CN107385217A - The processing method of metal waste liquid and the method for reclaiming metal - Google Patents
The processing method of metal waste liquid and the method for reclaiming metal Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/28—Fluorides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- 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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- C—CHEMISTRY; METALLURGY
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- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching 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
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
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- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
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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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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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
- C22B47/00—Obtaining manganese
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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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Abstract
The present invention relates to metal recovery field, and in particular to a kind of processing method of metal waste liquid and the method for reclaiming metal.The processing method of the metal waste liquid comprises the following steps：Raw material is carried out to the operation of preliminary deliming, separation copper, depth removing calcium and magnesium and separation of Zinc.Each metal ion species in original removal of impurities liquid can be formed different materials by the technique, are carried out secondary recovery and utilization, are economized on resources, while avoid the metal ion pollution environment in removal of impurities liquid.
Description
Technical field
The present invention relates to metal recovery field, and in particular to a kind of processing method of metal waste liquid and the side for reclaiming metal
Method.
Background technology
Hydrometallurgy is metalliferous mineral raw material to be chemically treated or organic in the aqueous solution of acid medium or alkaline medium
Solvent extraction, separation impurity, the process for extracting metal and its compound.Cobalt hydrometallurgical extraction is to extract cobalt from metallic ore material
The technique taken out, but because the complicated component of metalliferous mineral matter to the material being obtained by extraction, it is necessary to clean, but remove
During miscellaneous essential meeting by required cobalt ions be incorporated into removal of impurities liquid in, meanwhile, clean liquid in containing various metals from
Son, if simply excluding the removal of impurities liquid, the waste of resource can be caused, while the liquid that cleans arbitrarily is toppled over and also easily causes environment dirty
Dye.
The content of the invention
It is an object of the invention to provide a kind of processing method of metal waste liquid, the technique can will be each in original removal of impurities liquid
Metal ion species form various materials and carry out secondary recovery, economize on resources, while avoid metal waste liquor contamination environment.
, can be quickly by the Co-Mn metal in waste liquid another object of the present invention is to provide a kind of method for reclaiming metal
Ion is reclaimed.
The present invention is solved its technical problem and realized using following technical scheme：
The present invention proposes a kind of processing method of metal waste liquid, comprises the following steps：Raw material is subjected to preliminary deliming, separation
The operation of copper, depth removing calcium and magnesium and separation of Zinc.
The present invention proposes a kind of method for reclaiming metal, includes the processing method of above-mentioned metal waste liquid.
The processing method of metal waste liquid of the present invention and reclaim the beneficial effect of method of metal and be：Using calcium, copper, magnesium,
The characteristic of zinc metal ion, different precipitations and anti-stripping agent are formed, then using these precipitations and anti-stripping agent as production
The raw material of the materials such as cement, anode material for lithium-ion batteries, manganese-zinc ferrite magnetic material, avoids the waste of resource, simultaneously
Metal discharging of waste liquid can effectively be avoided and caused by environmental pollution.The processing method of whole metal waste liquid is simple to operate simultaneously,
Operating condition is easily achieved.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional production that can be obtained by commercially available purchase
Product.
In the description of the invention, it is necessary to which explanation, term " first ", " second " etc. are only used for distinguishing description, without
It is understood that to indicate or implying relative importance.
The processing method of metal waste liquid and the method for recovery metal of the embodiment of the present invention are specifically described below.
A kind of processing method of metal waste liquid provided in an embodiment of the present invention, comprises the following steps：
S1, preliminary deliming；
First, the raw material used for cobalt hydrometallurgical extraction in clean caused by P204 processes i.e. dioctylphosphoric acid ester process
Liquid, or P204 processes are that removal of impurities liquid forms slag containing Mn after alkali precipitation caused by dioctylphosphoric acid ester process.It is above-mentioned
Clean in liquid or slag containing Mn containing substantial amounts of calcium ion, copper ion, zinc ion, the cobalt ions of part and substantial amounts of manganese from
Son, calcium ion, copper ion, zinc ion are formed into different materials progress is separated from above-mentioned removal of impurities liquid or slag containing Mn
Secondary recovery and utilization again, meanwhile, it is capable to obtain the higher cobalt and manganese solution of purity, lift the production effect of Co-Mn metal
Rate.
The method of preliminary deliming needs to carry out appropriate regulation according to the difference of raw material, when raw material is in cobalt hydrometallurgy
Caused by P204 abstraction impurity removals process during removal of impurities liquid, removal of impurities liquid is mixed with sulfate, sulfate is dissolved in water and forms corresponding gold
Belong to ion and sulfate ion, sulfate ion reacts with calcium ion in removal of impurities liquid and generates calcium sulfate precipitation.The sulphur of formation
Sour calcium as the raw material of production cement, can improve the value of discarded metal.
Further, the mol ratio of calcium ion and sulfate is 1 in removal of impurities liquid：1.8-2.2, protected using the sulfate of excess
Calcium ion in card removal of impurities liquid can be acted on fully with sulfate radical, form precipitation.Then carry out filtering off sulfuric acid calcium so that
Calcium ion in removal of impurities liquid is removed.After filtering, reuse corresponding sulfate and rinse calcium sulfate precipitation so that original sulfuric acid
The calcium ion not being precipitated that calcium surface may be adhered to is precipitated completely, then lifts the deposition efficiency of calcium ion.
It is further preferred that the sulfate used is sodium sulphate, the purchase cost of sodium sulphate is low, can effectively reduce whole
The cost of the processing method of metal waste liquid.Calcium ion and the calcium sulfate of sulfate radical reaction generation are white precipitate, therefore, are carried out
Filter to remove calcium ion.
When raw material is the slag containing Mn obtained after alkali precipitation, contain part manganous compound in slag containing Mn,
Such as manganous hydroxide, manganese carbonate etc.；And high price manganese compound, such as manganese dioxide, manganese sesquioxide managnic oxide etc. and other metals
Compound (for example, copper compound, zinc compound and cobalt compound), and also contain high price cobalt compound, and bivalent manganese chemical combination
Thing and bivalent Co are dissolved in acid solution, and high price manganese compound and high price cobalt compound do not dissolve in acid solution then, still
High price manganese compound and high price cobalt compound can be changed into manganous compound and bivalent Co by redox reaction,
It can be dissolved in acid solution, then form the soluble-salt of cupric manganese cobalt zinc.Specifically, first slag containing Mn and sulfuric acid are mixed
Close so that the non-high price cobalt manganese such as manganous compound, copper compound, zinc compound and bivalent Co in slag containing Mn
Compound is dissolved in sulfuric acid.And the addition of sulfuric acid is determined according to the pH value of slag containing Mn and sulfuric acid mixture.
The pH of the mixed liquor of sulfuric acid and slag containing Mn is 1-2, ensure that the various non-high price Co-Mn compounds in slag containing Mn are all molten
Solution is in sulfuric acid.
Then reducing agent and sulfuric acid are mixed with the mixed liquor of slag containing Mn, reducing agent can with it is undissolved in mixed liquor
Redox reaction occurs for high price manganese compound and high price cobalt compound so that value Mn is reduced to bivalent manganese, high price cobalt quilt
Divalence cobalt is reduced to, is then dissolved in mixed solution.Wherein addition reducing agent causes the mixed of reducing agent, sulfuric acid and slag containing Mn
The black precipitate closed in liquid disappears, and represents all value Mn, high price cobalt has been reduced to bivalent manganese entirely and divalence cobalt is then molten
Solution is in sulfuric acid.
Further, reducing agent is any one in sodium sulfite, sulfur dioxide or hydrogen peroxide or at least two.It is above-mentioned
Reducing agent quickly can react with value Mn and high price cobalt, be reduced to bivalent manganese and divalence cobalt, then ensure slag containing Mn
All it is dissolved.
And the calcium ion in sulfuric acid is dissolved in, combined with sulfate ion, form the calcium sulfate precipitation of white.Then incited somebody to action
Sulfuric acid calcium is filtered off, tentatively to remove calcium ion.
S2, separation copper；
Raw material after preliminary deliming is further removed into copper ion, goes copper removal there are 3 kinds of methods, first, by after preliminary deliming
Raw material with extraction DDTC to be in a ratio of 1:1-1.5 ratio is mixed so that the copper ion in raw material after preliminary deliming
It is extracted into organic phase, then carries out Liquid liquid Separation, the raw material after preliminary deliming is divided into organic phase and aqueous phase, aqueous phase continues
Follow-up removal of impurities, and organic phase then utilizes sulfuric acid, and copper sulphate is formed with copper ion, then takes out copper ion back extraction.Back extraction
The copper sulphate obtained as the raw material of copper smelting plant, can then improve the utilization rate of copper ion.
Further, it is oxime compound or aldehyde oxime compound to extract DDTC.Oxime (oxime), is containing carbonyl
The organic compound that aldehyde, ketone compounds and azanol are acted on and generated, formula all have C=NOH bases.The oxime formed by aldehyde claims aldehyde
Oxime, the oxime formed by ketone claim ketoxime.Copper ion has good intersolubility with oxime compound or aldehyde oxime compound so that copper
Ion can be extracted by oxime compound or aldehyde oxime compound.
Oxime compound includes appointing in methyl ethyl ketoxime, DMKO, cyclohexanone oxime, acetophenone oxime and dimethylglyoxime
Meaning one kind or at least two.Methyl ethyl ketoxime, alias diacetylmonoxime, methyl ethyl ketone oxime, colourless oil liquid.It is mainly used in alkyd
Cold coating anti skinning agent and silicon curing agent, and boiler water system deoxidier etc..DMKO (English name
Dimethyl-Ketoxime acetoxime (Acetoneoxime), 2- acetoximes (2-Propanone oxime), abbreviation) are also known as
DMKO.It is white flaky crystals under normal temperature, volatilizees in atmosphere quickly, has like chloraldurate smell.It is soluble in water, it also is soluble in
The organic solvents such as alcohol, ether, ketone, hydrocarbon, petroleum ether.
Cyclohexanone oxime white prism-shaped crystal.89-90 DEG C of fusing point, 206-210 DEG C of boiling point.It is dissolved in water, ethanol, ether, methanol.
Acetophenone oxime is a kind of chemical substance, and molecular formula is:C8H9NO.Dimethylglyoxime, Chinese：Diacetyl dioxime；2,3- diacetyl
Dioxime；Dimethylglyoxime；Dimethyl glyoxime；Fourth dioxime；It is tiltedly crystallized for white three or crystalline powder.It is dissolved in ethanol, second
Ether, acetone and pyridine, are practically insoluble in water.238~240 DEG C of fusing point.Minimum lethal dose (rat, oral) 250mg/kg.
Aldehyde oxime compound includes formaldoxime, butyl aldoxime, trimethylacetaldoxime, Chinese cassia tree aldoxime, 9- anthracenes aldoxime, 4- nitro benzaldehydes
Any one in oxime, benzaldoxime, salicylaldoxime, acetaldoxime or at least two.Formaldoxime is colourless liquid, and chemical formula is
CH3NO, in chemistry for colorimetric estimation manganese, copper, nickel, cobalt.Butyl aldoxime is colourless, transparent, oily liquids, and molecular formula is
C4H9NO, it is mainly used as organic reagent.Chinese cassia tree aldoxime is a kind of chemicals, English name:CINNAMALDEHYDE OXIME, often
Eyes, respiratory system and skin are stimulated in medicine synthesis and cinnamylaldehyde derivatives.
Further, the concentration of the sulfuric acid used is 180-200g/l, and abundance can be provided using the sulfuric acid of the concentration
Sulfate ion, at the same will not due to sulfuric acid excessive concentration and initiated oxidation reduction reaction, ensure the raw material after preliminary deliming
The species and quantity of interior foreign ion will not increase or change.Meanwhile the sulfuric acid of the concentration can quickly with tentatively
Raw material mixing after deliming, and then accelerate the combination of sulfate radical and copper ion, accelerate the formation of copper sulphate, then ensure to remove copper removal
The effect of ion.And sulfuric acid and organic phase are to be in a ratio of 1:1-1.5 ratio mixing.Sulfuric acid using aforementioned proportion can completely by
Copper ion back extraction in organic phase.What the concentration of sulfuric acid represented be 1 liter of organic phase and sulfuric acid mixed solution in sulfuric acid contain
Measure as 180-200g.
When separation copper is carried out by the way of above-mentioned extraction and back extraction, it is necessary to repeatedly extract and be stripped, with this,
Ensure the effect of separation copper.For example, using Liquid liquid Separation after DDTC mixes with the raw material after preliminary deliming is extracted, extraction copper is recycled
Reagent mixes once and again Liquid liquid Separation with the raw material after preliminary deliming again, then by be obtained by extraction twice it is organic mix after
Mix, copper ion back extraction is taken out, while the organic phase mixed can also repeatedly mix with strippant with strippant again.
The embodiment of the present invention be also not necessarily limited to it is described twice, can also be 3 extractions, back extraction；Or 4 extractions, 3 back extraction.
The method of second of separation copper mix the raw material after preliminary deliming with alkaline matter so that alkaline matter and first
The pH value for walking the mixed solution of the raw material after deliming is 4-4.5.The pH value of raw material after preliminary deliming is 1-2, and it has strong acid
Property, then adds alkaline matter, the copper in raw material after the hydroxide ion that alkaline matter ionizes in water, with preliminary deliming from
Son combines, and generates the Kocide SD of blueness.If the pH value for the solution that the raw material after preliminary deliming mixes with alkaline matter is not sent out
Changing, illustrate that alkaline matter is not excessive, also have part copper ion not remove in the raw material after possible preliminary deliming.It is and if preliminary
The pH value for the solution that raw material after deliming mixes with alkaline matter changes, and illustrates that copper ion has removed totally, because hydrogen-oxygen
After the completion of radical ion is only combined with copper ion, it is only possible to that neutralization reaction occurs with the hydrogen ion in solution, then causes solution
PH value changes.
And the pH value set is set as 4-4.5, ensure that solution is still acidity so that other metal ions still have
In solution, it is easy to then cause corresponding metal from the isolated corresponding metallic compound of solution subsequently by metal ion
Compound can be applied to different fields, lift the utilization rate of waste liquid.Solution after preliminary deliming mixes and anti-with alkaline matter
Kocide SD precipitation should be obtained, then filters off except Kocide SD, then removes copper ion.And the Kocide SD generated can also be made
For the raw material of copper smelting plant.
Further, the alkaline matter used in the method for second of separation copper includes sodium hydroxide, potassium hydroxide, carbonic acid
Any one in sodium, potassium carbonate, sodium acid carbonate, saleratus, ammonium hydrogen carbonate, ammonium carbonate, ammoniacal liquor or at least two.
Method of the third separation copper is by the raw material after preliminary deliming and nickel powder either cobalt powder or manganese powder or its group
Compound is mixed, and displacement reaction then occurs so that copper ion is replaced out, and corresponding nickel, cobalt or manganese are with ion
Form is present with solution, then carrying out filtering off copper removal.
Further, either cobalt powder or manganese powder or its composition carry out mixing it raw material after preliminary deliming with nickel powder
Before, the pH value of the raw material after preliminary deliming is adjusted to 3-3.5 using alkaline matter, necessary reaction ring is provided for displacement reaction
Border.
S3, depth removing calcium and magnesium；
Although having eliminated the calcium in raw material in aforementioned operation, because calcium and magnesium is with respect to metals such as copper ion, zinc ions
Ion, it is more difficult to remove, therefore, it is necessary to carries out deep impurity-removing to it.
Specifically, depth removing calcium and magnesium is to mix the raw material after separation copper with villiaumite, then forms magnesium fluoride and calcirm-fluoride
Precipitate, then depth removes calcium ion and magnesium ion.Then filter off fluorinated calcium and fluorination magnesium precipitate.Finally cause in raw material
Calcium and magnesium be completely removed.The fluoride precipitation that depth removing calcium and magnesium obtains can be sent to fluorination factory and regard raw material, further, expand
The big utilization rate of waste liquid.
Further, the villiaumite of use include sodium fluoride, ammonium fluoride, cobaltous fluoride and manganous fluoride in any one or at least
Two kinds.Calcium ion and magnesium ion depth can be removed using above-mentioned substance, and can be avoided as much as introducing new impurity from
Son.
Further, the calcium ions and magnesium ions separated in the raw material after copper are the total amount of calcium ion and magnesium ion and mole of villiaumite
Than for 1:5-10, ensure that all calcium ions and magnesium ion in the raw material after separation copper can be gone completely using the villiaumite of excess
Except clean, guarantee impurity-eliminating effect.
S4, separation of Zinc；
By the raw material after depth removing calcium and magnesium and organo phosphoric extractant to be in a ratio of 1:1-1.3 ratio mix cause zinc from
It is sub to be all extracted into extractant, now there is a small amount of manganese ion to be also extracted into extractant, then carry out Liquid liquid Separation,
By organic phase and aqueous phase separation, organic phase is interior to contain substantial amounts of zinc ion and a small amount of manganese ion, and then contains in the aqueous solution
The solution of cobalt ions and substantial amounts of manganese ion.Extraction efficiency is ensure that compared to carrying out extraction using above-mentioned so that depth removing calcium and magnesium
The zinc ion in raw material afterwards fully can be extracted into extractant, ensure that impurity-eliminating effect.
Further, organo phosphoric extractant includes P204 (di-(2-ethylhexyl)phosphoric acid) or P507 (2- ethylhexyls
Phosphonic acids single 2-ethyl hexyl ester) or Cyanex272 (two (2,4,4- trimethyls) amyl group phosphonic acids) in any one or at least two
Kind, preferably P204.The favorable solubility of above-mentioned extractant and zinc ion, can be fully by zinc ion after depth removing calcium and magnesium
Raw material is extracted.
Extract and after the completion of liquid separation, organic phase is stripped using acid, then obtain zinc-manganese solution, and the acid used
1.1-1.3 is in a ratio of with organic phase:1, being compared using this can ensure that the zinc-manganese in organic phase can be fully stripped,
Then the efficiency of subsequent recovery zinc is ensured.Anti-stripping agent can be as the raw material of production manganese-zinc ferrite magnetic material.Acid is inorganic
Acid；Inorganic acid can be hydrochloric acid, sulfuric acid or nitric acid.
The content that the aqueous phase finally given finally passes through calcium in the aqueous phase that separation of Zinc obtains, magnesium, zinc and copper ion is small
In 0.01mg/l.
The embodiment of the present invention also provides a kind of method for reclaiming metal, and it includes the processing method of above-mentioned metal waste liquid.
The processing method of metal waste liquid provided in an embodiment of the present invention, using calcium, copper, magnesium, zinc metal ion characteristic, shape
Into different precipitations and anti-stripping agent, then using these precipitations and anti-stripping agent as production cement, lithium ion cell positive
The raw material of the materials such as material, manganese-zinc ferrite magnetic material, the waste of resource is avoided, while can effectively avoid metal waste liquid
Discharge and caused by environmental pollution.The processing method of whole metal waste liquid is simple to operate simultaneously, and operating condition is easily achieved.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of processing method of metal waste liquid, comprises the following steps：
S1, preliminary deliming；
First, the raw material used for cobalt hydrometallurgical extraction in clean caused by P204 processes i.e. dioctylphosphoric acid ester process
Liquid, removal of impurities liquid is mixed with sodium sulphate, the mol ratio of calcium ion and sulfate is 1 in the liquid that cleans：1.8, filtered after forming precipitation,
Calcium sulfate precipitation is removed, and calcium sulfate precipitation is rinsed with sodium sulphate.
S2, separation copper；
By the raw material after preliminary deliming and methyl ethyl ketoxime to be in a ratio of 1:1.5 ratio is mixed, and then carries out liquid liquid
Separation, the organic phase for then obtaining sulfuric acid and Liquid liquid Separation that concentration is 190g/l is to be in a ratio of 1:1.2 ratio is mixed into
Row back extraction, copper ion back extraction is taken out.
S3, depth removing calcium and magnesium；
Depth removing calcium and magnesium is to mix the raw material after separation copper with sodium fluoride, wherein, separate the calcium and magnesium in the raw material after copper
Ion is the total amount of calcium ion and magnesium ion and the mol ratio of villiaumite is 1:5.Magnesium fluoride and calcium fluoride precipitate are mixed to form, then
Filter off fluorinated calcium and fluorination magnesium precipitate.
S4, separation of Zinc；
By the raw material after depth removing calcium and magnesium and P204 to be in a ratio of 1:1 ratio, which mixes, causes zinc ion to be extracted into extraction
In agent, Liquid liquid Separation is then carried out, obtains organic phase and aqueous phase, then by hydrochloric acid and organic phase to be in a ratio of 1.2:1 ratio
Mixing is stripped.
The content of calcium ion in aqueous phase is 0.004mg/l, and the content of magnesium ion is that the content of 0.005mg/l zinc ions is
The content of 0.005mg/l and copper ion is 0.004mg/l.
The present embodiment also provides a kind of method for reclaiming metal, and it includes the processing method of above-mentioned metal waste liquid.
Embodiment 2
The present embodiment provides a kind of processing method of metal waste liquid, comprises the following steps：
S1, preliminary deliming；
First, the raw material used for cobalt hydrometallurgical extraction in clean caused by P204 processes i.e. dioctylphosphoric acid ester process
Liquid forms slag containing Mn after alkali precipitation, and slag containing Mn is mixed so that the pH value of the two mixed liquor is 1, then again with sulfuric acid
Mixed with sodium sulfite so that the black precipitate in the mixture of slag containing Mn, sulfuric acid and sodium sulfite is wholly absent, and calcium from
It is sub then with sulfate ion formed white precipitate, filter off except white precipitate, to remove calcium ion.
S2, separation copper；
Raw material after preliminary deliming is mixed with sodium hydroxide so that the mixture of raw material after sodium hydroxide and preliminary deliming
PH value be 4, then filter mixture in blue precipitate.
S3, depth removing calcium and magnesium；
Depth removing calcium and magnesium is to mix the raw material after separation copper with ammonium fluoride, wherein, separate the calcium and magnesium in the raw material after copper
Ion is the total amount of calcium ion and magnesium ion and the mol ratio of villiaumite is 1:10.Magnesium fluoride and calcium fluoride precipitate are mixed to form, and
After filter off fluorinated calcium and fluorination magnesium precipitate.
S4, separation of Zinc；
By the raw material after depth removing calcium and magnesium and P507 to be in a ratio of 1:1 ratio, which mixes, causes zinc ion to be extracted into extraction
In agent, Liquid liquid Separation is then carried out, obtains organic phase and aqueous phase, then by hydrochloric acid and organic phase to be in a ratio of 1.3:1 ratio
Mixing is stripped.
The content of calcium ion in aqueous phase is 0.002mg/l, and the content of magnesium ion is that the content of 0.002mg/l zinc ions is
The content of 0.006mg/l and copper ion is 0.002mg/l.
Embodiment 3
The present embodiment provides a kind of processing method of metal waste liquid, comprises the following steps：
S1, preliminary deliming；
First, the raw material used for cobalt hydrometallurgical extraction in clean caused by P204 processes i.e. dioctylphosphoric acid ester process
Liquid forms slag containing Mn after alkali precipitation, and slag containing Mn is mixed so that the pH value of the two mixed liquor is 1.5, then with sulfuric acid
Mixed again with hydrogen peroxide so that the black precipitate in the mixture of slag containing Mn, sulfuric acid and hydrogen peroxide is wholly absent, and calcium
Ion then forms white precipitate with sulfate ion, filters off except white precipitate, to remove calcium ion.
S2, separation copper；
Raw material after preliminary deliming is mixed with potassium hydroxide so that the mixture of raw material after sodium hydroxide and preliminary deliming
PH value be 3, then add nickel powder, reaction is filtered after terminating.
S3, depth removing calcium and magnesium；
Depth removing calcium and magnesium is to mix the raw material after separation copper with cobaltous fluoride, wherein, separate the calcium and magnesium in the raw material after copper
Ion is the total amount of calcium ion and magnesium ion and the mol ratio of villiaumite is 1:7.Magnesium fluoride and calcium fluoride precipitate are mixed to form, then
Filter off fluorinated calcium and fluorination magnesium precipitate.
S4, separation of Zinc；
By the raw material after depth removing calcium and magnesium and Cyanex272 to be in a ratio of 1:1.3 ratio, which mixes, make it that zinc ion is extracted
Take into extractant, then carry out Liquid liquid Separation, obtain organic phase and aqueous phase, then by hydrochloric acid and organic phase to be in a ratio of 1:1
Ratio mixing be stripped.
The content of calcium ion in aqueous phase is 0.006mg/l, and the content of magnesium ion is that the content of 0.004mg/l zinc ions is
The content of 0.007mg/l and copper ion is 0.005mg/l.
Embodiment 4
The present embodiment provides a kind of processing method of metal waste liquid, comprises the following steps：
S1, preliminary deliming；
First, the raw material used for cobalt hydrometallurgical extraction in clean caused by P204 processes i.e. dioctylphosphoric acid ester process
Liquid forms slag containing Mn after alkali precipitation, and slag containing Mn is mixed so that the pH value of the two mixed liquor is 2, then again with sulfuric acid
Mixed with sulfur dioxide so that the black precipitate in the mixture of slag containing Mn, sulfuric acid and sulfur dioxide is wholly absent.
S2, separation copper；
By the raw material after preliminary deliming and butyl aldoxime agent to be in a ratio of 1:1 ratio is mixed so that after preliminary deliming
Raw material in copper ion be extracted into organic phase, extracted twice using aforementioned proportion.Then organic phase is with concentration
200g/l sulfuric acid is to be in a ratio of 1:1.5 ratio mixing mixing, 3 back extraction are carried out using aforementioned proportion, and calcium ion is then
White precipitate is formed with sulfate ion, is filtered off except white precipitate, to remove calcium ion.
S3, depth removing calcium and magnesium；
Depth removing calcium and magnesium is to mix the raw material after separation copper with manganous fluoride, wherein, separate the calcium and magnesium in the raw material after copper
Ion is the total amount of calcium ion and magnesium ion and the mol ratio of villiaumite is 1:9.Magnesium fluoride and calcium fluoride precipitate are mixed to form, then
Filter off fluorinated calcium and fluorination magnesium precipitate.
S4, separation of Zinc；
By the raw material after depth removing calcium and magnesium and Cyanex272 and P204 mixture to be in a ratio of 1:1 ratio mixing makes
Obtain zinc ion to be extracted into extractant, then carry out Liquid liquid Separation, obtain organic phase and aqueous phase, then by hydrochloric acid and organic phase
To be in a ratio of 1:1.2 ratio mixing is stripped.
The content of calcium ion in aqueous phase is 0.004mg/l, and the content of magnesium ion is that the content of 0.004mg/l zinc ions is
The content of 0.002mg/l and copper ion is 0.003mg/l.
Embodiment 5
The present embodiment provides a kind of processing method of metal waste liquid, comprises the following steps：
S1, preliminary deliming；
First, the raw material used for cobalt hydrometallurgical extraction in clean caused by P204 processes i.e. dioctylphosphoric acid ester process
Liquid, removal of impurities liquid is mixed with sodium sulphate, the mol ratio of calcium ion and sulfate is 1 in the liquid that cleans：2.2, filtered after forming precipitation,
Calcium sulfate precipitation is removed, and calcium sulfate precipitation is rinsed with sodium sulphate.
S2, separation copper；
By the raw material after preliminary deliming and Chinese cassia tree aldoxime to be in a ratio of 1:1.2 ratio is mixed so that preliminary deliming
The copper ion in raw material afterwards is extracted into organic phase, then carries out Liquid liquid Separation, is extracted three times using aforementioned proportion.
The sulfuric acid that then organic phase and concentration are 180g/l is to be in a ratio of 1:1 ratio mixing mixing, 3 times are carried out instead using aforementioned proportion
Extraction.
S3, depth removing calcium and magnesium；
Depth removing calcium and magnesium is to be mixed the raw material after separation copper with the mixture of manganous fluoride and sodium fluoride, wherein, point
From the calcium ions and magnesium ions in the raw material after copper be calcium ion and magnesium ion total amount and villiaumite mol ratio be 1:8.It is mixed to form fluorine
Change magnesium and calcium fluoride precipitate, then filter off fluorinated calcium and fluorination magnesium precipitate.
S4, separation of Zinc；
By the raw material after depth removing calcium and magnesium and Cyanex272, P204 and P507 mixture to be in a ratio of 1:1.3 ratio
Mixing causes zinc ion to be extracted into extractant, then carries out Liquid liquid Separation, obtains organic phase and aqueous phase, then by hydrochloric acid and
Organic phase is to be in a ratio of 1:1.1 ratio mixing is stripped.
The content of calcium ion in aqueous phase is 0.004mg/l, and the content of magnesium ion is that the content of 0.002mg/l zinc ions is
The content of 0.002mg/l and copper ion is 0.003mg/l.
Embodiment 6
The present embodiment provides a kind of processing method of metal waste liquid, comprises the following steps：
S1, preliminary deliming；
First, the raw material used for cobalt hydrometallurgical extraction in clean caused by P204 processes i.e. dioctylphosphoric acid ester process
Liquid, removal of impurities liquid is mixed with sodium sulphate, the mol ratio of calcium ion and sulfate is 1 in the liquid that cleans：2.1, filtered after forming precipitation,
Calcium sulfate precipitation is removed, and calcium sulfate precipitation is rinsed with sodium sulphate.
S2, separation copper；
Raw material after preliminary deliming is mixed with ammonium hydrogen carbonate so that raw material and ammonium hydrogen carbonate after preliminary deliming
The pH value of mixture is 3.5, then the mixture of the raw material after preliminary deliming and ammonium hydrogen carbonate and manganese powder and the mixture of cobalt powder
Mixed, after reaction terminates, be filtrated to get copper powder.
S3, depth removing calcium and magnesium；
Depth removing calcium and magnesium is to be mixed the raw material after separation copper with the mixture of fluorine sodium fluoride, wherein, after separating copper
Raw material in calcium ions and magnesium ions be calcium ion and magnesium ion total amount and villiaumite mol ratio be 1:6.Be mixed to form magnesium fluoride and
Calcium fluoride precipitate, then filter off fluorinated calcium and fluorination magnesium precipitate.
S4, separation of Zinc；
By the raw material after depth removing calcium and magnesium and Cyanex272 and P507 mixture to be in a ratio of 1:1.2 ratio mixing
So that zinc ion is extracted into extractant, Liquid liquid Separation is then carried out, obtains organic phase and aqueous phase, then by hydrochloric acid and organic
Mutually to be in a ratio of 1:1.3 ratio mixing is stripped.
The content of calcium ion in aqueous phase is 0.002mg/l, and the content of magnesium ion is that the content of 0.003mg/l zinc ions is
The content of 0.005mg/l and copper ion is 0.004mg/l.
Embodiment 7
The present embodiment provides a kind of processing method of metal waste liquid, comprises the following steps：
S1, preliminary deliming；
First, the raw material used for cobalt hydrometallurgical extraction in clean caused by P204 processes i.e. dioctylphosphoric acid ester process
Liquid, removal of impurities liquid is mixed with sodium sulphate, the mol ratio of calcium ion and sulfate is 1 in the liquid that cleans：2, filter, go after forming precipitation
Sulfuric acid calcium precipitate, and rinse calcium sulfate precipitation with sodium sulphate.
S2, separation copper；
Raw material after preliminary deliming is mixed with sodium acid carbonate so that the mixing of raw material and sodium acid carbonate after preliminary deliming
The pH value of thing is 4.5, is then filtered off except the Kocide SD precipitation formed.
S3, depth removing calcium and magnesium；
Depth removing calcium and magnesium is to be mixed the raw material after separation copper with the mixture of manganous fluoride, sodium fluoride and cobaltous fluoride,
Wherein, separate copper after raw material in calcium ions and magnesium ions be calcium ion and magnesium ion total amount and villiaumite mol ratio be 1:6.Mixing
Magnesium fluoride and calcium fluoride precipitate are formed, then filters off fluorinated calcium and fluorination magnesium precipitate.
S4, separation of Zinc；
By the raw material after depth removing calcium and magnesium and P204 and P507 mixture to be in a ratio of 1:1.2 ratio, which mixes, causes zinc
Ion is extracted into extractant, then carries out Liquid liquid Separation, obtains organic phase and aqueous phase, then by hydrochloric acid and organic phase with phase
Than for 1:1 ratio mixing is stripped.Extraction and back extraction are carried out 2 times and 3 times respectively.
The content of calcium ion in aqueous phase is 0.002mg/l, and the content of magnesium ion is that the content of 0.002mg/l zinc ions is
The content of 0.002mg/l and copper ion is 0.002mg/l.
In summary, the processing method for the metal waste liquid that 1-7 of the embodiment of the present invention is provided can utilize calcium, copper, magnesium, zinc gold
Belong to ion characteristic, formed precipitation and anti-stripping agent, then using these precipitation and anti-stripping agent as produce cement, lithium from
The raw material of the materials such as sub- cell positive material, manganese-zinc ferrite magnetic material, expands the utilization rate of waste liquid, avoids resource
Waste, be effectively increased the income of enterprise, reduce the discharge of pollutant, then can effectively avoid metal discharging of waste liquid and caused by
Environmental pollution.The processing method of whole metal waste liquid is simple to operate simultaneously, and operating condition is easily achieved.
Embodiments described above is part of the embodiment of the present invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of processing method of metal waste liquid, it is characterised in that comprise the following steps：Raw material is subjected to preliminary deliming, separation
The operation of copper, depth removing calcium and magnesium and separation of Zinc.
2. the processing method of metal waste liquid according to claim 1, it is characterised in that the raw material is in cobalt hydrometallurgy
The slag containing Mn that removal of impurities liquid caused by P204 abstraction impurity removals process or the removal of impurities liquid obtain after alkali precipitation.
3. the processing method of metal waste liquid according to claim 2, it is characterised in that the raw material is the removal of impurities liquid,
Preliminary deliming is filtered after the removal of impurities liquid is mixed with sulfate, mole of calcium ion and the sulfate in the removal of impurities liquid
Than for 1:1.8-2.2.
4. the processing method of metal waste liquid according to claim 2, it is characterised in that the raw material is the removal of impurities liquid warp
The obtained slag containing Mn is crossed after alkali precipitation, and preliminary deliming is that the slag containing Mn is mixed to the pH for causing mixed liquor with sulfuric acid
It is worth and is filtered to add reducing agent after 1-2 again after black precipitate disappearance in the mixed liquor.
5. the processing method of metal waste liquid according to claim 4, it is characterised in that the reducing agent is adopted as sulfurous acid
Any one in sodium, sulfur dioxide or hydrogen peroxide or at least two.
6. the processing method of metal waste liquid according to claim 1, it is characterised in that separation copper is by after preliminary deliming
Raw material is with extraction DDTC to be in a ratio of 1:1-1.5 ratio mixing after isolated organic phase, then the organic phase again with sulphur
Acid is to be in a ratio of 1:1-1.5 ratio mixing is stripped.
7. the processing method of metal waste liquid according to claim 1, it is characterised in that separation copper is by after preliminary deliming
The pH value that raw material mixes the mixed solution of the raw material after causing the alkaline matter and the preliminary deliming with alkaline matter is 4-
4.5, then filtered.
8. the processing method of metal waste liquid according to claim 1, it is characterised in that depth removing calcium and magnesium is by after separation copper
Raw material mixed with villiaumite after refilter, the mol ratio of calcium ions and magnesium ions and the villiaumite is 1 in the raw material after the separation copper：5-
10。
9. the processing method of metal waste liquid according to claim 1, it is characterised in that separation of Zinc is by after depth removing calcium and magnesium
Raw material and organo phosphoric extractant to be in a ratio of 1:1-1.3 ratio hybrid separation obtains organic phase, organic phase again with acid with
It is in a ratio of 1:1-1.3 ratio mixing is stripped.
A kind of 10. method for reclaiming metal, it is characterised in that including the metal waste liquid described in claim 1-9 any one
Processing method.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439928A (en) * | 2018-11-12 | 2019-03-08 | 云南科力新材料股份有限公司 | The production method of de-magging Novel environment-friendlymaterial material in a kind of Zinc Hydrometallurgy Process |
| CN115140776A (en) * | 2022-08-03 | 2022-10-04 | 贵州金瑞新材料有限责任公司 | Novel process for producing manganese sulfate by using manganese waste liquid |
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| CN104480317A (en) * | 2014-11-13 | 2015-04-01 | 朱蕾 | Cobalt nickel metallurgy wastewater sludge recycling method |
| CN105274352A (en) * | 2015-09-30 | 2016-01-27 | 兰州金川新材料科技股份有限公司 | Method for separating copper, cobalt and manganese from mixture of copper, manganese, cobalt, calcium and zinc carbonate |
| CN105296754A (en) * | 2015-11-30 | 2016-02-03 | 北方工业大学 | Method for separating copper, cobalt and manganese from impurity-removed solution of copper, manganese, cobalt, calcium and zinc chloride |
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Patent Citations (3)
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| CN104480317A (en) * | 2014-11-13 | 2015-04-01 | 朱蕾 | Cobalt nickel metallurgy wastewater sludge recycling method |
| CN105274352A (en) * | 2015-09-30 | 2016-01-27 | 兰州金川新材料科技股份有限公司 | Method for separating copper, cobalt and manganese from mixture of copper, manganese, cobalt, calcium and zinc carbonate |
| CN105296754A (en) * | 2015-11-30 | 2016-02-03 | 北方工业大学 | Method for separating copper, cobalt and manganese from impurity-removed solution of copper, manganese, cobalt, calcium and zinc chloride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109439928A (en) * | 2018-11-12 | 2019-03-08 | 云南科力新材料股份有限公司 | The production method of de-magging Novel environment-friendlymaterial material in a kind of Zinc Hydrometallurgy Process |
| CN115140776A (en) * | 2022-08-03 | 2022-10-04 | 贵州金瑞新材料有限责任公司 | Novel process for producing manganese sulfate by using manganese waste liquid |
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