CN110257628A - A kind of method of iron in extraction cobalt sulfate solution - Google Patents
A kind of method of iron in extraction cobalt sulfate solution Download PDFInfo
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- CN110257628A CN110257628A CN201910673480.0A CN201910673480A CN110257628A CN 110257628 A CN110257628 A CN 110257628A CN 201910673480 A CN201910673480 A CN 201910673480A CN 110257628 A CN110257628 A CN 110257628A
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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
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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
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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
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- C22B7/007—Wet processes by acid leaching
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Abstract
The present invention provides a kind of methods of the iron in extraction cobalt sulfate solution, are related to technical field of wet metallurgy, and the method for the iron in the extraction cobalt sulfate solution includes the following steps: S1: preparing iron-containing cobalt sulfate solution；S2: surfactant, sulfonated kerosene, di (isooctyl) phosphate, atoleine are mixed, composite extractant is obtained；Hydrochloric acid is added dropwise in S3: Xiang Suoshu composite extractant, obtains mixture, stirring to the mixture is in emulsion form, obtains emulsion liquid film；S4: the iron-containing cobalt sulfate solution is mixed with the emulsion liquid film, and extraction obtains the raffinate phase and iron-containing extraction phase containing cobalt.The method of iron in extraction cobalt sulfate solution provided by the invention considerably increases the contact area of extractant Yu iron-containing cobalt sulfate solution by the way that extractant is prepared into emulsion form film, reducing Solvent quantity, while alleviating environmental pollution, extraction time is also shortened, extraction efficiency is improved.
Description
Technical field
The present invention relates to technical field of wet metallurgy, in particular to a kind of side of the iron in extraction cobalt sulfate solution
Method.
Background technique
In hydrometallurgy, when with sulfuric acid to leach metal waste, Tie Tong is often with the form of Fe (III) and valuable metal one
With entering in solution, Fe (III) facile hydrolysis can form complex with other ions, so that Fe (III) is removed in water phase
It is more difficult.
For the iron in removal cobalt sulfate solution, existing extracting process is mostly extraction with di (isooctyl) phosphate (P204)
Agent, kerosene are diluent, directly extraction iron, and whole process extractant usage amount is big, and environmental pollution is serious.
Summary of the invention
Problems solved by the invention is when extracting to the iron in cobalt sulfate solution, and extractant usage amount is big.
To solve the above problems, the present invention provides a kind of method for extracting the iron in cobalt sulfate solution, this method includes such as
Lower step:
S1: iron-containing cobalt sulfate solution is prepared；
S2: surfactant, sulfonated kerosene, di (isooctyl) phosphate, atoleine are mixed, composite extractant is obtained；
Hydrochloric acid is added dropwise in S3: Xiang Suoshu composite extractant, obtains mixture, stirring to the mixture is in emulsion form, is obtained
To emulsion liquid film；
S4: the iron-containing cobalt sulfate solution is mixed with the emulsion liquid film, and extraction obtains the raffinate phase containing cobalt and contains
The extraction phase of iron.
Optionally, the method for the iron in the extraction cobalt sulfate solution further include:
S5: heating the extraction phase, is centrifuged to the extraction phase after heating, obtains water phase and extracts oily phase；
S6: the extraction oil is mutually stripped through oxalic acid, anti-stripping agent and di (isooctyl) phosphate organic phase are obtained.
Optionally, the surfactant is oleic acid, sorbitan trioleate, polyoxyethylene sorbitol trioleate
One of.
Optionally, surfactant described in the composite extractant, the sulfonated kerosene, the di (isooctyl) phosphate,
The volume ratio range of the atoleine is (2~6): (80~85): (5~10): (5~10).
Optionally, the concentration range of hydrochloric acid described in step S3 is 3~5mol/L, the hydrochloric acid and the composite extractant
Volume ratio range be 0.8~1.2.
Optionally, the volume ratio range of iron-containing cobalt sulfate solution described in step S4 and the emulsion liquid film is 1~5:
1。
Optionally, the heating extraction phase includes: to carry out constant temperature water bath heating to the extraction phase, and the water-bath is permanent
The condition of temperature heating is in 80~100 DEG C of 80~100min of temperature range inside holding.
Optionally, extraction oil described in step S6 is mutually 0.8~1.2:1, the oxalic acid with the volume ratio range of the oxalic acid
Mass percent range be 3%~5%, the temperature range of the back extraction is 15~25 DEG C.
Optionally, described to prepare iron-containing cobalt sulfate solution and include:
S1-1: the iron content cobalt slag that gives up is placed in Muffle furnace, being warming up to temperature range with the heating rate of 5~10 DEG C/min is
500~600 DEG C, constant temperature keeps 2~4h, is cooled to room temperature, and grinds, and sieving obtains raw material waste residue；
S1-2: by the raw material waste residue through sulfuric acid leaching, filtering takes filtrate, obtains iron-containing cobalt sulfate solution.
Optionally, the concentration range of the sulfuric acid is 160~200g/L.
The method of iron in extraction cobalt sulfate solution provided by the invention, by the way that extractant is prepared into emulsion form film, greatly
The contact area for increasing extractant Yu iron-containing cobalt sulfate solution greatly is reducing Solvent quantity, is alleviating the same of environmental pollution
When, extraction time is also shortened, extraction efficiency is improved.
Detailed description of the invention
Fig. 1 is the schematic diagram that emulsion liquid film of the present invention extracts and is stripped metal ion；
Fig. 2 is the flow chart of the method for the iron in extraction cobalt sulfate solution of the present invention.
Specific embodiment
To make the above purposes, features and advantages of the invention more obvious and understandable, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.
When to solve in the prior art to extract the iron in cobalt sulfate solution, extractant usage amount is big, to environment dirt
Serious problem is contaminated, the present invention provides a kind of method for extracting the iron in cobalt sulfate solution, and this method comprises the following steps:
S1: iron-containing cobalt sulfate solution is prepared；
S2: surfactant, sulfonated kerosene, di (isooctyl) phosphate (P204), atoleine are mixed, compound extracting is obtained
Agent；
S3: hydrochloric acid being added dropwise into composite extractant, obtains mixture, and stirring to mixture is in emulsion form, obtains emulsion
Film；
S4: iron-containing cobalt sulfate solution is mixed with above-mentioned emulsion liquid film, extraction, obtains raffinate phase containing cobalt and iron-containing
Extraction phase.
It should be noted that iron, in particular to Fe (III) in the present invention.
Wherein above-mentioned P204 is extractant, and sulfonated kerosene is membrane solvent, and atoleine is stabilizer, provided by the invention
The method for extracting the iron in cobalt sulfate solution, by adding surfactant and stabilizer on the basis of conventional method, so that
Surfactant, stabilizer are mixed with sulfonated kerosene and P204, form composite extractant；It is added dropwise again into the composite extractant
Hydrochloric acid, and stir to emulsion form, obtain emulsion liquid film.
In the emulsion liquid film, surfactant, atoleine, sulfonated kerosene and P204 constitute interior phase, and interior phase is in emulsion film
Many microlayer models are inside dispersed into, is suspended in film phase liquid and constitutes emulsion.Wherein P204 plays carrier function, and surfactant plays cream
Change effect, the molecular orientation of surfactant is arranged on phase interface, for enhancing emulsion liquid film.Hydrochloric acid solution as foreign minister,
Outside liquid film.
Iron-containing cobalt sulfate solution is mixed with above-mentioned emulsion liquid film again, shown in Figure 1, P204 and sulphur as carrier
Iron phase in acidic cobalt solution combines, and migrates in film, realizes the extraction to iron, obtains the raffinate phase and iron-containing extraction containing cobalt
Phase.
The method of iron in extraction cobalt sulfate solution provided by the invention, during being extracted to iron, cobaltous sulfate
Iron in solution is transmitted to interior phase by film from foreign minister and achievees the purpose that extraction and separation, since emulsion liquid film has biggish ratio
Therefore surface area substantially increases the contact area of extractant and cobalt sulfate solution, the method phase with traditional extraction iron
Than with the extractant of same dosage, technical solution provided by the invention can extract a greater amount of iron, to avoid leading to
Crossing progress, repeatedly extraction is to separate iron, so that the method for the iron in extraction cobalt sulfate solution provided by the invention, is subtracting
Few Solvent quantity also shortens extraction time, improves extraction efficiency while alleviating environmental pollution.
Iron further to be recycled and reused to emulsion liquid film, in extraction cobalt sulfate solution provided by the invention
Method further include:
S5: heating extraction phase is centrifuged the extraction phase after heating, obtains water phase and extracts oily phase；
S6: extraction oil is mutually stripped through oxalic acid, anti-stripping agent and di (isooctyl) phosphate organic phase are obtained.
Carry out demulsification back extraction；By heating Centrifugical extraction phase, make the surfactant being located in extraction phase by emulsifying
State becomes water-oil separating state, obtains water phase and the extraction oil phase containing iron ion, realizes demulsification；Again through oxalic acid to extraction oil mutually into
One step is stripped, shown in Figure 1, and iron ion is separated with extractant P204, and obtaining iron-containing anti-stripping agent and P204 has
Machine phase, wherein P204 organic phase is the mixed liquor of surfactant, sulfonated kerosene, P204, atoleine, to reduce extractant
Dosage reduces the pollution to environment, shown in Figure 2, hydrochloric acid can be added dropwise by again into the mixed liquor, stir, form cream
Liquid film, to realize the recycling to extractant.
In emulsion liquid film, surfactant is to create liquid film, the most important component of fixed oil water surface, surfactant
The recycling of the stability, seepage velocity, separating effect and emulsion liquid film of film is directly affected, to improve emulsion liquid film
Stability, preferred surfactant of the present invention are oleic acid, in sorbitan trioleate, polyoxyethylene sorbitol trioleate
One kind.
For the performance for improving emulsion liquid film, the present invention is when preparing composite extractant, preferred surfactant, sulfonated coal
Oil, di (isooctyl) phosphate, atoleine volume ratio range be 2~6:80~85:5~10:5~10, in order to avoid because of compound extracting
The ratio of each ingredient is improper and lead to that emulsion form film properties are unstable or extracting power is poor in agent.
Specifically, it is 3~5mol/L and composite extractant that into composite extractant, dropwise addition hydrochloric acid, which includes: by concentration range,
The hydrochloric acid that volume ratio range is 0.8~1.2 is added dropwise in composite extractant.
Because hydrochloric acid is volatile, therefore, emulsion form is generated to guarantee that the concentration for the hydrochloric acid being added dropwise in composite extractant meets
The demand of film needs that quickly hydrochloric acid is added dropwise in composite extractant；For example, hydrochloric acid is preferably added dropwise in 1min by the present invention
In composite extractant, in order to avoid cause hydrochloric acid to volatilize because time for adding is too long and keep the concentration of hydrochloric acid being added dropwise too low, influence emulsion
The generation of film, or influence the effect of extracting of emulsion liquid film.
Equally, it is guarantee emulsion liquid film to the effect of extracting of iron, iron-containing cobalt sulfate solution is mixed into packet with emulsion liquid film
It includes: the iron-containing cobalt sulfate solution that volume ratio range is 1~5:1 is mixed with emulsion liquid film.
The volume ratio of iron-containing cobalt sulfate solution and emulsion liquid film is too small, and emulsion liquid film is using insufficient, so as to cause extraction
The unnecessary waste of agent is taken, while the pollution to environment can be aggravated；The volume ratio of iron-containing cobalt sulfate solution and emulsion liquid film is too
Greatly, the iron in cobalt sulfate solution cannot sufficiently be extracted, to influence the effect of extracting of emulsion liquid film；The present invention pass through by
The volume ratio range of iron-containing cobalt sulfate solution and emulsion liquid film is limited to 1~5:1, is guaranteeing to the same of the effect of extracting of iron
When, moreover it is possible to emulsion liquid film is made full use of, avoids wasting.
When carrying out demulsification back extraction, to enable extraction phase thermally equivalent, the present invention preferably adds extraction phase
The mode of heat is constant temperature water bath heating, specifically, the condition of constant temperature water bath heating is in 80~100 DEG C of temperature range inside holdings 80
~100min.
The temperature of the characteristics of according to extraction phase, heating are too low, are unfavorable for emulsion form film and are sufficiently demulsified；On the contrary, heating
Temperature it is excessively high, be easy to damage the ingredient in extraction phase, to influence the recycling and reusing of the ingredients such as extractant.
Equally, soaking time is too short, is unfavorable for emulsion form film and is sufficiently demulsified；On the contrary, soaking time is too long, will lead to
To the overlong time that iron is extracted, to influence the extraction efficiency extracted to iron.
The present invention is set as 80~100 DEG C by the temperature range for heating constant temperature water bath, and soaking time range is set
For 80~100min, while guaranteeing sufficiently to be demulsified to emulsion liquid film, additionally it is possible to guarantee the recycling of the ingredients such as extractant
Recycle and guarantee the extraction efficiency extracted to iron.
Specifically, when being stripped, will extraction oil mutually through oxalic acid back extraction include: by volume ratio range be 0.8~
The oxalic acid that the extraction oil of 1.2:1 is mutually 3%~5% with mass percent range is stripped, and the temperature range of back extraction is 15
~25 DEG C.
Similar with above-mentioned analytic process, the present invention passes through to extraction oil phase and the volume ratio range of oxalic acid, the quality hundred of oxalic acid
Score and the temperature range of back extraction are defined, and on the one hand can be guaranteed the effect of back extraction, on the other hand can also be protected
Demonstrate,prove the efficiency being stripped.
It is pointed out that iron-containing cobalt sulfate solution mentioned in the present invention, can refer to and be contained with what all forms obtained
The cobalt sulfate solution of iron；Specifically, the present invention is to give up cobalt slag as raw material, to iron-containing cobalt sulfate solution for iron content
Preparation process is illustrated.
Specifically, preparing iron-containing cobalt sulfate solution and including:
S1-1: the iron content cobalt slag that gives up is placed in Muffle furnace, being warming up to temperature range with the heating rate of 5~10 DEG C/min is
500~600 DEG C, constant temperature keeps 2~4h, is cooled to room temperature, and grinds, and sieving obtains raw material waste residue；
S1-2: by raw material waste residue through sulfuric acid leaching, filtering takes filtrate, obtains iron-containing cobalt sulfate solution.
By high-temperature calcination, the organic matter in the useless cobalt slag of iron content can be removed, to reduce the impurity in useless cobalt slag；Pass through journey
The mode of sequence heating heats up, so that iron content gives up cobalt slag when each temperature section all has certain stop in calcination process
Between, the different organic matters so that iron content is given up in cobalt slag can be efficiently removed.
500~600 DEG C are warming up to by the heating rate with 5~10 DEG C/min, after constant temperature keeps 2~4h, is removed
The iron content of organic impurities is given up cobalt slag；After the useless cobalt slag of the iron content is cooled to room temperature, the useless cobalt slag of iron content after cooling is carried out
It grinds and is sieved, obtain the raw material waste residue of certain particle size range, so that the raw material waste residue can be in subsequent processes sufficiently
It is reacted；The present invention preferably sieving process is to sieve with 100 mesh sieve.
Further raw material waste residue is impregnated by sulfuric acid, so that cobalt element and ferro element and sulphur in raw material waste residue
Acid is reacted, and iron-containing cobalt sulfate solution is obtained.
Specifically, by raw material waste residue through sulfuric acid leaching include: by raw material waste residue through concentration range be 160~200g/L sulphur
Ore Leaching.That is, impregnating using the sulfuric acid that concentration range is 160~200g/L to raw material waste residue, on the one hand avoid sulfuric acid dense
Spend it is low, lead to not by raw material waste residue cobalt element and ferro element leach, on the other hand avoid sulfuric acid concentration excessively high and
Cause unnecessary waste.
To sum up, the method for the iron in extraction cobalt sulfate solution provided by the invention, on the one hand by the way that extractant to be prepared into
Emulsion form film considerably increases the contact area of extractant Yu iron-containing cobalt sulfate solution, is reducing Solvent quantity, is alleviating ring
While border is polluted, extraction time is also shortened, extraction efficiency is improved；On the other hand, by the strip stage that is demulsified, so that
Extractant can be recycled, to while cost is reduced, can also reduce the pollution to environment.
Embodiment one
The present embodiment provides a kind of methods of the iron in extraction cobalt sulfate solution, and this method comprises the following steps:
S1-1: the iron content cobalt slag that gives up is placed in Muffle furnace, is warming up to 500 DEG C with the heating rate of 5 DEG C/min, constant temperature is kept
2h is cooled to room temperature, and grinding sieves with 100 mesh sieve, and is uniformly mixed, sample quarterlies, and the sample of taking-up is packed into transparent sampler bag
In, sealing is labelled, for use, obtains raw material waste residue；
S1-2: the sulfuric acid leaching by raw material waste residue through 160g/L, filtering take filtrate, obtain iron-containing cobalt sulfate solution；
S2: according to volume percentage, take 5% surfactant oleic acid, 80% sulfonated kerosene, 5%P204 extractant,
10% atoleine mixing, preservative film sealing, is placed on magnetic stirring apparatus, is mixed with the revolving speed of 1000r/min, obtains compound extraction
Take agent；
S3: in 1min, the hydrochloric acid that concentration is 3mol/L and composite extractant volume ratio is 0.8 is added dropwise to compound extraction
It takes in agent, obtains mixture, stirring to mixture is in emulsion form, obtains emulsion liquid film；
S4: iron-containing cobalt sulfate solution is mixed with above-mentioned emulsion liquid film for 1:1 according to volume ratio, with turning for 400r/min
Speed is extracted, and liquid extracted is poured into separatory funnel, and the iron-containing extraction phase in upper layer pours into colorimetric cylinder from above, under
Raffinate phase of the layer containing cobalt is from following discharge；
S5: the colorimetric cylinder for filling extraction phase is placed in thermostat water bath, in 80 DEG C of heat preservation 80min, is then in revolving speed
Centrifugation 3min is carried out to the extraction phase after heating in the centrifuge of 3000r/min, obtain water phase and extracts oily phase, by water phase and extraction oil
Mutually separated；
S6: will extract the oily oxalic acid for being mutually 3% with mass percent according to volume ratio is that 0.8:1 is mixed, in 15 DEG C of items
It is stripped under part, obtains anti-stripping agent and P204 organic phase.
It is molten to iron-containing cobaltous sulfate respectively by plasma scan spectrometer (ICP) to detect the effect of extracting to iron
Liquid, the raffinate phase in step S4 and the tenor in the anti-stripping agent in step S6 are measured, in which: iron-containing sulfuric acid
Iron (Fe) content is 5.65g/L in cobalt liquor, and cobalt (Co) content is 230mg/L, and nickel (Ni) content is 422mg/L, and aluminium (Al) contains
Amount is 3.64g/L；Iron (Fe) content is 76mg/L in raffinate phase, and cobalt (Co) content is 226mg/L, and nickel (Ni) content is 415mg/
L, aluminium (Al) content are 3.58g/L；The content of iron (Fe) is 5.44g/L in anti-stripping agent.
It is computed, the extraction yield of iron has reached 98.65% in the present embodiment, and micro aluminium is extracted, and cobalt, nickel are not extracted
It takes, the back extraction ratio of iron reaches 97.60%, so that the method for proving the iron in extraction cobalt sulfate solution provided by the invention is being reduced
Solvent quantity alleviates environmental pollution, shortens extraction time, while improving extraction efficiency, also has excellent extraction
Effect.
Comparative example one
For verifying, the present invention provides the advantage of technical solution, and the present embodiment provides the method extracted as follows to iron,
It is compared with the present invention:
S1-1: the iron content cobalt slag that gives up is placed in Muffle furnace, is warming up to 500 DEG C with the heating rate of 5 DEG C/min, constant temperature is kept
2h is cooled to room temperature, and grinding sieves with 100 mesh sieve, and is uniformly mixed, sample quarterlies, and the sample of taking-up is packed into transparent sampler bag
In, sealing is labelled, for use, obtains raw material waste residue；
S1-2: the sulfuric acid leaching by raw material waste residue through 160g/L, filtering take filtrate, obtain iron-containing cobalt sulfate solution；
S2: according to volume percentage, 30%P204 extractant, the mixing of 70% sulfonated kerosene are taken, preservative film sealing is placed in
On magnetic stirring apparatus, is mixed with the revolving speed of 1000r/min, obtain mixed extractant；
S3: iron-containing cobalt sulfate solution is mixed with above-mentioned mixed extractant for 1:1 according to volume ratio, with 400r/min's
Revolving speed is extracted, and liquid extracted is poured into separatory funnel, and the iron-containing extraction phase in upper layer pours into colorimetric cylinder from above,
Raffinate phase of the lower layer containing cobalt is from following discharge；
S4: according to volume ratio being that 0.8:1 is mixed by the oxalic acid that extraction phase and mass percent are 3%, in 15 DEG C of items
It is stripped under part, obtains anti-stripping agent and P204 organic phase.
By plasma scan spectrometer (ICP) respectively to iron-containing cobalt sulfate solution, raffinate phase and anti-stripping agent
In tenor be measured, calculate the extraction yield of iron；It is computed, after carrying out level-one extraction to iron in aforementioned manners, iron
Extraction yield is only 77%, the extraction yield of the iron in the method for the iron in extraction cobalt sulfate solution far smaller than provided by the invention.
By being compared with comparative example, it was demonstrated that the method for the iron in extraction cobalt sulfate solution provided by the invention,
Level-one extraction can be greatlyd improve to the extraction yield of iron, to prove the iron in extraction cobalt sulfate solution provided by the invention
Method is reducing Solvent quantity, alleviates environmental pollution, shortens extraction time, while improving extraction efficiency, also have
Excellent effect of extracting.
Embodiment two
The present embodiment provides a kind of methods of the iron in extraction cobalt sulfate solution, and this method comprises the following steps:
S1-1: the iron content cobalt slag that gives up is placed in Muffle furnace, is warming up to 550 DEG C with the heating rate of 8 DEG C/min, constant temperature is kept
3h is cooled to room temperature, and grinding sieves with 100 mesh sieve, and is uniformly mixed, sample quarterlies, and the sample of taking-up is packed into transparent sampler bag
In, sealing is labelled, for use, obtains raw material waste residue；
S1-2: the sulfuric acid leaching by raw material waste residue through 180g/L, filtering take filtrate, obtain iron-containing cobalt sulfate solution；
S2: according to volume percentage, take 5% surfactant sorbitan trioleate, 80% sulfonated kerosene,
8%P204 extractant, the mixing of 7% atoleine, preservative film sealing are placed on magnetic stirring apparatus, mixed with the revolving speed of 1200r/min
It is even, obtain composite extractant；
S3: in 1min, the hydrochloric acid that concentration is 4mol/L and composite extractant volume ratio is 1 is added dropwise to compound extracting
In agent, mixture is obtained, stirring to mixture is in emulsion form, obtains emulsion liquid film；
S4: iron-containing cobalt sulfate solution is mixed with above-mentioned emulsion liquid film according to volume ratio for 3:1, with 500r/min
Revolving speed extracted, liquid extracted is poured into separatory funnel, the iron-containing extraction phase in upper layer pours into colorimetric cylinder from above
In, raffinate phase of the lower layer containing cobalt is from following discharge；
S5: the colorimetric cylinder for filling extraction phase is placed in thermostat water bath, in 90 DEG C of heat preservation 90min, is then in revolving speed
Centrifugation 3min is carried out to the extraction phase after heating in the centrifuge of 3000r/min, obtain water phase and extracts oily phase, by water phase and extraction oil
Mutually separated；
S6: will extract the oily oxalic acid for being mutually 4% with mass percent according to volume ratio is that 1:1 is mixed, in 20 DEG C of conditions
Under be stripped, obtain anti-stripping agent and P204 organic phase.
It is molten to iron-containing cobaltous sulfate respectively by plasma scan spectrometer (ICP) to detect the effect of extracting to iron
Liquid, the raffinate phase in step S4 and the tenor in the anti-stripping agent in step S6 are measured, in which: iron-containing sulfuric acid
Iron (Fe) content is 4.84g/L in cobalt liquor, and cobalt (Co) content is 178mg/L, and nickel (Ni) content is 634mg/L, and aluminium (Al) contains
Amount is 4.27g/L；Iron (Fe) content is 43mg/L in raffinate phase, and cobalt (Co) content is 173mg/L, and nickel (Ni) content is 630mg/
L, aluminium (Al) content are 4.16g/L；The content of iron (Fe) is 4.68g/L in anti-stripping agent.
It is computed, the extraction yield of iron has reached 99.11% in the present embodiment, and micro aluminium is extracted, and cobalt, nickel are not extracted
It takes, the back extraction ratio of iron reaches 97.56%, so that the method for proving the iron in extraction cobalt sulfate solution provided by the invention is being reduced
Solvent quantity alleviates environmental pollution, shortens extraction time, while improving extraction efficiency, also has excellent extraction
Effect.
Embodiment three
The present embodiment provides a kind of methods of the iron in extraction cobalt sulfate solution, and this method comprises the following steps:
S1-1: the iron content cobalt slag that gives up is placed in Muffle furnace, is warming up to 600 DEG C with the heating rate of 10 DEG C/min, constant temperature is protected
4h is held, is cooled to room temperature, grinds, sieves with 100 mesh sieve, is uniformly mixed, sample quarterlies, the sample of taking-up is packed into transparent sampler bag
In, sealing is labelled, for use, obtains raw material waste residue；
S1-2: the sulfuric acid leaching by raw material waste residue through 200g/L, filtering take filtrate, obtain iron-containing cobalt sulfate solution；
S2: according to volume percentage, 4% surfactant polyoxyethylene sorbitol olein, 83% sulfonated coal are taken
Oil, the mixing of 8%P204 extractant, 5% atoleine, preservative film sealing are placed on magnetic stirring apparatus, with turning for 1400r/min
Speed mixes, and obtains composite extractant；
S3: in 1min, the hydrochloric acid that concentration is 4mol/L and composite extractant volume ratio is 1.2 is added dropwise to compound extraction
It takes in agent, obtains mixture, stirring to mixture is in emulsion form, obtains emulsion liquid film；
S4: iron-containing cobalt sulfate solution is mixed with above-mentioned emulsion liquid film according to volume ratio for 5:1, with 600r/min
Revolving speed extracted, liquid extracted is poured into separatory funnel, the iron-containing extraction phase in upper layer pours into colorimetric cylinder from above
In, raffinate phase of the lower layer containing cobalt is from following discharge；
S5: the colorimetric cylinder for filling extraction phase is placed in thermostat water bath, in 100 DEG C of heat preservation 100min, then in revolving speed
To carry out centrifugation 3min to the extraction phase after heating in the centrifuge of 3000r/min, obtaining water phase and extracting oily phase, by water phase and extraction
Oil is mutually separated；
S6: will extract the oily oxalic acid for being mutually 5% with mass percent according to volume ratio is that 1.2:1 is mixed, in 25 DEG C of items
It is stripped under part, obtains anti-stripping agent and P204 organic phase.
It is molten to iron-containing cobaltous sulfate respectively by plasma scan spectrometer (ICP) to detect the effect of extracting to iron
Liquid, the raffinate phase in step S4 and the tenor in the anti-stripping agent in step S6 are measured, in which: iron-containing sulfuric acid
Iron (Fe) content is 5.72g/L in cobalt liquor, and cobalt (Co) content is 363mg/L, and nickel (Ni) content is 541mg/L, and aluminium (Al) contains
Amount is 4.23g/L；Iron (Fe) content is 26mg/L in raffinate phase, and cobalt (Co) content is 359mg/L, and nickel (Ni) content is 537mg/
L, aluminium (Al) content are 4.18g/L；The content of iron (Fe) is 5.62g/L in anti-stripping agent.
It is computed, the extraction yield of iron has reached 99.55% in the present embodiment, and micro aluminium is extracted, and cobalt, nickel are not extracted
It takes, the back extraction ratio of iron reaches 98.70%, so that the method for proving the iron in extraction cobalt sulfate solution provided by the invention is being reduced
Solvent quantity alleviates environmental pollution, shortens extraction time, while improving extraction efficiency, also has excellent extraction
Effect.
Although the disclosure discloses as above, the protection scope of the disclosure is not limited only to this.Those skilled in the art, not
Under the premise of being detached from spirit and scope of the present disclosure, it can make various changes and modify, these changes will fall into this with modification
The protection scope of invention.
Claims (10)
1. a kind of method of the iron in extraction cobalt sulfate solution, which comprises the steps of:
S1: iron-containing cobalt sulfate solution is prepared；
S2: surfactant, sulfonated kerosene, di (isooctyl) phosphate, atoleine are mixed, composite extractant is obtained；
Hydrochloric acid is added dropwise in S3: Xiang Suoshu composite extractant, obtains mixture, stirring to the mixture is in emulsion form, obtains cream
Shape liquid film；
S4: the iron-containing cobalt sulfate solution is mixed with the emulsion liquid film, extraction, obtains raffinate phase containing cobalt and iron-containing
Extraction phase.
2. the method for the iron in extraction cobalt sulfate solution as described in claim 1, which is characterized in that the extraction cobaltous sulfate is molten
The method of iron in liquid further include:
S5: heating the extraction phase, is centrifuged to the extraction phase after heating, obtains water phase and extracts oily phase；
S6: the extraction oil is mutually stripped through oxalic acid, anti-stripping agent and di (isooctyl) phosphate organic phase are obtained.
3. the method for the iron in extraction cobalt sulfate solution as described in claim 1, which is characterized in that the surfactant is
One of oleic acid, sorbitan trioleate, polyoxyethylene sorbitol trioleate.
4. the method for the iron in extraction cobalt sulfate solution as described in claim 1, which is characterized in that in the composite extractant
The surfactant, the sulfonated kerosene, the di (isooctyl) phosphate, the atoleine volume ratio range be (2~
6): (80~85): (5~10): (5~10).
5. the method for the iron in extraction cobalt sulfate solution as described in claim 1, which is characterized in that hydrochloric acid described in step S3
Concentration range be 3~5mol/L, the volume ratio range of the hydrochloric acid and the composite extractant is 0.8~1.2.
6. the method for the iron in extraction cobalt sulfate solution as described in claim 1, which is characterized in that iron content described in step S4
Cobalt sulfate solution and the emulsion liquid film volume ratio range be 1~5:1.
7. the method for the iron in extraction cobalt sulfate solution as claimed in claim 2, which is characterized in that the heating extraction
It mutually include: that constant temperature water bath heating is carried out to the extraction phase, the condition of the constant temperature water bath heating is in 80~100 DEG C of temperature models
Enclose 80~100min of inside holding.
8. the method for the iron in extraction cobalt sulfate solution as claimed in claim 2, which is characterized in that extract oil described in step S6
It is mutually 0.8~1.2:1 with the volume ratio range of the oxalic acid, the mass percent range of the oxalic acid is 3%~5%, described
The temperature range of back extraction is 15~25 DEG C.
9. the method for the iron in extraction cobalt sulfate solution as described in any one of claims 1 to 8, which is characterized in that the system
Include: for iron-containing cobalt sulfate solution
S1-1: the iron content cobalt slag that gives up is placed in Muffle furnace, is warming up to temperature range with the heating rate of 5~10 DEG C/min as 500
~600 DEG C, constant temperature keeps 2~4h, is cooled to room temperature, and grinds, and sieving obtains raw material waste residue；
S1-2: by the raw material waste residue through sulfuric acid leaching, filtering takes filtrate, obtains iron-containing cobalt sulfate solution.
10. the method for the iron in extraction cobalt sulfate solution as claimed in claim 9, which is characterized in that the concentration of the sulfuric acid
Range is 160~200g/L.
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