CN109055744A - A method of the extraction of indium from the methane sulfonic acid lead solution containing indium - Google Patents
A method of the extraction of indium from the methane sulfonic acid lead solution containing indium 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
- 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
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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Abstract
The invention belongs to technical field of wet metallurgy；More particularly to a kind of method of extraction of indium from the methane sulfonic acid lead solution containing indium, lead-cerium alloy electrorefining under the system added with additive obtains the methane sulfonic acid lead solution containing indium；Methane sulfonic acid lead solution containing indium handle except lead, is obtained except liquid after lead；The pH value except liquid after lead is adjusted, indium extraction stoste is obtained；Stoste will be extracted to be in contact, extract with organic comprising extractant.The present invention can solve the problems, such as that methane sulfonic acid system extraction of indium process is generated third phase due to the ratio and dosage of additive package, plumbum ion concentration, pH value, temperature and emulsion occurs, increase the recovery efficiency of indium, simplify isolated difficulty, belongs to low cost method simple to operation.
Description
Technical field
The present invention relates to a kind of methane sulfonic acid systems to extract the new method for preventing third phase and emulsion from generating during indium,
Belong to technical field of wet metallurgy.
Background technique
Having not found the enrichment mine of indium in the world at present, indium exists only in the mines such as low-grade oxide ore, sulphide ore,
Content is seldom, is often identified as impurity, smelting process accumulation in by-product in, these raw materials containing indium, complicated component, object
Physicochemical property is different, therefore hydrometallurgy route has unique advantage when handling these complex materials, passes through leaching
Stage out, can by various raw materials metal target and some other foreign metal be transferred in leachate, become ion shape
Metal target indium is then selectively extracted by distinct methods from solution, achievees the purpose that enrichment and recycling by state.
In lead, zinc metallurgical process, in addition to lost part, most indium is enriched in metallurgical intermediate product or byproduct, such as lead bullion, cigarette
Dirt, leached mud, refining dross, hard zinc block, scum, replacement slag etc..China's indium metal mainly by lead, zinc abstraction intermediate product or
It is extracted in by-product.
Solvent extraction is commonly used for selective extraction separation metal, in terms of being typically employed in metallurgy and chemical industry.For example, existing
The method of extraction and recovery indium in the more aqueous solution from inorganic acid is disclosed in technology.However, if generating three in extraction process
Mutually and emulsification, the loss for not only resulting in extractant increase, and also will cause extraction split-phase difficulty when serious, production can not carry out.
Third phase and emulsification are mainly as caused by organic phase composition, water phase subparticle.Demulsifier is added in organic phase,
It is current most commonly used breaking method.This method specificity is strong, can be directed to emulsion of different nature, destroy surface
Film discharges the droplet of package, reaches water-oil phase separation, to achieve the effect that demulsification.The demulsification of the method can reach
90% or more, but the limited amount of demulsifier, limited skin covering of the surface can only be destroyed, for emulsion caused by other reasons,
Demulsifier need further to study.
The solid particle in water phase is eliminated using sand filtration or active carbon, initial stage can have very high adsorption effect, but
Using for a long time, surface meeting particle concentrations layer, adsorption capacity can decline, and cannot also reach the solid particle eliminated in water phase
Purpose, therefore the sand filtration for wanting periodic replacement new or active carbon, workload increases, and sand filtration or active carbon selective absorption have
Limit, some solid particles of water phase cannot completely eliminate.
Summary of the invention
The purpose of the present invention is to provide prevent third phase and emulsion from producing during a kind of methane sulfonic acid system extraction indium
Raw new method, can pre- anti-emulsion and third phase formation, realize the efficient mistake for realizing extraction of indium, oil-water separation two-phase
Journey.
The extraction solution system of existing indium is strong corrosive inorganic acid aqueous solution system, and treatment process is to personnel health
Threaten it is larger, in addition, there is also for example to the indium for extracting solution system taste is more demanding, the undesirable long flow path of the rate of recovery,
Reagent consumption, metal are accounted for and are deposited and volume of the circular flow is big, other valuable metals are lost serious, and it is many that spent process water emission treatment difficulty is big etc.
Defect.In view of many defects of the prior art, the present inventor is intended to provide separation, recovery indium in a kind of system using organic acid
Method.But the extraction of indium from organic system, be easy to appear extractant dissolve each other in organism, aging damage, poor selectivity etc.
Problem, these problems seriously hinder the technology development that indium is extracted from organic aqueous phase system.By numerous studies, the present inventor
Finally find, using under the solution of indium system of methane sulfonic acid, there is good effect；However, by further investigation discovery, methylsulphur
There can be preferable effect of extracting in acid system, but extraction process easily occurs emulsifying and the problems such as third phase, the problem one
Determine the recycling effect of extracting that degree affects indium, is asked to solve emulsification and third phase existing for methylsulphur acid system extraction process
Topic, the present invention provides following technical schemes:
A method of the extraction of indium from the methane sulfonic acid lead solution containing indium, comprising the following steps:
Step (1): the methane sulfonic acid lead solution containing indium is obtained；
Lead-cerium alloy is including additive, Pb2+Source, methane sulfonic acid electrolyte in be electrolysed, obtain comprising Pb2+、In3+'s
Methane sulfonic acid lead solution containing indium；
The additive includes gelatine and wooden sodium sulfonate；
Step (2): lead is removed:
Methane sulfonic acid lead solution containing indium handle except lead, is obtained except liquid after lead；Except the pb after lead in liquid2+Content is not high
In 0.7gL-1；
Step (3): extraction:
PH≤2.5 of the regulation except liquid after lead；It is then extracted using extractant, by indium (In3+) be enriched with into organic phase；
Recycling obtains indium from the organic phase for be enriched with indium again.
Indium field of purification is being proposed, the present inventor originally extracts indium from the system of this organic acid of methane sulfonic acid.
The methane sulfonic acid that the present invention uses has that higher boiling, metal salt saturation solubility are high, conductivity is high, stability is good, recycles
The advantages that rate is high, liquid waste processing is easy and hypotoxicity.Using the method for the present invention can efficiently recovery indium, not only facilitating realization has
The high price of valence material utilizes, reduces environmental pressure, additionally aids lead-cerium alloy electrolytic process, shadow of the indium to lead main product quality
It rings.However, carrying out extraction to methylsulphur acid system is easy to appear emulsification and third phase, this will influence the extraction of indium to a certain extent
Effect and efficiency；It is inscribed between the technology to overcome, the invention proposes above-mentioned improvement projects, i.e., innovatively in the condition of additive
Methane sulfonic acid lead solution described in lower acquisition containing indium then cooperates again to the Pb in solution2+The pH's of control, the extraction of content
Control, can unexpectedly pre- anti-emulsion and third phase appearance, help further to promote effect of extracting, simplification extracts
Operating procedure.Different from it is existing occur emulsifying or third phase after means to save the situation, the method for the present invention passes through the processing line
Road and parameter are precisely controlled, can pre- anti-emulsion and third phase formation, there is higher practical value.
In the electrolyte, the Pb2+Source is preferably basic lead carbonate.
In the present invention, under the electrolyte, by the use of the additive, help to control subsequent solution
Emulsification is formed.
The present inventor the study found that control additive type, ratio and usage amount, help further to play its function
Can, facilitate the appearance for further avoiding extraction process emulsification.
Preferably, additive is the mixed solution of gelatine and wooden sodium sulfonate.
Preferably, gelatine and wooden sodium sulfonate's ratio are 1: (0.1~6) in additive.The study found that preferred at this
Ratio under, can help to it is subsequent extraction journey in emulsify and/or third phase generation.
Preferably, additive amount is 0.02~0.17gL-1.The dosage of the additive refers to: certain volume electricity
Solve the gross mass that two kinds of additives are added in liquid；It that is to say, the concentration of additive in electrolyte.The study found that control is excellent at this
It, can be to avoid emulsification in subsequent extraction process and/or the generation of third phase under the range of choosing.
Further preferably, in electrolyte, the concentration of gelatine is 0.01~0.11g.L-1；The concentration of wooden sodium sulfonate is 0.05
~0.06g.L-1.The study found that can help to emulsification and/or the production of third phase in subsequent extraction journey under the preferred ratio
It is raw.
It include In in methane sulfonic acid lead solution of the present invention containing indium3+、Pb2+, methanesulfonic acid solution.
In methane sulfonic acid lead solution containing indium, acidity (CH3SO3The concentration of H) it is 60~150g.L-1。
In methane sulfonic acid lead solution containing indium, Pb2+Concentration is not higher than 130gL-1, preferably 50~130gL-1。
The present invention can handle In3+The lower solution system of content.For example, in the methane sulfonic acid lead solution containing indium, In3+
Concentration is 0.3~5.0g.L-1。
In methane sulfonic acid lead solution containing indium, also allow containing not higher than 0.9gL-1Zn2+, it is not higher than 1g.L-1's
Sn2+。
Preferably, the ingredient of solution is (gL in the methane sulfonic acid lead solution containing indium-1): Pb2+50~130,
CH3SO3H 50~300,0.3≤In3+≤5.0、Zn2+≤0.9、Sn2+≤1.0。
The research of the invention finds that methane sulfonic acid system of the present invention is based on, further to the methane sulfonic acid lead containing indium
Pb in solution2+Content, except the solution after lead pH control and extraction process the selection of extractant, extraction process phase
Than, the control of solution acidity, extraction temperature etc., it can further cooperate with and avoid that emulsification in treatment process, effect of extracting is not high, occurs
The problems such as third phase.
The research of the invention finds that handle except lead to the methane sulfonic acid lead solution containing indium, and innovatively find, by solution
In Pb2+Control is being not higher than 0.7g.L-1Level under, can unexpectedly avoid emulsification and third phase appearance.
Except existing known method can be used in lead processing method.Preferably, except lead processing uses electrodeposition method and chemical precipitation
Method.Electrodeposition method and sulfuric acid precipitation method, that is to say, using the methane sulfonic acid lead solution containing indium as electrolyte, first be removed using electrodeposition
Part lead adds theoretical sulfuric acid amount, removes part lead precipitating, obtains the methanesulfonic acid solution containing indium for subtracting lead.
Preferably, removing after lead in liquid, Pb2+≤0.5g.L-1.The study found that control is avoiding under the concentration range
Under the premise of emulsification and third phase are formed, additionally aids and further promote In3+Effect of extracting, for example, facilitate further
Promote In3+Extraction yield.
Present invention research also found, will control except the pH of liquid after lead≤2.5, can contribute to avoid newborn in treatment process
Change, effect of extracting is not high, the problems such as third phase occurs.
Preferably, regulation is 0.5~1 except the pH of liquid after lead in step (3).The study found that at the preferred pH,
Under the premise of being emulsified to avoid extraction process, additionally aids and promote In3+Extraction yield.
In step (3), existing material can be used come the pH of the solution after regulating and controlling except lead；It is preferred that using methanesulfonic acid solution and
PH of the ammonium hydroxide regulation except the solution after lead.
Preferably, extractant is P204。
Extractant is before extraction in advance through dilution dilution agent processing；The diluent is preferably sulfonated kerosene；After dilution
Extractant in, the percentage by volume of extractant is 20%~70%.
Preferably, the temperature of extraction process is 10 DEG C~50 DEG C；Preferably 20~30 DEG C.
Extraction process can be used the mode of being stirred and/or use counter-current extraction mode；
It stirs in extraction process, mixing time 2~15 minutes, 800~1300rmin of mixing speed-1；
During counter-current extraction, series 1-5 grades is extracted, compares Vo∶VA=1: (2~7).
The organic phase for being enriched with indium being obtained by extraction is stripped, In3+ is transferred to water phase, passes through conventional concentration
Etc. means, obtain indium.
Beneficial effects of the present invention:
Can prevent methane sulfonic acid system extraction of indium process generate third phase and occur emulsion, make extraction process smoothly into
Row, it is easy to operate, it is at low cost, industrial applications can be suitble to.
Detailed description of the invention
The phenomenon that Fig. 1 is 1 extraction process of embodiment is schemed；It shows that water-oil phase effect is good, does not occur emulsifying and third phase；
The phenomenon that Fig. 2 is 1 extraction process of comparative example is schemed；There is third phase in display；
The phenomenon that Fig. 3 is 2 extraction process of comparative example is schemed；There is emulsion in display.
The phenomenon that Fig. 4 is 3 extraction process of comparative example is schemed；There is emulsion in display.
The phenomenon that Fig. 5 is 4 extraction process of comparative example is schemed；There is emulsion in display.
Specific embodiment
Below in conjunction with example the present invention is described further the content of present invention.
Following embodiment and comparative example, unless specified or limited otherwise, VoRefer both to the volume of organic phase, VARefer to the volume of water phase.
The elemental composition of lead-cerium alloy is (wt%):
Embodiment 1:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.01gL-1Gelatine and 0.05gL-1Wooden sodium sulfonate, 124.77gL-1Alkali formula carbon
The methane sulfonic acid of lead plumbate；
The ingredient for being electrolysed the obtained methane sulfonic acid lead solution containing indium is (gL-1): Pb2+50、CH3SO3H 80、In3+
2.11
2. by methane sulfonic acid lead solution electrodeposition four hours；
3. theoretical sulfuric acid amount, after room temperature magnetic agitation one hour, vacuum filter, except there is liquid after lead is added in liquid after electrodeposition
0.7g·L-1Pb2+；
4. the pH for adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide is 0.5, extraction stoste is obtained；
5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；
6. extracting series is 1 grade, Vo∶VA=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, stirring speed
Spend 1000r.min-1.The extraction yield of indium is greater than 96%, does not generate third phase or emulsion occurs.
Embodiment 2:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.11gL-1Gelatine and 0.06gL-1Wooden sodium sulfonate, 124.77gL-1Alkali formula carbon
The methane sulfonic acid of lead plumbate；
The ingredient for being electrolysed the obtained methane sulfonic acid lead solution containing indium is (gL-1): Pb2+63、CH3SO3H 90、In3+
2.54
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.45g.L after lead-1Pb2+；4. adjusting the pH of liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
It is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA=1
:2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000rmin-1.The extraction yield of indium is greater than
96%, it does not generate third phase or emulsion occurs.
Embodiment 3:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.05gL-1Gelatine and 0.05gL-1Wooden sodium sulfonate, 124.77gL-1Alkali formula carbon
The methane sulfonic acid of lead plumbate；
The ingredient for being electrolysed obtained methane sulfonic acid lead solution is (gL-1): Pb2+55、CH3SO3H 87、In3+2.23
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.45gL after lead-1Pb2+；4. adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
PH is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA
=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000rmin-1.The extraction yield of indium is greater than
96%, it does not generate third phase or emulsion occurs.
Embodiment 4:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.1gL-1Gelatine and 0.05gL-1Wooden sodium sulfonate, 124.77gL-1Basic carbonate
The methane sulfonic acid of lead；
The ingredient for being electrolysed obtained methane sulfonic acid lead solution is (gL-1): Pb2+50、CH3SO3H 80、In3+2.11
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.45gL after lead-1pb2+；4. adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
PH is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA
=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000rmin-1.The extraction yield of indium is greater than
98%, it does not generate third phase or emulsion occurs.
Embodiment 5:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.01gL-1Gelatine and 0.06gL-1Wooden sodium sulfonate, 124.77gL-1Alkali formula carbon
The methane sulfonic acid of lead plumbate；
The ingredient for being electrolysed obtained methane sulfonic acid lead solution is (gL-1): Pb2+50、CH3SO3H 80、In3+2.11
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.45gL after lead-1pb2+；4. adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
PH is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA
=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000rmin-1.The extraction yield of indium is greater than
97%, it does not generate third phase or emulsion occurs.
Comparative example 1:
It is compared with embodiment 1, difference essentially consists in, except the Pb of the solution after lead2+Content is higher, specific as follows:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.01gL-1Gelatine and 0.05gL-1Wooden sodium sulfonate, 124.77gL-1Alkali formula carbon
The methane sulfonic acid of lead plumbate；
The ingredient for being electrolysed obtained methane sulfonic acid lead solution is (gL-1): Pb2+50、CH3SO3H 80、In3+2.11
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.76gL after lead-1Pb2+；4. adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
PH is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA
=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000r.min-1.The extraction yield of indium is
93%, generate third phase.
Comparative example 2:
It is compared with embodiment 2, difference essentially consists in, and additive level is higher when electrolysis, specific as follows:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.07gL-1Gelatine and 0.11gL-1Wooden sodium sulfonate, 124.77gL-1Alkali formula carbon
The methane sulfonic acid of lead plumbate；
The ingredient for being electrolysed obtained methane sulfonic acid lead solution is (gL-1): Pb2+63、CH3SO3H 90、In3+2.54
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.45gL after lead-1Pb2+；4. adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
PH is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA
=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000rmin-1.The extraction yield of indium is
93%, emulsion occurs.
Comparative example 3:
It is compared with embodiment 3, difference essentially consists in, the pH higher of the starting soln before extraction, specific as follows:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.05gL-1Gelatine and 0.05gL-1Wooden sodium sulfonate, 124.77gL-1Alkali formula carbon
The methane sulfonic acid of lead plumbate；
The ingredient for being electrolysed obtained methane sulfonic acid lead solution is (gL-1): Pb2+55、CH3SO3H 87、In3+2.33
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.45gL after lead-1Pb2+；4. adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
PH is 3, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA=1
:2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000rmin-1.The extraction yield of indium is 91%,
Emulsion occurs.
Comparative example 4:
It is compared with embodiment 4, difference essentially consists in, and the temperature of extraction process is higher, specific as follows:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.1gL-1Gelatine and 0.05gL-1Wooden sodium sulfonate, 124.77gL-1Basic carbonate
The methane sulfonic acid of lead；
The ingredient for being electrolysed obtained methane sulfonic acid lead solution is (gL-1): Pb2+50、CH3SO3H 80、In3+2.11
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.45gL after lead-1 Pb2+；4. adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
PH is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA
=1: 2；7. extraction is 60 DEG C, oscillation and time of repose are 5min, mixing speed 1000rmin-1.The extraction yield of indium is
93%, emulsion occurs.
Comparative example 5:
It is compared with embodiment 5, difference essentially consists in, and additives ratio is higher when electrolysis, specific as follows:
1. lead-cerium alloy be anode, with stainless steel plate be to electrode, electrolyte in be electrolysed 72h, obtain comprising Pb2+、
In3+The methane sulfonic acid lead solution containing indium (present case is also referred to as methane sulfonic acid lead solution)；
In electrolyte, to include 0.01gL-1Gelatine and 0.07gL-1Wooden sodium sulfonate, 124.77gL-1Alkali formula carbon
The methane sulfonic acid of lead plumbate；
The ingredient for being electrolysed obtained methane sulfonic acid lead solution is (gL-1): Pb2+50、CH3SO3H 80、In3+2.11
2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount, room temperature magnetic agitation one is added in liquid after electrodeposition
After hour, vacuum filter, except liquid has 0.45gL after lead-1Pb2+；4. adjusting liquid after removing lead with methanesulfonic acid solution and ammonium hydroxide
PH is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting series is 1 grade, Vo∶VA
=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000rmin-1.The extraction yield of indium is
94%, emulsion occurs.
Comparative example 6:
It is that in electrolyte, additive is only gelatine with embodiment difference, specific as follows:
1. 0.117gL is added when electrolysis-1Gelatine, obtaining the methane sulfonic acid lead solution containing indium, (ingredient is (gL-1): Pb2 +56、CH3SO3H 73、In3+1.83)；2. by methane sulfonic acid lead solution electrodeposition four hours；3. theoretical sulfuric acid amount is added in liquid after electrodeposition,
After room temperature magnetic agitation one hour, vacuum filter, except liquid has 0.45g.L after lead-1Pb2+；4. with methanesulfonic acid solution and ammonium hydroxide tune
Section is 0.5 except the pH of liquid after lead, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；6. extracting grade
Number is 1 grade, Vo∶VA=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed 1000r.min-1.Indium
Extraction yield be 93%, occur emulsion.
Comparative example 7:
It is that in electrolyte, additive is only wooden sodium sulfonate with embodiment difference, specific as follows:
1. 0.067g.L is added when electrolysis-1Wooden sodium sulfonate, obtaining the methane sulfonic acid lead solution containing indium, (ingredient is (gL-1): Pb2+55、CH3SO3H 71、In3+2.05)；2. by methane sulfonic acid lead solution electrodeposition four hours；3. liquid is added theoretical after electrodeposition
Sulfuric acid amount, after room temperature magnetic agitation one hour, vacuum filter, except liquid has 0.45gL after lead-1Pb2+；4. using methanesulfonic acid solution
It adjusts with ammonium hydroxide except the pH of liquid after lead is 0.5, obtains extraction stoste；5. organic phase composition P204With 3: 7 volume ratio of sulfonated kerosene；
6. extracting series is 1 grade, Vo∶VA=1: 2；7. extraction is 25 DEG C, oscillation and time of repose are 5min, mixing speed
1000r.min-1.The extraction yield of indium is 93%, and emulsion occurs.
Claims (10)
1. a kind of method of the extraction of indium from the methane sulfonic acid lead solution containing indium, which comprises the following steps:
Step (1): the methane sulfonic acid lead solution containing indium is obtained；
Lead-cerium alloy is including additive, Pb2+Source, methane sulfonic acid electrolyte in be electrolysed, obtain comprising Pb2+、In3+Contain indium
Methane sulfonic acid lead solution；
The additive includes gelatine and wooden sodium sulfonate；
Step (2): lead is removed:
Methane sulfonic acid lead solution containing indium handle except lead, the pb in solution is made2+Content is not higher than 0.7gL-1, obtain except lead
Liquid afterwards；
Step (3): extraction:
PH≤2.5 of the regulation except liquid after lead；It is then extracted using extractant, by In3+Enrichment is into organic phase；Again from enrichment
There is recycling in the organic phase of indium to obtain indium.
2. the method as described in claim 1, which is characterized in that gelatine and wooden sodium sulfonate's ratio are 1: (0.1~6).
3. method according to claim 2, it is characterised in that: in electrolyte, dosage is 0.02~0.17gL in additive-1；
Further preferably, in electrolyte, the concentration of gelatine is 0.01~0.11gL-1；The concentration of wooden sodium sulfonate be 0.05~
0.06g·L-1。
4. the method as described in claim 1, it is characterised in that: in the methane sulfonic acid lead solution containing indium, acidity be 60~
150g·L-1；
Pb2+Concentration is preferably no greater than 130gL-1, further preferably 50~130gL-1。
5. the method as described in claim 1, it is characterised in that: in step (2), except the pb of liquid after lead2+Content is not higher than
0.5g·L-1。
6. the method as described in claim 1, it is characterised in that: in step (3), regulation is 0.5~1 except the pH of liquid after lead.
7. method as claimed in claim 6, it is characterised in that: the extractant is P204；
Preferably, extractant is before extraction in advance through dilution dilution agent processing；The diluent is preferably sulfonated kerosene；
In extractant after dilution, the percentage by volume of extractant is preferably 20%~70%.
8. the method as described in claim 1, it is characterised in that: the temperature of extraction process is 10 DEG C~50 DEG C.
9. the method as described in claim 1, it is characterised in that: extraction process can be used the mode of being stirred and/or using inverse
Flow extraction mode；
It stirs in extraction process, mixing time 2~15 minutes, 800~1300rminw of mixing speed1；
During counter-current extraction, series 1-5 grades is extracted, compares VO∶VA=1: (2~7).
10. the method as described in claim 1, which is characterized in that in stripping process, carried out to the organic phase for being enriched with indium anti-
Extraction, indium is transferred in water phase, subsequent concentration and recovery obtains indium.
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| CN114892008A (en) * | 2022-05-25 | 2022-08-12 | 中南大学 | Method for purifying lead electrolytic refining waste liquid of methanesulfonic acid system |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333605A (en) * | 2007-06-28 | 2008-12-31 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Technology for extracting indium from indium-rich bottom lead |
| JP2012072480A (en) * | 2010-09-27 | 2012-04-12 | Jx Nippon Mining & Metals Corp | Method for selectively recovering indium from mixture of indium and tin |
| CN102899687A (en) * | 2012-11-13 | 2013-01-30 | 云南天浩稀贵金属股份有限公司 | Separation and extraction process for crude lead containing indium |
| CN103101966A (en) * | 2011-11-10 | 2013-05-15 | 财团法人工业技术研究院 | Method for recovering indium tin oxide |
| CN106399703A (en) * | 2016-09-27 | 2017-02-15 | 贵州宏达环保科技有限公司 | Method for extracting Pb, In and Ag from indium-containing lead silver residues |
| CN107557596A (en) * | 2016-07-01 | 2018-01-09 | 吕芳贤 | By the method for recovery indium and tin element in acid etching waste liquid |
| CN108486392A (en) * | 2018-03-16 | 2018-09-04 | 湖南腾驰环保科技有限公司 | A method of improving the material indium leaching rate of antimony lead containing indium |
-
2018
- 2018-09-25 CN CN201811117691.8A patent/CN109055744B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333605A (en) * | 2007-06-28 | 2008-12-31 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Technology for extracting indium from indium-rich bottom lead |
| JP2012072480A (en) * | 2010-09-27 | 2012-04-12 | Jx Nippon Mining & Metals Corp | Method for selectively recovering indium from mixture of indium and tin |
| CN103101966A (en) * | 2011-11-10 | 2013-05-15 | 财团法人工业技术研究院 | Method for recovering indium tin oxide |
| CN102899687A (en) * | 2012-11-13 | 2013-01-30 | 云南天浩稀贵金属股份有限公司 | Separation and extraction process for crude lead containing indium |
| CN107557596A (en) * | 2016-07-01 | 2018-01-09 | 吕芳贤 | By the method for recovery indium and tin element in acid etching waste liquid |
| CN106399703A (en) * | 2016-09-27 | 2017-02-15 | 贵州宏达环保科技有限公司 | Method for extracting Pb, In and Ag from indium-containing lead silver residues |
| CN108486392A (en) * | 2018-03-16 | 2018-09-04 | 湖南腾驰环保科技有限公司 | A method of improving the material indium leaching rate of antimony lead containing indium |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114892008A (en) * | 2022-05-25 | 2022-08-12 | 中南大学 | Method for purifying lead electrolytic refining waste liquid of methanesulfonic acid system |
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