
To antimony chloride and middle temperature condensation tail gas.Antimony chloride send hydrolysis to make the transition, and middle temperature condensation tail gas send cryogenic condensation.
5. cryogenic condensation.Middle temperature condensation tail gas passes through 100-130 DEG C of low-temperature condenser, condenses 0.5-5.0 hours, obtains
To arsenic chloride and ammonia-containing exhaust.Ammonia-containing exhaust send hydrolysis to make the transition.
6. hydrolysis transition.Middle temperature is condensed to obtained antimony chloride with 1.0-20.0 kg/h speed to be added to the water, simultaneously
With 1.0-20.0 Nm3/ h speed is passed through the ammonia-containing exhaust that cryogenic condensation is obtained, and keeps antimony chloride:Water is 1:5-1:20 kg/
L, temperature are 25-95 DEG C, the time is 0.5-3.0 hours, are filtrated to get antimonial, are used as precipitating reagent to return to copper electrolyte precipitation
Removing impurities process.
The various reagents are technical grade reagent.
Compared with copper electrolyte arsenic, antimony, bismuth removing existing method, the invention has the advantages that：By the arsenic in copper electrolyte,
Antimony, bismuth efficient removal, and by carbon thermal chlorination and gradient temperature control condensation technology, by arsenic, antimony and bismuth with high-purity compound form list
Solely reclaim, so as to realize arsenic, antimony, the efficient removal of bismuth impurity and open circuit, and precipitating reagent reuse, with technological process
Short, simple to operate, removal efficiency is high, without " three wastes " discharge, it is with low cost the advantages of, be adapted to large-scale industrial production.
The present invention can be widely used in removing and comprehensively reclaiming arsenic, antimony and bismuth from various acid solutions, be particularly suitable for place
Manage high arsenic, high antimony, the copper electrolyte of high bismuth, it can also be used to nickel, the arsenic of zinc electrolyte, antimony, bismuth removing impurities process.
Brief description of the drawings
Fig. 1：Present invention process flow chart schematic diagram.
Embodiment
With reference to embodiment, the invention will be further described, and following examples are intended to illustrate invention rather than right
The further restriction of the present invention.
Embodiment 1.
Toward 1 m3The kg of antimony oxide 15 is added in copper electrolyte, is reacted 1.0 hours at 85 DEG C of temperature, filtering to take off
The miscellaneous m of rear copper electrolyte 0.993With containing arsenic, antimony, bismuth the kg of precipitation 24.46, the removal efficiency difference of arsenic, antimony, bismuth in copper electrolyte
For 68.89 %, 64.22 % and 92.75 %, influence of the precipitation reaction to copper in copper electrolyte and acid content is little, precipitation to remove impurities
As a result it is as follows.
| Element | Cu | As | Sb | Bi | H2SO4 |
| Copper electrolyte g/L before removing impurities | 43.50 | 7.60 | 0.25 | 1.12 | 175.00 |
| Copper electrolyte g/L before removing impurities | 43.85 | 2.38 | 0.09 | 0.08 | 176.39 |
By containing arsenic, antimony, the precipitation of bismuth and ammonium chloride and coke value 10 in mass ratio:20:1 is mixed, and is in temperature
800 DEG C carry out carbon thermal chlorination 3.0 hours, obtain containing arsenic, antimony, bismuth chloride the Nm of mixed gas 22.693；Mixed gas is passed through
380 DEG C of warm condenser, is condensed 2.0 hours, obtains bismuth chloride and 22.58 Nm that 1.55 kg purity are 95.47%3's
High temperature condenses tail gas；High temperature condensation tail gas passes through 200 DEG C of middle temperature condenser, condenses 1.5 hours, obtaining 23.54 kg purity is
96.23% antimony chloride and 20.26 Nm3Middle temperature condensation tail gas；Middle temperature condensation tail gas passes through 110 DEG C of low-temperature condenser,
Condensation 1.5 hours, obtains arsenic chloride and 18.71 Nm that 12.54 kg purity are 94.27%3Ammonia-containing exhaust；By middle Wen Leng
Solidifying obtained antimony chloride is added to the water with 8.0 kg/h speed, while with 6.5 Nm3/ h speed is passed through what cryogenic condensation was obtained
Ammonia-containing exhaust, keeps antimony chloride:Water is 1:8 kg/L, temperature are 35 DEG C, the time is 3.0 hours, are filtrated to get 15.04 kg
Purity is 99.54% Sb2O3, copper electrolyte precipitation to remove impurities process is returned as precipitating reagent.
Embodiment 2.
Toward 1 m3The kg of antimony oxide 20 is added in copper electrolyte, is reacted 1.5 hours at 75 DEG C of temperature, filtering to take off
The miscellaneous m of rear copper electrolyte 0.993With containing arsenic, antimony, bismuth the kg of precipitation 34.96, the removal efficiency difference of arsenic, antimony, bismuth in copper electrolyte
For 72.56 %, 85.71 % and 94.25 %, influence of the precipitation reaction to copper in copper electrolyte and acid content is little, precipitation to remove impurities
As a result it is as follows.
| Element | Cu | As | Sb | Bi | H2SO4 |
| Copper electrolyte g/L before removing impurities | 37.48 | 10.50 | 0.86 | 2.13 | 199.00 |
| Copper electrolyte g/L before removing impurities | 37.93 | 3.31 | 0.12 | 0.16 | 201.41 |
By containing arsenic, antimony, the precipitation of bismuth and ammonium chloride, frerrous chloride and coke value 10 in mass ratio:15:5:2 are mixed
Close, being 900 DEG C in temperature carries out carbon thermal chlorination 2.5 hours, obtain containing arsenic, antimony, bismuth chloride the Nm of mixed gas 24.583；
Mixed gas passes through 350 DEG C of warm condenser, condenses 1.5 hours, obtain bismuth chloride that 3.00 kg purity are 95.98% and
24.36 Nm3High temperature condensation tail gas；High temperature condensation tail gas passes through 180 DEG C of middle temperature condenser, condenses 2.0 hours, obtains
32.36 kg purity are 97.14% antimony chloride and 21.18 Nm3Middle temperature condensation tail gas；Middle temperature condensation tail gas passes through 105 DEG C
Low-temperature condenser, condense 2.5 hours, obtain 18.25 kg purity be 95.24% arsenic chloride and 18.93 Nm3Contain ammonia
Tail gas；Middle temperature is condensed to obtained antimony chloride with 16.5 kg/h speed to be added to the water, while with 9.5 Nm3/ h speed is passed through
The ammonia-containing exhaust that cryogenic condensation is obtained, keeps antimony chloride:Water is 1:10 kg/L, temperature are 45 DEG C, the time is 2.0 hours,
It is filtrated to get the Sb that 20.67 kg purity are 99.21%2O3, copper electrolyte precipitation to remove impurities process is returned as precipitating reagent.
Embodiment 3.
Toward 1 m3The kg of antimony oxide 35 is added in copper electrolyte, is reacted 2.5 hours at 70 DEG C of temperature, filtering to take off
The miscellaneous m of rear copper electrolyte 0.983With containing arsenic, antimony, bismuth the kg of precipitation 57.73, the removal efficiency difference of arsenic, antimony, bismuth in copper electrolyte
For 70.69 %, 80.52 % and 93.54 %, influence of the precipitation reaction to copper in copper electrolyte and acid content is little, precipitation to remove impurities
As a result it is as follows.
| Element | Cu | As | Sb | Bi | H2SO4 |
| Copper electrolyte g/L before removing impurities | 67.45 | 18.37 | 1.09 | 1.58 | 156.00 |
| Copper electrolyte g/L before removing impurities | 68.75 | 5.49 | 0.22 | 0.10 | 159.01 |
By containing arsenic, antimony, the precipitation of bismuth and ammonium chloride, frerrous chloride, magnesium chloride and coke value 10 in mass ratio:15:3:2:2
Mixed, being 700 DEG C in temperature carries out carbon thermal chlorination 4.0 hours, obtain containing arsenic, antimony, bismuth chloride mixed gas 39.75
Nm3；Mixed gas passes through 300 DEG C of warm condenser, condenses 2.5 hours, obtains the bismuth chlorination that 2.21 kg purity are 96.28%
Thing and 39.60 Nm3High temperature condensation tail gas；High temperature condensation tail gas passes through 160 DEG C of middle temperature condenser, condenses 2.5 hours, obtains
To the antimony chloride and 34.11 Nm that 55.86 kg purity are 97.59%3Middle temperature condensation tail gas；Middle temperature condensation tail gas passes through 120
DEG C low-temperature condenser, condense 2.0 hours, obtain 31.11 kg purity be 96.68% arsenic chloride and 30.26 Nm3Contain
Ammonia tail gas；Middle temperature is condensed to obtained antimony chloride with 16.0 kg/h speed to be added to the water, while with 8.5 Nm3/ h speed is led to
Enter the ammonia-containing exhaust that cryogenic condensation is obtained, keep antimony chloride:Water is 1:6 kg/L, temperature are 25 DEG C, the time is 3.5 hours,
It is filtrated to get the Sb that 35.69 kg purity are 99.19%2O3, copper electrolyte precipitation to remove impurities process is returned as precipitating reagent.
Claims (3)
1. a kind of copper electrolyte precipitation to remove impurities and precipitating reagent chlorination regeneration method, it is characterised in that comprise the following steps：
A. precipitation to remove impurities
Copper electrolyte is put into tank diameter, the one or more added in antimony oxide, antimony tetroxide, antimony pentoxide
Mixture carries out precipitation to remove impurities as precipitating reagent, through filter after removing impurities copper electrolyte and containing arsenic, antimony, bismuth precipitation, after removing impurities
Copper electrolyte directly returns to copper electrolysis system；Precipitation to remove impurities process conditions are：The concentration of copper is 20.0-70.0 in copper electrolyte
G/L, the concentration of sulfuric acid are that 100.0-500.0 g/L, the concentration of arsenic are that 2.0-40.0 g/L, the concentration of antimony are 0.01-5.0 g/
L, the concentration of bismuth are 0.01-5.0 g/L, and precipitating reagent addition is 5.0-30.0 g/L, and temperature is 25-95 DEG C, and the time is 0.5-
5.0 hour；
B. carbon thermal chlorination
By containing arsenic, antimony, the precipitation of bismuth and chlorinating agent and coke value 10 in mass ratio:5:0.5-10:25:5 are mixed, in temperature
Carry out carbon thermal chlorination 0.5-5.0 hours for 500-1000 DEG C, obtain containing arsenic, antimony, bismuth chloride mixed gas；Chlorinating agent is
NH4Cl, or NH4Cl and FeCl2、MgCl2、AlCl3、Cl2Middle one or more of mixture；
C. high temperature is condensed
Mixed gas passes through 300-400 DEG C of warm condenser, condenses 0.5-5.0 hours, obtains bismuth chloride and high temperature condensation
Tail gas, high temperature condensation tail gas send middle temperature to condense；
D. middle temperature condensation
High temperature condensation tail gas passes through 150-220 DEG C of middle temperature condenser, condenses 0.5-5.0 hours, obtains antimony chloride and middle temperature
Tail gas is condensed, antimony chloride send hydrolysis to make the transition, middle temperature condensation tail gas send cryogenic condensation；
E. cryogenic condensation
Middle temperature condensation tail gas passes through 100-130 DEG C of low-temperature condenser, condenses 0.5-5.0 hours, obtains arsenic chloride and containing ammonia
Tail gas, ammonia-containing exhaust send hydrolysis to make the transition；
F. hydrolysis transition
Middle temperature is condensed to obtained antimony chloride with 1.0-20.0 kg/h speed to be added to the water, while with 1.0-20.0 Nm3/ h speed
Degree is passed through the ammonia-containing exhaust that cryogenic condensation is obtained, and keeps antimony chloride:Water is 1:5-1:20 kg/L, temperature be 25-95 DEG C, when
Between be 0.5-3.0 hour, be filtrated to get antimonial, be used as precipitating reagent return copper electrolyte precipitation to remove impurities process.
2. the method for a kind of copper electrolyte precipitation to remove impurities according to claim 1, it is characterised in that methods described can be used for
The arsenic of nickel electrolyte, antimony, bismuth removing impurities process.
3. the method for a kind of copper electrolyte precipitation to remove impurities according to claim 1, it is characterised in that methods described can be used for
The arsenic of zinc electrolyte, antimony, bismuth removing impurities process.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109022785A (en) * | 2018-10-10 | 2018-12-18 | 江西理工大学 | A method of bismuth is removed from copper electrolyte |
| CN109055775A (en) * | 2018-09-14 | 2018-12-21 | 阳谷祥光铜业有限公司 | A kind of method of living again of the complex precipitant for purifying copper electrolyte |
| CN109437385A (en) * | 2018-10-30 | 2019-03-08 | 金川集团股份有限公司 | The process of antimony and bismuth in a kind of removing copper electrolyte |
| 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 |
| CN112742131A (en) * | 2020-12-31 | 2021-05-04 | 成都易态科技有限公司 | Treatment system and treatment method for flue gas generated in copper matte preparation by pyrogenic process |
| CN113529137A (en) * | 2021-07-16 | 2021-10-22 | 兰溪自立环保科技有限公司 | Copper-nickel-containing waste acid solution treatment and recycling process |
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| CN109055775A (en) * | 2018-09-14 | 2018-12-21 | 阳谷祥光铜业有限公司 | A kind of method of living again of the complex precipitant for purifying copper electrolyte |
| CN109055775B (en) * | 2018-09-14 | 2021-05-04 | 阳谷祥光铜业有限公司 | Regeneration method of complexing precipitator for purifying copper electrolyte |
| CN109022785A (en) * | 2018-10-10 | 2018-12-18 | 江西理工大学 | A method of bismuth is removed from copper electrolyte |
| CN109022785B (en) * | 2018-10-10 | 2020-05-01 | 江西理工大学 | Method for removing bismuth from copper electrolyte |
| CN109437385A (en) * | 2018-10-30 | 2019-03-08 | 金川集团股份有限公司 | The process of antimony and bismuth in a kind of removing copper electrolyte |
| 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 |
| CN112742131A (en) * | 2020-12-31 | 2021-05-04 | 成都易态科技有限公司 | Treatment system and treatment method for flue gas generated in copper matte preparation by pyrogenic process |
| CN113529137A (en) * | 2021-07-16 | 2021-10-22 | 兰溪自立环保科技有限公司 | Copper-nickel-containing waste acid solution treatment and recycling process |
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| Publication number | Publication date |
|---|---|
| CN107164785B (en) | 2019-03-15 |
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