CN108342569A - Method of the foreign metal cobalt to obtain zinc-containing solution is removed from crude zinc raw material - Google Patents
Method of the foreign metal cobalt to obtain zinc-containing solution is removed from crude zinc raw material Download PDFInfo
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- CN108342569A CN108342569A CN201711484554.3A CN201711484554A CN108342569A CN 108342569 A CN108342569 A CN 108342569A CN 201711484554 A CN201711484554 A CN 201711484554A CN 108342569 A CN108342569 A CN 108342569A
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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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
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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Abstract
Method of the foreign metal cobalt to obtain zinc-containing solution is removed from crude zinc raw material, this method includes：1) crude zinc solution is prepared with sulfuric acid dissolution crude zinc raw material；2) zinc powder that first part is added in crude zinc solution, is precipitated Spongy Cadmium, obtains the crude zinc solution for tentatively removing cadmium；3) potassium carbonate and resistance solvent are added, pH=4.8 5.8 times reactions generates nickel hydroxide precipitate, then heats up, zinc powder is added again and is reacted, removes cadmium again, obtains the zinc-containing solution except cadmium and nickel；4) potassium permanganate of addition first part is formed simultaneously manganese dioxide MnO by a part of ferrous ions in solution at the iron ion of trivalent2Precipitation, then hydrogen peroxide is added to be reacted, form the mangaic acid cobalt precipitation of indissoluble, then it heats up, continues the potassium permanganate for adding second part, reaction solution is rendered as blush or light red, then the pH of solution is adjusted in 5.0 5.8 ranges with calcium carbonate powder, then reaction is further heated up until red disappears, is separated off sediment, is obtained except the qualified zinc-containing solution after cobalt, iron and manganese.
Description
Technical field
The present invention relates to the purification techniques of zinc liquid, and in particular to removes foreign metal cobalt from crude zinc raw material and contains zinc to obtain
The method of solution.
Background technology
In existing zinc sulfate, zinc carbonate, electrolytic zinc production process, need purification remove harmful metal for example cobalt, nickel, cadmium,
Iron, manganese etc..In the factory, processes, the spelter liquid such as a net process, two net processes is typically provided with to remove by these cleaning procedures
Decontamination metal, to reach the control requirement of product.
Existing production zinc sulfate, zinc carbonate, electrolytic zinc centre Cobalt Purification, nickel, mainly use antimony-zinc alloy Zhi Change and sulphur
Change plus arsenic purifies, need that purification purpose can be reached, but still there are many shortcomings, embodies as follows：
1, of high cost using alloy zinc powder Zhi Change cobalts, nickel.It is mutually set because alloy zinc powder is homo-ion bilayer, first, the expensive conjunctions of Hao Ji
Golden zinc powder dosage is three times of molal quantity, therefore dosage is big；Second is that since potential difference is big, effect must be can be only achieved at high temperature, consumed
When consume energy；
2, there is the safety hazard hidden danger of burst to operating personnel.Since want in the solution can be single point with ionic condition for cobalt, nickel salt
From precipitation, the conversion of members of the same clan's ion is needed, thus is plus arsenic and sulphurizing salt play members of the same clan's transformation, when being saturated setting Change
When, metal ion participates in acid reaction and generates hydrogen effusion, and arsenate is closed with hydrogenation at this time, forms arsenic hydride distillation, pole
Poison, if people absorbs and is poisoned；Second is that having asphyxia hydrogen sulfide to generate with sulfide, people can also be poisoned after absorbing；
3, narrow to control claimed range, purification probability is low.Zinc sulfate, zinc carbonate use feed addictive, and extremely tight, nickel is required to nickel
Control is at 5 ppm grades, and alloy arsenic method, vulcanization can hardly reach, and causes current potential uneven in electrolysis, and short circuit rises
Pole plate, in addition to influencing electrolytic zinc quality, the also suspicion of halt production are burnt in boiling.
The zinc-containing solution that the prior art obtains is for generating zinc sulfate, zinc carbonate and electrolysis zinc solution.And works as and be used to be electrolysed
When zinc solution, nickel, cobalt difficulty are removed, and are led to zinc carbonate product colour greening, are blacked, downstream product quality are influenced, when as electrolytic zinc
When, since nickel and cobalt containing is excessively high in electrolyte, it is be easy to cause electric current short circuit of polar, burns pole plate, loss is big.
Invention content
The present invention removes nickel, cobalt in view of the deficiencies of the prior art, especially for long-standing problem those skilled in the art
Problem provides a kind of method except foreign metal cobalt in zinc liquid, can during except cadmium cleared nickel simultaneously, and except iron, manganese mistake
Disposable cleared cobalt in journey.
According to the present invention, the method that foreign metal cobalt is removed from crude zinc raw material is provided, this method includes：
1) crude zinc solution is prepared：Sulfuric acid is added in crude zinc raw material to be leached, crude zinc solution is obtained；
2) cadmium is tentatively removed：The zinc powder of first part is added in crude zinc solution, additive amount is enough to replace in crude zinc solution contained
Cadmium ion a part (such as 45-70% of cadmium ion total amount), cause Spongy Cadmium to be precipitated, obtain tentatively except cadmium crude zinc it is molten
Liquid；
3) it removes nickel and removes cadmium again：Add potassium carbonate in the crude zinc solution tentatively except cadmium, the additive amount of the potassium carbonate relative to
Be for nickel ion content in crude zinc solution molar excess (preferably, potassium carbonate is 1.3-2.5 times of the mole of nickel ion,
More preferably 1.6-2 times), and add resistance solvent (such as white sugar or tartaric acid, malic acid) hinder it is molten, at pH=4.8-5.8,
It is preferred that being reacted at pH=5.1-5.5, unstable nickelous carbonate NiCO is firstly generated3, then it is hydrolyzed into the hydroxide of indissoluble
Nickel (OH)2), that is, nickel hydroxide precipitate is generated, the is then added in the case of heating (such as being warming up to 45 DEG C -60 DEG C)
The zinc powder of two parts is reacted, and the addition of zinc powder is enough to replace in crude zinc solution the remaining whole cadmium ions of institute (such as cadmium
The remaining or remaining 55-30% of total ion concentration), it is separated by solid-liquid separation (such as being separated by filtration), obtains the zinc-containing solution except cadmium and nickel；
4) cobalt, iron and manganese are removed：In the zinc-containing solution except cadmium and nickel,（Such as in room temperature, such as 5-45 DEG C）Add first part
The additive amount of potassium permanganate, the potassium permanganate is sufficient to make manganese molar excess for cobalt, to which sulfuric acid in solution is sub-
Iron FeSO4Ferrous ion a part be oxidized to trivalent/iron ion, be formed simultaneously manganese dioxide MnO2Precipitation and optionally
Generate a small amount of MnSO4, （Its oxidation reaction is 5Fe2++ Mn7+=5Fe3++ Mn2+), hydrogen peroxide is then added, and (its dosage makes
Obtain H2O2For 1.5-5 times of the mole of potassium permanganate, preferably 2-3 times), (such as at PH=3.5-4.3, preferably 3.8-4.) into
Row oxidation reaction, this reaction is that the manganese dioxide that will be generated is allowed to be further oxidized to Manganate ions (MnO32+), and and cobalt
Ion forms mangaic acid cobalt [(the CoMnO3 2H of indissoluble2O) ↓] precipitation, then continue to add while heating (preferably slowly heating)
Add the potassium permanganate of second part so that until reaction solution is rendered as blush or light red, the potassium permanganate of second part
Additive amount be sufficient to make residual sulfuric acid ferrous iron by oxidation ferric sulfate, ferric sulfate hydrolysis generates iron hydroxide and optional a small amount of sulphur
Sour manganese is oxidized to manganese dioxide precipitate and optional a small amount of manganese sulfate MnSO4It is oxidized to generation manganese dioxide, the sulphur being precipitated at this time
Acid ion by with calcium carbonate powder adjust solution pH carried out in 5.0-5.8 ranges, preferably in 5.1-5.5 ranges in and
It is ferrous iron to prevent ferric iron from redissolving, then further heat up (such as it is warming up to 75-85 DEG C, and such as 78-82 DEG C, such as 80
DEG C), the reaction was continued until red disappears, you can separation (such as being separated by filtration) removes sediment (Fe (OH)3、MnO2And manganese
Sour cobalt (CoMnO3 2H2O) ↓) precipitation, obtain the qualified zinc-containing solution for removing cobalt, iron and manganese.
Above step 2) in, add a part of cadmiums of Xin Fen Zhi Change of first part, the purpose is to the current potentials of stablizing solution, prevent
Cadmium consumes potassium carbonate to heavy nickel.
Above step 3) in, due to the raising of hydrogen ion concentration under being acted in zinc, nickelous carbonate is made to be hydrolyzed into hydroxide rapidly
Nickel precipitates, and it is nickel sulfate that nickel hydroxide react back dissolving easily under faintly acid at this time, therefore plus such as 0.5 times of nickel mole organic
Resistance solvent (such as tartaric acid or multitudinous sugar, malic acid) hinders it.
Generally, above-mentioned crude zinc raw material is one or more in following raw materials according：
1) secondary zinc oxide of steel mill's volatilization, 2) copper (cigarette) ash and 3 that copper work volatilization is gathered dust) deposition of lead smeltery, contain Zn
Environmentally friendly slag.
Generally, crude zinc raw material contains the cadmium (atomic weight of the cadmium of 1.5-10wt%, preferably 2-7wt%, more preferable 3-5wt%：
112.41) nickel (atomic weight of, nickeliferous 0.5-5wt%, preferably 0.7-4wt%, more preferable 1-3wt%：58.69), 0.5- containing cobalt
5wt%, preferably 0.3-4wt%, more preferably (the cobalt atom amounts of 0.1-1.5wt% containing cobalt:And iron (the atom of 0.5-15wt% 58.933)
Amount：55.85).Key component is zinc (atomic weight：65.38).Generally, the molar content of iron is higher than the molar content of cobalt, such as Fe
:Co molar ratios=1.05-2: 1.
Generally, organic resistance solvent is organic reducing agent, preferably one kind or more in tartaric acid, sucrose or malic acid
Kind；Preferably, the dosage of resistance solvent is 0.1-3 times of the mole relative to nickel ion（It is preferred that 0.3-1.5 times, more preferably
0.4-1.2 times, such as 0.5 times）.
Preferably, in step 2), the additive amount of zinc powder is enough to replace cadmium ion total amount contained in crude zinc solution
45-70% (preferably 50-65%), and the addition of the zinc powder of second part is enough to replace and is remained in crude zinc solution in step 3)
Whole cadmium ions, i.e. the 55-30% (preferably 50-35%) of cadmium ion total amount.
It preferably,, can be when the mole of solution ferrous ions is less than the mole of cobalt ions in step 4)
Ferrous sulfate is added in solution so that the mole of solution ferrous ions is higher than the mole of cobalt ions.
It is preferred that in step 4), the additive amount of the potassium permanganate of first part accounts for the 20- of the total addition level of potassium permanganate
30wt%, the additive amount of the potassium permanganate of second part account for the 80-70wt% of the total addition level of potassium permanganate.
In this application, " optional " expression is with or without.
In the step 3) of the above method, by nickel ion mole 1.5-5 times (preferably 1.8-4.5 times, more preferable 2-
3.5 times) potassium carbonate is added.Because sulfuric acid can also consume potassium carbonate.
In step 3), by 0.1-3 times of nickel ion mole（It is preferred that 0.3-1.5 times, more preferable 0.4-1.2 times, such as
0.5 times）Organic resistance solvent (such as tartaric acid, sucrose and/or malic acid) is added.
In the qualified zinc-containing solution that the method for the present invention is obtained, nickel concentration is in 0.1-0.5MMg/L, and cobalt is in 0.1-
0.5MMg/L。
This invention simplifies purification process, during Zhi Change, disposable zincification powder, potassium carbonate, in auxiliary agent tartaric acid or
Under the action of sucrose or malic acid, during except cadmium simultaneously cleared nickel；In subsequent removing of iron and manganese process, same kettle increases manganese
Sour potassium, hydrogen peroxide, disposable cleared cobalt, ferrimanganic, to reach in solution of zinc sulfate to nickel cobalt requirement and electrolyte requirement.
The qualified zinc-containing solution that the present invention obtains can be used for generating zinc sulfate, zinc carbonate and electrolysis zinc solution.
The cleared nickel of the present invention, the chemism of cobalt are as follows：
1, nickel is removed:NiSO4+k2CO3=k2SO4+NiCO3
NiCO3+H2O=Ni(OH)2↓+CO2↑
2, cobalt is removed:2CoSO4+2kMnO4+5H2O2
=2(CoMnO3•2H2O)↓+k2SO4+H2SO4+4O2
Note：This reaction equation is that cobaltous sulfate is oxidized to one formula of cobaltous sulfate into simplified style, the reaction of really two steps, i.e. potassium permanganate
In hydrogen peroxide initial oxidation at Manganate ions, mangaic acid and sulfuric acid are then reacted into cobaltous sulfate again and releases oxygen
The present invention is used except nickel is in the crude zinc liquid for enter leaching using mechanism 1 plus potassium carbonate, and Zhi Change processes carry out；It is first surveyed
When PH4.5 to 5, the 15-35 ℅ of zincification powder total amount An Zhi Change cadmium moles total numbers, at this time a part of cadmium Yi Zhi Change.For example, in reality
It applies in example, first adds 15kg (i.e. 50%) zinc powder, add 15kg (i.e. 50%) zinc powder afterwards, for the sake of guarding, calculate lower zinc powder 15 by volume
Kilogram amount just becomes 50 ℅ of practical zinc total amount.The purpose is to stable potentials, and cadmium is prevented to consume potassium carbonate, sponge to be had to heavy nickel
After cadmium is precipitated, by 1.6-2 times (such as 1.8 times) plus potassium carbonate of nickel mole；Due to the liter of hydrogen ion concentration under being acted in zinc
Height makes nickelous carbonate be hydrolyzed into nickel hydroxide precipitate rapidly, and it is nickel sulfate that nickel hydroxide reacts back dissolving easily under faintly acid at this time, therefore
0.3 times of the tartaric acid or multitudinous sugar, malic acid for adding nickel (mole) amount hinder it；It, will be remaining after this reaction controlling 30 minutes or 1 hour
Zinc powder is added, and temperature is controlled at 45 DEG C -60 DEG C, and the qualified zinc sulfate solution of nickel is obtained by filtration in time 1-3 hour；
Then, the cobalt that removes of the invention is carried out at the same time in except iron, manganese process, it is will to remove nickel, cadmium, copper filtered fluid in low Warm
The 20-30 ℅ amounts except ferromanganese potassium permanganate total amount are added in by processing solution, then potassium permanganate molar amount is added
2-3 times of hydrogen peroxide of calculation, is warming up to 60 DEG C after twenty minutes, and surplus potassium permanganate is added to blush, is warming up to 75-85 DEG C,
PH value is adjusted to 5.1-5.5 with 80 mesh Paris whites, and after 1 hour, red, which disappears, may filter that, solid phase is iron, manganese, cobalt
Slag, liquid phase are qualifying liquid, for production zinc sulfate, zinc carbonate, electrolytic zinc.
Advantages of the present invention
Compared with prior art, the present invention provides a kind of zinc sulfate, zinc carbonate, electrolytic zinc production in solution purification when except cobalt,
The new method of nickel, it has instead of conventional alloy zinc powder, the classical way of arsenic trioxide Fa Zhi Change cobalts, nickel except cobalt, nickel
Thoroughly, the advantages that at low cost, environmentally friendly and technology controlling and process is easy.
Description of the drawings
Fig. 1 is that the purification of the prior art removes nickel cobalt control flow；
Fig. 2 is that the purification of the present invention removes nickel cobalt control flow.
Specific implementation mode
It is crude zinc or wash slag or secondary zinc oxide suitable for the zinc-containing raw materials in the present invention, such as：1) steel mill waves
The secondary zinc oxide of hair, 2) copper (cigarette) ash that copper work volatilization is gathered dust, 3) deposition of lead smeltery, the environmentally friendly slag containing Zn and Pb, etc.
Deng.
For the assay method of metal element content in zinc-containing raw materials, using analysis method well known in the prior art.Zn
Volumetric precipitation method is used with Cd contents, uses EDTA as complexing agent, xylenol orange is as indicator.And Ni, Co, Fe and Mn contain
Amount then uses atomic absorption spectrography (AAS).
1) cadmium and nickel are removed：Zinc-containing raw materials sulfuric acid to leach obtains crude zinc solution after filtering.It is added for the first time into solution
Zinc powder is interference of the cadmium sulfate to later separation in order to prevent, cadmium ion is allowed to be precipitated in the form of Spongy Cadmium.Then, in solution
After middle addition potassium carbonate, pH=5.1-5.5 is controlled, nickelous carbonate is settled out.But due to nickelous carbonate NiCO3It is unstable, it is easy hydrolysis
Form hydroxide nickel (OH)2Precipitation since easily reaction back dissolving is nickel sulfate to nickel hydroxide under mildly acidic conditions at this time, therefore adds
Enter a certain amount of tartaric acid or sucrose, malic acid prevent nickel hydroxide back dissolving；Then remaining zinc powder is added, further allows solution
In remaining cadmium sulfate restore and Spongy Cadmium be precipitated.
2) iron (Fe), manganese (Mn) and cobalt (Co) are removed：Add in the solution for having removed cadmium and nickel obtained in step 1)
Increase potassium manganate, by ferrous sulfate FeSO4In (part) ferrous ions at the iron ion of trivalent, and form titanium dioxide
Manganese MnO2Precipitation, generates a small amount of MnSO4.Then hydrogen peroxide is added, PH=4.8-5 is controlled, manganese dioxide is allowed further to aoxidize simultaneously
And mangaic acid cobalt [(the CoMnO3 2H of indissoluble are formed with cobalt ions2O) ↓] precipitation.Mangaic acid root is easiest to that cobalt ions is combined to form precipitation
Object.Contain ferrous sulfate FeSO in solution4With potassium permanganate (KMnO4), be added hydrogen peroxide after be precipitated mangaic acid cobalt after, however add
Remaining potassium permanganate, allows solution that blush is presented, and heating adjusts solution ph to 5.1-5.5 with calcium carbonate, reacts 1 hour
Afterwards, red disappearance, wherein potassium permanganate with manganese sulfate MnSO of this part4With remaining ferrous sulfate pH is adjusted in calcium carbonate
In the case of reacted, generate K2SO4、Fe(OH)3With Mn (OH)2, and unstable Mn (OH)2Resolve into MnO2Precipitation, table
Bright Fe, Mn and Co coloured ion is substantially all to be removed from solution.
Generally, in above-mentioned the 1) stage, the cadmium ion of 50-65% is removed first, then removes the cadmium ion of 50-35%.
Preferably, the cadmium ion for first removing about 50%, then removes about 50% cadmium ion.
Embodiment 1
In the present embodiment, the secondary zinc oxide of steel mill's volatilization is used as crude zinc raw material.It contains the cadmium of 4.0wt%, the nickel of 2.0wt%,
With the cobalt of 1.8wt% and the iron of 3.2wt%.
The crude zinc raw material of 1290 kg is added in the washings of 3870 kilograms of cycles, the concentrated sulfuric acid (98 of addition
℅), it participates in that sulfuric acid concentration is in 50wt ℅ or so after being reacted into kettle, after allowing it fully react, leach, dissolving, filters acquisition crude zinc
Solution.
Gained crude zinc solution is put into 15 M3In the replacement reaction kettle of volume.Stirring is started, at normal temperatures, 15kg is added
Metal zinc prevents cadmium sulfate from interfering subsequent separation, there is Spongy Cadmium precipitation, obtains the crude zinc solution for tentatively removing cadmium.Work as sponge
Cadmium be precipitated after, in solution nickel concentration be 0.015g/L, add 40 kilograms of potassium carbonate and as resistance solvent 5 kilograms of tartaric acid (or
Multitudinous sugared 6 kilograms), pH=5.1-5.5 reacts 30 minutes to 1 hour, is warming up to 45 DEG C -60 DEG C, remaining 15 kilograms of zinc powders are added
Enter, the reaction was continued to after -1 hour 30 minutes, and the nickel content surveyed in solution is 0.01mg/L, by being filtered with plate and frame filter press,
Implement to be separated by solid-liquid separation；Obtain the zinc-containing solution (filtrate) except cadmium and nickel；Cadmium content is that nickel content is 0.01 mg/L.
The zinc-containing solution obtained is transferred to 15 M3 and removes iron reaction kettle, stirring is opened, surveys its temperature at 30-45 DEG C, add
Enter the potassium permanganate 15kg calculated by cobalt mole, after having manganese dioxide precipitation, hydrogen peroxide (a concentration of 35wt%) 40 is added
Kg reacts 0.5h, and PH is 4.8-5 at this time, after mangaic acid cobalt is precipitated, remaining potassium permanganate is added in heating, until liquid is in micro- red
Color adjusts pH to 5.1 with calcium carbonate powder, increases temperature to 80 DEG C, reacts 2h, after red disappears, detecting its cobalt content is
0.01mg/L obtains the qualified zinc-containing solution except cobalt, iron and manganese.
From the point of view of the feedback in downstream producer application process, when above-mentioned qualified zinc-containing solution is used as electrolysis zinc solution, success
Ground avoids electric current short circuit of polar, burns the phenomenon that pole plate.
Claims (9)
1. removing method of the foreign metal cobalt to obtain zinc-containing solution from crude zinc raw material, this method includes：
1) crude zinc solution is prepared：Sulfuric acid is added in crude zinc raw material to be leached, crude zinc solution is obtained；
2) cadmium is tentatively removed：The zinc powder of first part is added in crude zinc solution, additive amount is enough to replace in crude zinc solution contained
Cadmium ion a part (such as 45-70% of cadmium ion total amount), cause Spongy Cadmium to be precipitated, obtain tentatively except cadmium crude zinc it is molten
Liquid；
3) it removes nickel and removes cadmium again：Add potassium carbonate in the crude zinc solution tentatively except cadmium, the additive amount of the potassium carbonate relative to
Be for nickel ion content in crude zinc solution molar excess (preferably, potassium carbonate is 1.3-2.5 times of the mole of nickel ion,
More preferably 1.6-2 times), and resistance solvent is added, it is reacted at pH=4.8-5.8, preferably at pH=5.1-5.5, generates hydrogen
Nickel oxide precipitates, and the zinc powder that second part is then added in the case of heating (such as being warming up to 45 DEG C -60 DEG C) is reacted,
The addition of zinc powder be enough to replace in crude zinc solution remaining whole cadmium ions (such as 55-30% of cadmium ion total amount), solid-liquid
It detaches (such as being separated by filtration), obtains the zinc-containing solution except cadmium and nickel；
4) cobalt, iron and manganese are removed：In the zinc-containing solution except cadmium and nickel,（Such as in room temperature, such as 5-45 DEG C）Add first part
The additive amount of potassium permanganate, the potassium permanganate is sufficient to make manganese molar excess for cobalt, to which sulfuric acid in solution is sub-
Iron FeSO4The part of ferrous ion be oxidized to the iron ion of trivalent, be formed simultaneously manganese dioxide MnO2It precipitates and optionally raw
At a small amount of MnSO4, hydrogen peroxide is then added, and (its dosage makes H2O2For 1.5-5 times of the mole of potassium permanganate, preferably 2-3
Times), (such as at PH=4.5-5.3, preferably 4.8-5) carry out oxidation reaction, allow manganese dioxide further aoxidize and with cobalt from
Son forms mangaic acid the cobalt [(CoMnO of indissoluble3•2H2O) ↓] precipitation, then continue to add while heating (preferably slowly heating)
The potassium permanganate of second part so that until reaction solution is rendered as blush or light red, the potassium permanganate of second part
Additive amount is sufficient to make residual sulfuric acid ferrous iron by oxidation ferric sulfate, and ferric sulfate hydrolysis generates iron hydroxide and optional a small amount of sulfuric acid
Manganese is oxidized to manganese dioxide precipitate and optional a small amount of manganese sulfate MnSO4Be oxidized to generation manganese dioxide, the sulfate radical of precipitation from
Son by with calcium carbonate powder adjust solution pH carried out in 5.0-5.8 ranges, preferably in 5.1-5.5 ranges in and, prevent
It is ferrous iron that ferric iron, which redissolves, then further heat up (such as it is warming up to 75-85 DEG C, and such as 78-82 DEG C, such as 80 DEG C), continue to add
Potassium permanganate so as to oxidized residual manganese sulfate to blush, be heated up under conditions of red disappear, you can separation (such as mistake
Filter separation) remove sediment (Fe (OH)3、MnO2With mangaic acid cobalt (CoMnO3 2H2O) ↓ precipitation), obtain remove cobalt, iron and manganese it
Zinc-containing solution afterwards.
2. according to the method described in claim 1, it is characterized in that：Crude zinc raw material is one kind or more in following raw materials according
Kind：
1) steel mill volatilization secondary zinc oxide, 2) copper work volatilization gather dust copper ash or Bellamya aeruginosa and 3) deposition of lead smeltery, contain
The environmentally friendly slag of Zn.
3. method according to claim 1 or 2, it is characterised in that：Crude zinc raw material contains the cadmium of 1.5-10wt% (more typically
The cadmium of 2-7wt%), the nickel of 0.5-5wt%, the cobalt (atomic weight of 0.5-4.5wt%:And iron (the atomic weight of 0.5-9wt% 58.933)：
55.85)。
4. according to the method described in any one of claim 1-3, it is characterised in that：The resistance solvent is tartaric acid, sucrose
Or it is one or more in malic acid；Preferably, the dosage of resistance solvent is 0.1-3 times of the mole relative to nickel（It is preferred that
0.3-1.5 times）.
5. according to the method described in any one of claim 1-4, it is characterised in that：In step 2), the additive amount of zinc powder
It is enough to replace the 45-70% (preferably 50-65%) of cadmium ion total amount contained in crude zinc solution, and the second part in step 3)
The addition of zinc powder is enough to replace the remaining whole cadmium ions of institute in crude zinc solution, i.e. the 55-30% of cadmium ion total amount is (preferably
50-35%)。
6. according to the method described in any one of claim 1-5, it is characterised in that：In step 4), when ferrous in solution
When the mole of ion is less than the mole of cobalt ions, ferrous sulfate can be added in the solution so that solution ferrous ions
Mole is higher than the mole of cobalt ions.
7. according to the method described in any one of claim 1-6, it is characterised in that：In step 4), the height of first part
The additive amount of potassium manganate accounts for the 20-30wt% of the total addition level of potassium permanganate, and the additive amount of the potassium permanganate of second part accounts for Gao Meng
The 80-70wt% of the total addition level of sour potassium.
8. according to the method described in any one of claim 1-7, it is characterised in that：In the step 3) of the above method, press
1.5-5 times of (preferably 1.8-4.5 times, more preferable 2-3.5 times) addition potassium carbonate of nickel ion mole.
9. according to the method described in any one of claim 1-8, it is characterised in that：In step 3), by nickel ion mole
0.1-3 times of amount（It is preferred that 0.3-1.5 times, more preferable 0.4-1.2 times, such as 0.5 times）Organic resistance solvent (such as winestone is added
Acid, sucrose and/or malic acid).
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| CN109666800A (en) * | 2019-01-22 | 2019-04-23 | 中南大学 | One kind removing cobalt agent and its application |
| CN110358915A (en) * | 2019-07-11 | 2019-10-22 | 兰州理工大学 | A kind of method of nickel and cobalt ions in separation electrolytic solution |
| CN111172408A (en) * | 2020-01-20 | 2020-05-19 | 昆明瀚创科技有限公司 | Equipment for continuously and deeply purifying zinc sulfate solution to remove nickel, cobalt and germanium and control method |
| CN111235407A (en) * | 2020-03-04 | 2020-06-05 | 济源市鲁泰纳米材料有限公司 | Method for purifying aluminum-containing secondary zinc oxide leaching solution and aluminum removal method |
| CN113383115A (en) * | 2019-02-08 | 2021-09-10 | 阿文尼公司 | Electrodeposition of cobalt or copper alloys and their use in microelectronics |
| CN113785080A (en) * | 2019-05-01 | 2021-12-10 | 维诺德·秦塔马尼·玛尔什 | Effective utilization of jarosite waste |
| CN115710011A (en) * | 2022-11-30 | 2023-02-24 | 中冶瑞木新能源科技有限公司 | Method for recovering and preparing basic zinc carbonate from nickel-cobalt impurity-removing extraction back-extraction zinc liquid |
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| CN109666800A (en) * | 2019-01-22 | 2019-04-23 | 中南大学 | One kind removing cobalt agent and its application |
| CN109666800B (en) * | 2019-01-22 | 2020-11-24 | 长沙华时捷环保科技发展股份有限公司 | Cobalt removing agent and application thereof |
| CN113383115A (en) * | 2019-02-08 | 2021-09-10 | 阿文尼公司 | Electrodeposition of cobalt or copper alloys and their use in microelectronics |
| CN113785080A (en) * | 2019-05-01 | 2021-12-10 | 维诺德·秦塔马尼·玛尔什 | Effective utilization of jarosite waste |
| CN110358915A (en) * | 2019-07-11 | 2019-10-22 | 兰州理工大学 | A kind of method of nickel and cobalt ions in separation electrolytic solution |
| CN111172408A (en) * | 2020-01-20 | 2020-05-19 | 昆明瀚创科技有限公司 | Equipment for continuously and deeply purifying zinc sulfate solution to remove nickel, cobalt and germanium and control method |
| CN111235407A (en) * | 2020-03-04 | 2020-06-05 | 济源市鲁泰纳米材料有限公司 | Method for purifying aluminum-containing secondary zinc oxide leaching solution and aluminum removal method |
| CN115710011A (en) * | 2022-11-30 | 2023-02-24 | 中冶瑞木新能源科技有限公司 | Method for recovering and preparing basic zinc carbonate from nickel-cobalt impurity-removing extraction back-extraction zinc liquid |
| CN115710011B (en) * | 2022-11-30 | 2024-03-19 | 中冶瑞木新能源科技有限公司 | Method for recycling and preparing basic zinc carbonate from nickel cobalt impurity removal extraction strip zinc liquid |
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