CN106756069A - A kind of method that valuable metal is reclaimed in the waste residue from zinc abstraction - Google Patents
A kind of method that valuable metal is reclaimed in the waste residue from zinc abstraction 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
- C22B7/04—Working-up slag
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
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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
- C22B15/0091—Treating solutions by chemical methods by cementation
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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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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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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Abstract
A kind of method the invention discloses valuable metal is reclaimed in waste residue from zinc abstraction, including recovery silver, copper and recovery zinc, nickel, two stages of cobalt, comprise the following steps：Zinc abstraction waste residue is made slurries, is floatingly selected and add after the slag rich in silver-bearing copper lime-roasting and obtain the calcining rich in silver-bearing copper, then calcining is leached from electrolyte be filtrated to get after iron powder reducing rich in silver, the fine powder of copper；By zinc abstraction waste residue crush it is uniform, determine that waste residue most preferably leaches condition test, zinc dust precipitation except nickel cobalt experiment, Selectively leaching experiment, zinc and nickel, the experiment of cobalt extract and separate, the back extraction experiment of zinc, the experiment of nickel cobalt extract and separate, the back extraction experiment of cobalt, deep purifying experiment, electrodeposition recovery zinc, nickel, cobalt are tested；Zinc metallurgy zinc abstraction waste residue is raw material to the present invention in a wet process, and the valuable metals such as silver, copper, zinc, nickel, the cobalt in waste residue are reclaimed by serial of methods step, had not only protected environment but also had saved resource, with Social benefit and economic benefit higher.
Description
Technical field
The invention belongs to metal recovery technical field, the side of valuable metal is reclaimed in more particularly to a kind of waste residue from zinc abstraction
Method.
Background technology
Although China's non-ferrous metal gross reserves is larger, positioned at the former positions in the world, average resource per capita comes the whole world
Several afterwards, or even much closely bound up with national economy mineral resources are all in very short state, therefore, to secondary money
The recycling in source is particularly important.Zinc as important parent metal, have in national economy widely should
With, and containing more than ten kinds of precious metals such as zinc, nickel, cobalts in zinc abstraction waste residue, every kind of metal all has for the development of national economy
Play the role of particularly important, be the treasure of human society；Recovery value highest nickel and cobalt can be used in zinc abstraction waste residue
The industries such as manufacture alloy, machining, demand is huge, it is seen then that the metal in zinc abstraction waste residue has considerable recovery
Value, additionally, the recovery to heavy metal in zinc abstraction waste residue is also to follow sustainable development, response world environmental protection theme, protection
The performance of environment.Therefore, there is the double meaning to economic development and environmental protection to the recovery of heavy metal in zinc abstraction waste residue.
The recovery method of the precious metal such as zinc in zinc abstraction waste residue, mainly there is two kinds of techniques of pyrogenic process and wet method at present.Pyrogenic process
Recovery process is due to producing the spy such as substantial amounts of pernicious gas, high to production equipment requirement in high energy consumption, complex process, production process
Put and be rarely used；Simply and beneficial to environmental protection accepted extensively by professional, hydrometallurgic recovery work due to wet recycling process
Skill mainly includes three steps：Acidleach, purification separation, electrodeposition are reclaimed, and are dissolved zinc abstraction waste residue by acidleach, and second step is
It is finally to reclaim various metals difference electrodeposition by various metal isolation of purified on the basis of acidleach dissolving.It is domestic at present right
The recovery research of zinc has been mature on the whole in zinc abstraction waste residue, and has substantial amounts of experiment to have been used for industrial production.
The new method of zinc abstraction is sought in effort in spite of many scientific research personnel, but smelting process is still led both at home and abroad at present
Will in a wet process based on zinc metallurgy, this has just inevitably produced zinc abstraction waste residue a large amount of, for these waste residues, once largely pile up
If, negative impact is not only caused to environment, but also be a kind of wasting of resources.
The content of the invention
Valuable metal method is reclaimed from zinc abstraction waste residue the invention provides one kind, through a series of experiments, is further returned
The valuable metals such as silver therein, copper, zinc, nickel, cobalt are received, environment had not only been protected but also had been saved resource.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method that valuable metal is reclaimed in waste residue from zinc abstraction, the zinc abstraction waste residue is by net after iron purification
Slugging, the method for valuable metal is reclaimed in the waste residue from zinc abstraction to be included reclaiming silver, copper and reclaims zinc, nickel, two ranks of cobalt
Section, the silver, the stage of copper of reclaiming is that the silver and copper in the purification slag, the recovery are reclaimed by the fine powder rich in silver, copper
Zinc, nickel, the stage of cobalt include that waste residue is leached, isolation of purified and electrode reclaim three phases again, and the waste residue leaching stage is main
It is by a series of waste residue leaching test, to determine optimal leaching condition when zinc abstraction waste residue is leached, the purification separation
Stage is the property according to the various metals such as zinc, nickel, cobalt, is tested by zinc dust precipitation experiment, Selectively leaching, extracted and back extraction
The purpose that experiment etc. reaches the mutual isolation of purified of various metals is taken, the electrodeposition recovery stage is mainly distinguished using embrane method electrodeposition
Zinc, nickel, three kinds of metals of cobalt are reclaimed, its process is comprised the following steps：
S1：It is 1.45~1.55 × 10 that the zinc abstraction waste residue is made into density3 kg/m3, the slurries that pH value is 5~5.8,
Activating agent is added in slurries, is floatingly selected rich in silver, the slag of copper, the slag rich in silver, copper is added the stone of certain mass
After ash the calcining rich in silver, copper is obtained in 880~950 DEG C of roastings；
S2：The calcining rich in silver, copper is immersed in the electrolyte that temperature is 65~72 DEG C, pH value is 1.8~2.2, instead
1.5~2 hours between seasonable, then the calcining rich in silver, copper is leached from the electrolyte, then filtered after iron powder reducing
Can obtain rich in silver, the fine powder of copper；
S3：The zinc abstraction waste residue is crushed uniform, and prepares to reclaim the instrument and medicine and reagent used by valuable metal；
S4：Determine that waste residue most preferably leaches condition test：The dry zinc abstraction waste residue several pieces of 20g are accurately weighed respectively to be tried
Test, the waste residue most preferably leach need in condition test control variable include leaching agent species, leaching agent concentration, liquid-solid ratio,
Leaching time and temperature, the waste residue most preferably leach the principle using single-factor variable during condition test, by optimal leaching
Take agent and determine experiment, the experiment of optimal leaching agent concentration tests, liquid-solid ratio, leaching time experiment and leaching temperature experiment, successively really
Make the optimal leaching condition of zinc abstraction waste residue in acid leaching stage；
S5：Zinc dust precipitation is tested except nickel cobalt：After the completion of the S4 steps, it is determined that optimal leaching under the conditions of, by the zinc
Melting waste slag dissolution filter, measures several pieces filtrate and is placed in beaker in right amount respectively, and being heated under identical mixing speed is carried out
Experiment, in process of the test, controls different alloy zinc powders or addition Sb respectively2O3High-purity zinc powder dosage, different reactions
Temperature, different reaction PH and reaction time, with nickel, cobalt displacement clearance as index, determine zinc dust precipitation except nickel cobalt try
The optimal displacement condition tested；
S6：Selectively leaching is tested：It is determined that optimal leaching under the conditions of dissolve waste residue obtained by filtrate, through displacement reaction after, zinc
Do not react completely, zinc, nickel and cobalt are still contained in the sediment after filtering, but the percentage composition of zinc has been substantially reduced, institute
It is exactly the percentage composition that zinc in sediment is further reduced on the basis of Zn content reduction to state Selectively leaching experiment,
The content of nickel and cobalt is improved, is beneficial to being smoothed out for follow-up test；
S7：Zinc is tested with nickel cobalt extract and separate：After the completion of the step S5 and S6, zinc in the zinc abstraction waste residue is remained in
Comparision contents are low, after filter residue is dissolved again with sulfuric acid, carry out zinc extraction test, zinc is entered organic phase through extracting, and nickel cobalt
It is not extracted, in remaining on raw water phase, so as to reach the purpose that zinc and nickel cobalt are completely separated；
S8：The back extraction experiment of zinc：After the completion of the step S7, zinc-rich organic phase is obtained, the back extraction experiment of the zinc is
On the basis of step S7, by organic phase after simply washing, the zinc taken out in organic phase is stripped with strippant, obtained in accordance with electricity
The pure zinc electrolyte that product is required；
S9：Nickel cobalt extract and separate is tested：After zinc and nickel cobalt extract and separate, nickel is not separated also with cobalt, in remaining on water phase, due to
Cobalt is more easy to enter organic phase compared with nickel, therefore nickel cobalt extract and separate experiment still uses solvent-extracted method；
S10：The back extraction experiment of cobalt：After the completion of the step S9, obtain rich cobalt organic phase, the rich cobalt organic phase through go from
After sub- water washing, with strippant through the available more pure cobalt electrolyte of multi-stage counter current extraction；
S11：Deep purifying is tested：After the completion of step S7, S8, S9, S10, more pure zinc electrolyte, nickel can be obtained
Electrolyte and cobalt electrolyte, by the available more pure electrolyte of the deep purifying；
S12：Electrodeposition reclaims zinc, nickel, cobalt experiment：In electrodeposition recovery stage, can respectively carry out electrodeposition and reclaim the zinc electrolyte, nickel
Metal in electrolyte and cobalt electrolyte, and by electrodeposition recovery test, optimal electricity when determining that zinc, nickel and cobalt electrodeposition are reclaimed
Product condition and the rate of recovery；
The stage for reclaiming silver-colored, copper includes above S1 and S2 step, the recovery zinc, nickel, waste residue leaching rank in the stage of cobalt
Section includes above S3, S4, S5 and S6 steps, and the isolation of purified stage includes above S7, S8, S9, S10 and S11 step, described
Electrode recovery stage includes S12 steps.
The instrument includes 721 spectrophotometers, linear DC current regulator power supply, TB-1 types agitator, PHS-2
Type acidometer, universal electric furnace, electronic balance, counter balance, six magnetic stirrers, atomic absorption spectrophotometer；The medicine
Product reagent include 98% concentrated sulfuric acid, nitric acid, hydrochloric acid, without zinc water, perchloric acid, acetone, zinc sulfate, sodium chloride, common zinc powder, alloy
Zinc powder, high-purity zinc powder, antimony oxide, cupral, NaOH, kerosene, potassium permanganate etc..
Further, the lime quality is described rich in silver, the 6%~10% of the fine powder quality of copper, oxygen in the lime
The quality for changing calcium is more than 80%, and sulfuric acid content is 160~200g/L in the electrolyte, and the iron powder quality is silver, copper in calcining
1.2 times of quality comprehensive, iron content is more than 90% in the iron powder.
Further, the 20g zinc abstractions waste residue is placed in six constant temperature blender with magnetic force, sulfuric acid, salt is respectively adopted
Acid, three kinds of common acids of nitric acid as leaching agent, be respectively adopted concentration for 0.25mol/L, 0.50 mol/L, 0.75 mol/L and
The sulfuric acid solution of 1.00 mol/L, leaching time is 0.50h, 0.75h, 1.00h, 1.25h, 1.50h, 1.75h, difference respectively
Temperature be 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, waste residue leaching experiment is carried out at 90 DEG C, its can be obtained optimal
Leaching agent is sulfuric acid, and optimal leaching agent concentration is 0.5mol/L, and optimal leaching time is 1h, and optimal test temperature is 25 DEG C, most
Good liquid-solid ratio is 10:1.
Further, optimal alloy zinc powder dosage is 12.50g/L in every liter of filtrate in the S5 steps；Optimal Sb2O3
Consumption is 15mg/L, and optimal high-purity zinc powder consumption is 20g/L.
Further, it is 85 DEG C that the optimal reaction temperature of reaction is replaced in the S5 steps, and optimum reacting time is
90min, optimal pH value are 4.5.
Further, in the S6 steps during selectively leaching with process pH value 3.5, terminal PH is optimal when being 4.0 or so.
Further, zinc extraction test uses zinc synergic solvent extraction in the S7 steps, and extractant used is N235（Amine extracts
Take agent）And TBP（Tributyl phosphate）, diluent is kerosene, and extractant proportion of composing is 25%N235+30%TBP during synergic solvent extraction
+ 45% kerosene, optimal chlorine ion concentration is 70g/L, is most preferably in a ratio of 3:1, optimal extraction time of contact is 4min.
Further, it is kerosene that diluent used is tested in the S9 steps, and extractant is N235, due to N235 extractions
Taking the ionic compound generated during cobalt has certain polarity, third phase is easily produced in extraction process, therefore use TBP（Tricresyl phosphate
Butyl ester）Third phase is eliminated as additive, extractant proportion of composing is when nickel cobalt is extracted in the S9 steps：25%N235+
30%TBP+45% kerosene, separates the optimal of nickel cobalt and is in a ratio of 2:1~3:1, optimal extraction time of contact is 3min.
Further, in the S12 steps zinc using single cavity block electrodeposition method, using single anode membrane electrodeposition method, cobalt is using double for nickel
Membranes and three chambers electrodeposition method, single cavity block electrodeposition method optimum condition is：25 DEG C of normal temperature, pH value 4.5, electric current 400mA, electrodeposition time
34h；Single anode membrane electrodeposition method optimum condition is：When 25 DEG C of normal temperature, pH value 4.0~4.5, size of current are 350mA, electrodeposition
Between 44h；The dual membranes and three chambers electrodeposition method optimum condition is：25 DEG C of normal temperature, pH value 4.0, size of current 350mA, electrodeposition time
44h。
The present invention is so as to environmental protection and to economize on resources be starting point, zinc metallurgy zinc abstraction waste residue is raw material in a wet process, is passed through
Serial of methods and step further reclaim the valuable metals such as silver therein, copper, zinc, nickel, cobalt, have not only protected environment but also have saved
Resource, with Social benefit and economic benefit higher.
Brief description of the drawings
Fig. 1 is recovery silver, the process chart of copper in the present invention；
Fig. 2 is recovery zinc, nickel, the process chart of cobalt in the present invention.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments, is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, any modification, equivalent substitution and improvements made etc., should be included within the scope of the present invention.
As shown in Figure 1 and Figure 2, in a kind of waste residue from zinc abstraction reclaim valuable metal method, the zinc abstraction waste residue be through
The purification slag crossed after iron purification, in the waste residue from zinc abstraction reclaim valuable metal method include reclaim silver, copper and
Reclaim zinc, nickel, two stages of cobalt, the recovery silver, the stage of copper are by rich in silver, the fine powder recovery purification slag of copper
Silver and copper, the recovery zinc, nickel, cobalt stage again include waste residue leach, isolation of purified and electrode recovery three phases, it is described
Waste residue leaching stage is mainly by a series of waste residue leaching test, to determine optimal leaching bar when zinc abstraction waste residue is leached
Part, the purification separation stage is the property according to the various metals such as zinc, nickel, cobalt, by zinc dust precipitation experiment, Selectively leaching
Experiment, extraction and back extraction experiment etc. reach the purpose of the mutual isolation of purified of various metals, and the electrodeposition recovery stage is mainly adopted
Zinc, nickel, three kinds of metals of cobalt are separately recovered with embrane method electrodeposition, its process is comprised the following steps：
S1：It is 1.45~1.55 × 10 that the zinc abstraction waste residue is made into density3 kg/m3, the slurries that pH value is 5~5.8,
Activating agent is added in slurries, is floatingly selected rich in silver, the slag of copper, the slag rich in silver, copper is added the stone of certain mass
After ash the calcining rich in silver, copper is obtained in 880~950 DEG C of roastings；
S2：The calcining rich in silver, copper is immersed in the electrolyte that temperature is 65~72 DEG C, pH value is 1.8~2.2, instead
1.5~2 hours between seasonable, then the calcining rich in silver, copper is leached from the electrolyte, then filtered after iron powder reducing
Can obtain rich in silver, the fine powder of copper；
S3：The zinc abstraction waste residue is crushed uniform, and prepares to reclaim the instrument and medicine and reagent used by valuable metal；
S4：Determine that waste residue most preferably leaches condition test：The dry zinc abstraction waste residue several pieces of 20g are accurately weighed respectively to be tried
Test, the waste residue most preferably leach need in condition test control variable include leaching agent species, leaching agent concentration, liquid-solid ratio,
Leaching time and temperature, the waste residue most preferably leach the principle using single-factor variable during condition test, by optimal leaching
Take agent and determine experiment, the experiment of optimal leaching agent concentration tests, liquid-solid ratio, leaching time experiment and leaching temperature experiment, successively really
Make the optimal leaching condition of zinc abstraction waste residue in acid leaching stage；
S5：Zinc dust precipitation is tested except nickel cobalt：After the completion of the S4 steps, it is determined that optimal leaching under the conditions of, by the zinc
Melting waste slag dissolution filter, measures several pieces filtrate and is placed in beaker in right amount respectively, and being heated under identical mixing speed is carried out
Experiment, in process of the test, controls different alloy zinc powders or addition Sb respectively2O3High-purity zinc powder dosage, different reactions
Temperature, different reaction PH and reaction time, with nickel, cobalt displacement clearance as index, determine zinc dust precipitation except nickel cobalt try
The optimal displacement condition tested；
S6：Selectively leaching is tested：It is determined that optimal leaching under the conditions of dissolve waste residue obtained by filtrate, through displacement reaction after, zinc
Do not react completely, zinc, nickel and cobalt are still contained in the sediment after filtering, but the percentage composition of zinc has been substantially reduced, institute
It is exactly the percentage composition that zinc in sediment is further reduced on the basis of Zn content reduction to state Selectively leaching experiment,
The content of nickel and cobalt is improved, is beneficial to being smoothed out for follow-up test；
S7：Zinc is tested with nickel cobalt extract and separate：After the completion of the step S5 and S6, zinc in the zinc abstraction waste residue is remained in
Comparision contents are low, after filter residue is dissolved again with sulfuric acid, carry out zinc extraction test, zinc is entered organic phase through extracting, and nickel cobalt
It is not extracted, in remaining on raw water phase, so as to reach the purpose that zinc and nickel cobalt are completely separated；
S8：The back extraction experiment of zinc：After the completion of the step S7, zinc-rich organic phase is obtained, the back extraction experiment of the zinc is
On the basis of step S7, by organic phase after simply washing, the zinc taken out in organic phase is stripped with strippant, obtained in accordance with electricity
The pure zinc electrolyte that product is required；
S9：Nickel cobalt extract and separate is tested：After zinc and nickel cobalt extract and separate, nickel is not separated also with cobalt, in remaining on water phase, due to
Cobalt is more easy to enter organic phase compared with nickel, therefore nickel cobalt extract and separate experiment still uses solvent-extracted method；
S10：The back extraction experiment of cobalt：After the completion of the step S9, obtain rich cobalt organic phase, the rich cobalt organic phase through go from
After sub- water washing, with strippant through the available more pure cobalt electrolyte of multi-stage counter current extraction；
S11：Deep purifying is tested：After the completion of step S7, S8, S9, S10, more pure zinc electrolyte, nickel can be obtained
Electrolyte and cobalt electrolyte, by the available more pure electrolyte of the deep purifying；
S12：Electrodeposition reclaims zinc, nickel, cobalt experiment：In electrodeposition recovery stage, can respectively carry out electrodeposition and reclaim the zinc electrolyte, nickel
Metal in electrolyte and cobalt electrolyte, and by electrodeposition recovery test, optimal electricity when determining that zinc, nickel and cobalt electrodeposition are reclaimed
Product condition and the rate of recovery；
The stage for reclaiming silver-colored, copper includes above S1 and S2 step, the recovery zinc, nickel, waste residue leaching rank in the stage of cobalt
Section includes above S3, S4, S5 and S6 steps, and the isolation of purified stage includes above S7, S8, S9, S10 and S11 step, described
Electrode recovery stage includes S12 steps.
The instrument includes 721 spectrophotometers, linear DC current regulator power supply, TB-1 types agitator, PHS-2
Type acidometer, universal electric furnace, electronic balance, counter balance, six magnetic stirrers, atomic absorption spectrophotometer；The medicine
Product reagent include 98% concentrated sulfuric acid, nitric acid, hydrochloric acid, without zinc water, perchloric acid, acetone, zinc sulfate, sodium chloride, common zinc powder, alloy
Zinc powder, high-purity zinc powder, antimony oxide, cupral, NaOH, kerosene, potassium permanganate etc..
The lime quality is described rich in silver, the 6%~10% of the fine powder quality of copper, the quality of calcium oxide in the lime
More than 80%, sulfuric acid content is 160~200g/L in the electrolyte, and the iron powder quality is silver, copper mass synthesis in calcining
1.2 times, iron content is more than 90% in the iron powder.
The 20g zinc abstractions waste residue is placed in six constant temperature blender with magnetic force, sulfuric acid, hydrochloric acid, nitric acid three is respectively adopted
Common acid is planted as leaching agent, concentration is respectively adopted for 0.25mol/L, 0.50 mol/L, 0.75 mol/L and 1.00
The sulfuric acid solution of mol/L, leaching time is 0.50h, 0.75h, 1.00h, 1.25h, 1.50h, 1.75h respectively, respectively in temperature
Spend to carry out waste residue leaching experiment at 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, its optimal leaching can be obtained
Agent is sulfuric acid, and optimal leaching agent concentration is 0.5mol/L, and optimal leaching time is 1h, and optimal test temperature is 25 DEG C, optimal liquid
Gu than being 10:1.
Optimal alloy zinc powder dosage is 12.50g/L in every liter of filtrate in the S5 steps；Optimal Sb2O3Consumption is
15mg/L, optimal high-purity zinc powder consumption is 20g/L.
It is 85 DEG C that the optimal reaction temperature of reaction is replaced in the S5 steps, and optimum reacting time is 90min, optimal PH
Be worth is 4.5.
With process pH value 3.5 during selectively leaching in the S6 steps, terminal PH is optimal when being 4.0 or so.
Zinc extraction test uses zinc synergic solvent extraction in the S7 steps, and extractant used is N235（Amine extractant）With
TBP（Tributyl phosphate）, diluent is kerosene, and extractant proportion of composing is 25%N235+30%TBP+45% coals during synergic solvent extraction
Oil, optimal chlorine ion concentration is 70g/L, is most preferably in a ratio of 3:1, optimal extraction time of contact is 4min.
It is kerosene that diluent used is tested in the S9 steps, and extractant is N235, is generated when extracting cobalt due to N235
Ionic compound have certain polarity, third phase is easily produced in extraction process, therefore use TBP（Tributyl phosphate）As
Additive eliminates third phase, and extractant proportion of composing is when nickel cobalt is extracted in the S9 steps：25%N235+30%TBP+45%
Kerosene, separates the optimal of nickel cobalt and is in a ratio of 2:1~3:1, optimal extraction time of contact is 3min.
Using single cavity block electrodeposition method, nickel uses dual membranes and three chambers electrodeposition to zinc using single anode membrane electrodeposition method, cobalt in the S12 steps
Method, single cavity block electrodeposition method optimum condition is：25 DEG C of normal temperature, pH value 4.5, electric current 400m A, electrodeposition time 34h；The list
Anode membrane electrodeposition method optimum condition is：25 DEG C of normal temperature, pH value 4.0~4.5, size of current are 350mA, electrodeposition time 44h；It is described
Dual membranes and three chambers electrodeposition method optimum condition is：25 DEG C of normal temperature, pH value 4.0, size of current 350mA, electrodeposition time 44h.
Claims (9)
1. a kind of method that valuable metal is reclaimed in waste residue from zinc abstraction, it is characterised in that the zinc abstraction waste residue is by net
The purification slag after iron is eliminated, the method for valuable metal is reclaimed in the waste residue from zinc abstraction to be included reclaiming silver, copper and recovery
Zinc, nickel, two stages of cobalt, the recovery silver, the stage of copper are that the silver in the purification slag is reclaimed by the fine powder rich in silver, copper
And copper, the recovery zinc, nickel, the stage of cobalt include that waste residue is leached, isolation of purified and electrode reclaim three phases again, including following
Step：
S1：It is 1.45~1.55 × 10 that the zinc abstraction waste residue is made into density3 kg/m3, the slurries that pH value is 5~5.8, slurry
Activating agent is added in liquid, is floatingly selected rich in silver, the slag of copper, the slag rich in silver, copper is added the lime of certain mass
Afterwards the calcining rich in silver, copper is obtained in 880~950 DEG C of roastings；
S2：The calcining rich in silver, copper is immersed in the electrolyte that temperature is 65~72 DEG C, pH value is 1.8~2.2, instead
1.5~2 hours between seasonable, then the calcining rich in silver, copper is leached from the electrolyte, filtering is after iron powder reducing
Can obtain rich in silver, the fine powder of copper；
S3：The zinc abstraction waste residue is crushed uniform again, prepares to reclaim the instrument and medicine and reagent used by zinc, nickel, cobalt；
S4：Determine that waste residue most preferably leaches condition test：The dry zinc abstraction waste residue several pieces of 20g are accurately weighed respectively to be tried
Test, the waste residue most preferably leach need in condition test control variable include leaching agent species, leaching agent concentration, liquid-solid ratio,
Leaching time and temperature, the waste residue most preferably leach the principle using single-factor variable during condition test, by optimal leaching
Take agent and determine experiment, the experiment of optimal leaching agent concentration tests, liquid-solid ratio, leaching time experiment and leaching temperature experiment, successively really
Make the optimal leaching condition of zinc abstraction waste residue in acid leaching stage；
S5：Zinc dust precipitation is tested except nickel cobalt：After the completion of the S4 steps, it is determined that optimal leaching under the conditions of, by the zinc
Melting waste slag dissolution filter, measures several pieces filtrate and is placed in beaker in right amount respectively, and being heated under identical mixing speed is carried out
Experiment, in process of the test, controls different alloy zinc powders or addition Sb respectively2O3High-purity zinc powder dosage, different reactions
Temperature, different reaction PH and reaction time, with nickel, cobalt displacement clearance as index, determine zinc dust precipitation except nickel cobalt try
The optimal displacement condition tested；
S6：Selectively leaching is tested：It is determined that optimal leaching under the conditions of dissolve waste residue obtained by filtrate, through displacement reaction after, zinc
Do not react completely, zinc, nickel and cobalt are still contained in the sediment after filtering, but the percentage composition of zinc has been substantially reduced, institute
It is exactly the percentage composition that zinc in sediment is further reduced on the basis of Zn content reduction to state Selectively leaching experiment,
The content of nickel and cobalt is improved, is beneficial to being smoothed out for follow-up test；
S7：Zinc is tested with nickel cobalt extract and separate：After the completion of the step S5 and S6, zinc in the zinc abstraction waste residue is remained in
Comparision contents are low, after filter residue is dissolved again with sulfuric acid, carry out zinc extraction test, zinc is entered organic phase through extracting, and nickel cobalt
It is not extracted, in remaining on raw water phase, so as to reach the purpose that zinc and nickel cobalt are completely separated；
S8：The back extraction experiment of zinc：After the completion of the step S7, zinc-rich organic phase is obtained, the back extraction experiment of the zinc is
On the basis of step S7, by organic phase after simply washing, the zinc taken out in organic phase is stripped with strippant, obtained in accordance with electricity
The pure zinc electrolyte that product is required；
S9：Nickel cobalt extract and separate is tested：After zinc and nickel cobalt extract and separate, nickel is not separated also with cobalt, in remaining on water phase, due to
Cobalt is more easy to enter organic phase compared with nickel, therefore nickel cobalt extract and separate experiment still uses solvent-extracted method；
S10：The back extraction experiment of cobalt：After the completion of the step S9, obtain rich cobalt organic phase, the rich cobalt organic phase through go from
After sub- water washing, with strippant through the available more pure cobalt electrolyte of multi-stage counter current extraction；
S11：Deep purifying is tested：After the completion of step S7, S8, S9, S10, more pure zinc electrolyte, nickel can be obtained
Electrolyte and cobalt electrolyte, by the available more pure electrolyte of the deep purifying；
S12：Electrodeposition reclaims zinc, nickel, cobalt experiment：In electrodeposition recovery stage, can respectively carry out electrodeposition and reclaim the zinc electrolyte, nickel
Metal in electrolyte and cobalt electrolyte, and by electrodeposition recovery test, optimal electricity when determining that zinc, nickel and cobalt electrodeposition are reclaimed
Product condition and the rate of recovery；
The stage for reclaiming silver-colored, copper includes above S1 and S2 step, the recovery zinc, nickel, waste residue leaching rank in the stage of cobalt
Section includes above S3, S4, S5 and S6 steps, and the isolation of purified stage includes above S7, S8, S9, S10 and S11 step, described
Electrode recovery stage includes S12 steps.
2. the method that valuable metal is reclaimed in the waste residue from zinc abstraction according to claim 1, it is characterised in that the lime
Quality is described rich in silver, the 6%~10% of the fine powder quality of copper, and the quality of calcium oxide is more than 80%, the electrolysis in the lime
Sulfuric acid content is 160~200g/L in liquid, and the iron powder quality is silver-colored in calcining, copper mass sum total 1.2 times, in the iron powder
Iron content is 90%.
3. the method that valuable metal is reclaimed in the waste residue from zinc abstraction according to claim 1, it is characterised in that the 20g
Zinc abstraction waste residue is respectively adopted sulfuric acid, hydrochloric acid, three kinds of common acids of nitric acid as leaching agent, and concentration is respectively adopted for 0.25mol/
The sulfuric acid solution of L, 0.50 mol/L, 0.75 mol/L and 1.00 mol/L, respectively leach 0.50h, 0.75h, 1.00h,
1.25h, 1.50h, 1.75h, carry out waste residue leaching at 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C respectively
Experiment is taken, is placed in six constant temperature blender with magnetic force, optimal leaching agent is sulfuric acid, optimal leaching agent concentration is 0.5mol/L, most
Good leaching time is 1h, and optimal test temperature is 25 DEG C, and optimal liquid-solid ratio is 10:1.
4. the method that valuable metal is reclaimed in the waste residue from zinc abstraction according to claim 1, it is characterised in that the S5 steps
Optimal alloy zinc powder dosage is 12.50g/L in every liter of filtrate in rapid；Optimal Sb2O3Consumption is 15mg/L, optimal high-purity zinc powder
Consumption is 20g/L.
5. the method that valuable metal is reclaimed in the waste residue from zinc abstraction according to claim 1, it is characterised in that the S5 steps
Suddenly the optimal reaction temperature of displacement reaction is 85 DEG C in, and optimum reacting time is 90min, optimal pH value is 4.5.
6. the method that valuable metal is reclaimed in the waste residue from zinc abstraction according to claim 1, it is characterised in that the S6 steps
With process pH value 3.5 during selectively leaching in rapid, terminal PH is optimal when being 4.0 or so.
7. the method that valuable metal is reclaimed in the waste residue from zinc abstraction according to claim 1, it is characterised in that the S7 steps
Zinc extraction test uses zinc synergic solvent extraction in rapid, and extractant proportion of composing is 25%N235+30%TBP+45% coals during synergic solvent extraction
Oil, optimal chlorine ion concentration is 70g/L, is most preferably in a ratio of 3:1, optimal extraction time of contact is 4min.
8. the method that valuable metal is reclaimed in the waste residue from zinc abstraction according to claim 1, it is characterised in that the S9 steps
Extractant proportion of composing is when nickel cobalt is extracted in rapid：25%N235+30%TBP+45% kerosene, separates the optimal of nickel cobalt and is in a ratio of 2:
1~3:1, optimal extraction time of contact is 3min.
9. the method that valuable metal is reclaimed in the waste residue from zinc abstraction according to claim 1, it is characterised in that the S12
Using single cavity block electrodeposition method, using single anode membrane electrodeposition method, cobalt uses dual membranes and three chambers electrodeposition method, single cavity block electricity to nickel to zinc in step
Area method optimum condition is：25 DEG C of normal temperature, pH value 4.5, electric current 400m A, electrodeposition time 34h；Single optimal bar of anode membrane electrodeposition method
Part is：25 DEG C of normal temperature, pH value 4.0~4.5, size of current are 350mA, electrodeposition time 44h；The dual membranes and three chambers electrodeposition method is most
Good condition is：25 DEG C of normal temperature, pH value 4.0, size of current 350m A, electrodeposition time 44h.
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| CN110862180A (en) * | 2018-08-28 | 2020-03-06 | 淄博泰典新材料有限公司 | Method and device for treating and recycling high-acid mercury-containing wastewater |
| CN108977666A (en) * | 2018-08-30 | 2018-12-11 | 河南豫光锌业有限公司 | The recovery method of zinc cobalt in a kind of purification slag of zinc hydrometallurgy |
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