CN108715935A - A kind of method of sulfuric acid lead skim wet clean processes - Google Patents
A kind of method of sulfuric acid lead skim wet clean processes Download PDFInfo
- Publication number
- CN108715935A CN108715935A CN201810618688.8A CN201810618688A CN108715935A CN 108715935 A CN108715935 A CN 108715935A CN 201810618688 A CN201810618688 A CN 201810618688A CN 108715935 A CN108715935 A CN 108715935A
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- lead
- solution
- electrodeposition
- chlorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of method of sulfuric acid lead skim wet clean processes, this method is first coordination leaching agent with chloride solution, and carrying out chlorination coordination to sulfuric acid lead skim leaches, and obtains lead chlorination coordination leachate and leached mud.Leachate filters postcooling crystallization while hot, carries out solid-liquor separation again later, respectively obtains liquid after chlorination leading crystal and crystallization.Liquid is back to chlorination coordination and leaches after crystallization, and the chlorination leading crystal crystallized, which is added in Acetate Solution system, carries out conversion leaching.Leachate is not purified after conversion is leached extracts lead directly as catholyte using diaphragm electrodeposition technology.After diaphragm electrolysis, cathode obtains 99.9% or more electric lead, and cathode and anode stripped solution can return to system use, realize the closed cycle of technological process.The technique can carry out clean and effective processing to sulfuric acid lead skim, directly obtain the higher electric lead product of purity, strong with adaptability to raw material, technological process is simple, the valuable element rate of recovery is high, clean environment firendly outstanding advantages.
Description
Technical field
The invention belongs to field of hydrometallurgy, and in particular to a kind of method of sulfuric acid lead skim wet clean processes.
Background technology
In Zinc Hydrometallurgy Process, the normal a large amount of sulfuric acid lead skims of output.In addition, zinc leaching residue converter dust, steel plant's flue dust, refining
Copper work flue dust etc. is through fire reduction volatilization treated zinc oxide equally contains lead, and after sulfuric acid leaching, lead mostly concentrates on leached mud
In, also form sulfuric acid lead skim.Lead in these sulfuric acid lead skims is most of with PbSO4Object mutually exists, lead content generally 10~
50% differs, and it is significant to realize that its recycling, minimizing recycle.
The treatment process of sulfuric acid lead skim can be divided into two kinds of pyrometallurgy and hydrometallurgy at present.Pyrometallurgy is mainly by it
As refining leady raw materials, arranges in pairs or groups together with lead concentrate and recycle lead into pyrogenic process lead smelting system.But due to lead content phase in sulfuric acid lead skim
To relatively low, and compared with PbS concentrate meltings, the decomposition sheerly endothermic reaction of lead sulfate needs outside to be provided with a large amount of thermal energy.Therefore
It is arranged in pairs or groups into stove together with PbS concentrate when melting, collocation amount is limited, is otherwise difficult to maintain the thermal balance of lead smelting system.
In addition, fire metallurgy process processing sulfuric acid lead skim can not only consume height, and it is also easy to produce SO2, the atmosphere pollutions such as volatility lead dust,
Melting fume treatment cost is relatively higher；Wet recycling process most common lead sulfate Slag treatment method at present, mainly with
Na2CO3Or NaHCO3For desulfurizing agent, by PbSO in sulfuric acid lead skim under the conditions of strong mixing4It is converted into PbCO3, then it is roasted or
Supplying fluosilicic acid system is electrolysed to obtain lead powder.But it was verified that there are conversion ratios is low, waste water row for sulfuric acid lead skim wet processing process
High-volume greatly, the problems such as toxic and harmful gas such as HF are easily discharged when fluosilicic acid system is electrolysed.China is maximum wet method refining in the world
Zinc producing country, in addition steel mill's cigarette ash, converter dust processing etc., the sulfuric acid lead skim of annual output flood tide.As Environmental is protected
Shield dynamics continues to increase, develop it is a kind of cleaning, efficient lead sulfate Slag treatment new process have huge realistic meaning,
It is worth with good energy economy & environment.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of sides of sulfuric acid lead skim wet clean processes
Method, to realize the cleaning, high efficiente callback of lead in sulfuric acid lead skim.
A kind of method of sulfuric acid lead skim wet clean processes of the present invention, includes the following steps：
Step 1：The chlorination coordination of sulfuric acid lead skim is leached
It is that coordination leaching agent carries out chlorination coordination leaching, solid-liquid point after leaching to sulfuric acid lead skim with chloride solution
From obtaining the leachate containing lead source and leached mud；
Step 2：Leachate crystallizes
The leachate crystallization containing lead source that step 1 is obtained, is separated by solid-liquid separation, after obtaining chlorination leading crystal and crystallization
Liquid；
Step 3：The conversion of chlorination leading crystal is leached
Acetate Solution is configured as conversion leaching agent, and Acetate Solution is added in the chlorination leading crystal that step 2 is obtained
In carry out conversion leach obtain conversion leachate；
Step 4：The diaphragm electrodeposition of conversion leachate carries lead
The conversion leachate that step 3 is obtained is carried out as catholyte, using ammonium chloride solution as anolyte
Diaphragm electrodeposition extracts lead；Electric lead, cathode stripped solution, anode stripped solution are obtained after electrodeposition.
The technical scheme is that：It is first coordination leaching agent with chloride solution, carrying out chlorination to sulfuric acid lead skim matches
Position is leached, and lead chlorination coordination leachate and leached mud are obtained.Lead chlorination coordination leachate is crystallized, carries out liquid again later
Gu separation respectively obtains liquid after chlorination leading crystal and crystallization.Liquid can be back to chlorination coordination and leach after crystallization, crystallize
Chlorination leading crystal, which is added in Acetate Solution system, carries out conversion leaching.Conversion leach after leachate it is not purified directly as
Catholyte extracts lead using diaphragm electrodeposition technology.After diaphragm electrolysis, cathode obtains 99.9% or more electric lead, and yin, yang
Pole stripped solution can be used with return system, realize the closed cycle of technological process.The technique can clean sulfuric acid lead skim
Efficient process directly obtains the higher electric lead product of purity, has that adaptability to raw material is strong, technological process is simple, valuable element returns
The outstanding advantages of high income, clean environment firendly.
In the present invention, it is leached by the conversion of Acetate Solution system, being smoothed out for diaphragm electrodeposition has been effectively ensured,
If inventor has found that directly carrying out diaphragm electrodeposition using the leachate containing lead source obtained by step 1 as catholyte carries
Take lead.In electrolytic deposition process, as leachate gradually cools down, will constantly there be the precipitation of chlorination leading crystal in catholyte.Cathode
Plumbum ion concentration constantly reduces in liquid.Product is precipitated in cathode can not be at plate, but loose lead powder.
In the present invention during diaphragm electrodeposition, using ammonium chloride solution as anolyte, sun when electrodeposition can avoid
Chlorine is precipitated in pole.Inventor find, the present invention electrodeposition system in, when in anolyte simultaneously have Cl-And NH4 +When, sun
Pole occur reaction be：6NH4 +- 6e=3N2↑+24H+, what anode was precipitated is harmless nitrogen rather than chlorine.It realizes this and contains chlorine
The cleaning treatment of compound solution system electrolytic deposition process.
Preferred scheme, in the step one, comprising reacting the chlorination to form precipitation with sulfate radical in chloride solution
Object A, and not sedimentable chloride B is reacted with sulfate radical.
Further preferred, in the chloride solution, the amount of chloride A is by the sulfate radical whole shape in sulfuric acid lead skim
At 1 times or more of theoretical amount needed for sulfate precipitation.
As further preferably, in the chloride solution, the amount of chloride A is by the sulfate radical in sulfuric acid lead skim
It is completely formed 1.0~3.5 times of theoretical amount needed for sulfate precipitation.
As further preferably, in the chloride solution, the amount of chloride A is by the sulfate radical in sulfuric acid lead skim
It is entirely formed to 1.5~3 times of theoretical amount needed for sulfate precipitation.
Preferred scheme, in the chloride solution, the ratio between mole of chloride B and chloride A >=1.
Further preferred, in the chloride solution, the ratio between mole of chloride B and chloride A is 1~5:1.
As further preferably, in the chloride solution, the ratio between mole of chloride B and chloride A is 1.5
~4:1.
Further preferred, the chloride A is selected from CaCl2、BaCl2At least one of.
Further preferred, the chloride B is selected from NH4At least one of Cl, NaCl.
Preferred scheme, extraction temperature is 20~95 DEG C in the step one.
Further preferred, extraction temperature is 45~90 DEG C in the step one.
Preferred scheme, extraction time is 30~180min in the step one.
Further preferred, extraction time is 90~160min in the step one.
Preferred scheme, in the step one, the solid-liquid mass volume ratio of sulfuric acid lead skim and chloride solution is 1:3~
9(g:ml)。
Further preferred, in the step one, the solid-liquid mass volume ratio of sulfuric acid lead skim and chloride solution is 1:4
~8 (g:ml).
Preferred scheme in the step one, filters while hot after leaching, obtain leachate containing lead source and
Leached mud.
Preferred scheme crystallizes the leachate cooled to room temperature containing lead source that step 1 obtains.
Preferred scheme, in the step three, acetate is selected from least one of sodium acetate, ammonium acetate.
Further preferred, the addition of the acetate is to convert the Chlorine in Solution lead to theory needed for lead acetate
1~3 times of amount.
As it is further preferably, the addition of the acetate is converts the Chlorine in Solution lead to lead acetate institute
Need 1.5~2.5 times of theoretical amount.
Preferred scheme, the temperature that leaching is converted in the step three are 20~90 DEG C.
Further preferred, the temperature that leaching is converted in the step three is 50~80 DEG C.
Preferred scheme, the time that leaching is converted in the step three are 30~180min.
Further preferred, the time that leaching is converted in the step three is 60~160min.
Preferred scheme, in the step three, the solid-liquid mass volume ratio for converting leaching is 1:3~7 (g:ml).
Preferred scheme fills into chloride A in liquid after being crystallized obtained by step 3 and obtains solution return to step one as chlorine
Change coordination leaching agent；Sulfate radical in sulfuric acid lead skim is is completely formed sulfate precipitation institute by the amount of the Chlorine in Solution compound A
Need 1.0~3.5 times of theoretical amount.
The conversion leachate that step 3 obtains is pumped into the cathode chamber in diaphragm cell as cathode electricity by preferred scheme
Liquid is solved, using ammonium chloride solution as anolyte, diaphragm electrodeposition is carried out and extracts lead.
Preferred scheme, the diaphragm are anionic membrane.
Preferred scheme, when the step four septation electrodeposition, current density 50A/m2~500A/m2。
Further preferably, when the step four septation electrodeposition, current density is 220~350A/m2。
Preferred scheme, when the step four septation electrodeposition, temperature is 20~80 DEG C.
Further preferably, when the step four septation electrodeposition, temperature is 30~50 DEG C.
Preferred scheme, it is heteropolar away from for 3~12cm when the step four septation electrodeposition.
It is further preferably, it is heteropolar away from for 4~6cm when the step four septation electrodeposition.
Preferred scheme, in the step four, cathode is graphite cake, titanium plate, plating ruthenium titanium plate, stainless steel plate, lead beginning pole
One kind in piece.
Preferred scheme, in the step four, anode is paliform anode.
Further preferred, the paliform anode is made of n root fence sticks, n >=2, described any adjacent two
The spacing of fence stick is 1~4cm.
Inventor has found that the spacing of fence stick has a certain impact to electrodeposition, and spacing is excessive, then its electricity formed with cathode
Field is uneven, and obtained cathode electrodeposition product morphology is bad；Spacing is too small, then it is close with tabular anode effect, and anode is easy
Passivation, slot pressure increase very fast.
As further preferably, the n is 3~5.
In the present invention, the fence stick of paliform anode is in the same plane.
As further preferably, the spacing of any adjacent two fence stick is 1~3.5cm.
Preferred scheme, the anode material are one kind in graphite, titanium, plating ruthenium titanium.
Preferred scheme, when the step four septation electrodeposition, the electrodeposition period >=20h/ times.
Further preferably, when the step four septation electrodeposition, the electrodeposition period is 24~30h/ times.
Preferred scheme, in the step four, a concentration of 3~8mol/L of the ammonium chloride solution.
Preferred scheme, in the step four, a concentration of 4~6mol/L of the ammonium chloride solution.
Preferred scheme, the cathode stripped solution return to step three are used as conversion leaching agent.
Anode electricity when return to step four after neutralizer is used for diaphragm electrodeposition is added in preferred scheme, the anode stripped solution
Solve liquid；The neutralizer that anode stripped solution is added is ammonium hydroxide；Ammonium hydroxide is added to adjust the pH value of anode stripped solution to step 4 middle-jiao yang, function of the spleen and stomach
Initial pH value before the electrolyte diaphragm electrodeposition of pole.
Present invention advantage compared with the prior art and the advantageous effects brought：
The present invention has that " long flow path, metal recovery rate be low, cost for existing sulfuric acid lead skim pyrogenic process, wet processing process
The present situation of high, pollution weight ", it is proposed that a kind of " chlorination is coordinated leaching-decrease temperature crystalline-acetate conversion leaching-diaphragm electrodeposition extraction
The technical combinations of lead-electrodeposition stripped solution difference reuse ".The high selectivity of lead in sulfuric acid lead skim not only may be implemented in the technical combinations
Effect extraction, can also realize that the conversion of sulfate radical in sulfuric acid lead skim is fixed.And acetate ion is used in the technical combinations to carry
" carrier " for taking lead is electrolysed and is electrolysed by specific diaphragm electrolysis system stripped solution post-processing, can directly obtain the same of electric lead
When again can regenerate coordination leaching agent return for coordination leaching, realize the closed cycle of flow.
In the electrolytic deposition process of the present invention, using NH4Cl is anolyte, can avoid anode when electrodeposition and chlorine is precipitated.
The present invention electrodeposition system in, when in anolyte simultaneously have Cl-And NH4 +When, the reaction that anode occurs is：6NH4 +-6e
=3N2↑+24H+, what anode was precipitated is harmless nitrogen rather than chlorine.Realize the chloride solution system electrolytic deposition process
Cleaning treatment.It can be used with regeneration cycle in anode stripped solution by the way that neutralizer is added.
Pb when being directed to more lead transition-metal ions, conventional electrolysis simultaneously2+Oxidation reaction easily occurs in anode and forms indissoluble PbOxResistance
It is the problem of hindering reaction to carry out, proposed by the present invention to use Diaphragm Electrolysis Technology be by Pb (Ac)i 2-i(i=1,2,3,4) conversion leaching
Go out liquid directive electrodeposition and obtain high-purity electricity lead product, anode surface is without Pb2+Conventional method is not present in the generation of oxidation reaction
Easily generate PbOxThe problem of leading to anodic passivity and electrodeposition recycling lead can not be continued.In addition, being found by lot of experiments, adopt
With the paliform anode of specific shape, anode surface PbO when being also beneficial to avoid being electrolysedxGeneration.In the present invention, electrodeposition terminates
Afterwards, anolyte regenerates NH after ammonium hydroxide adjusts pH4Cl solution may continue as anolyte and return for diaphragm electrodeposition.And by
It is not consumed in electrolytic deposition process acetate ion, therefore cathode stripped solution can directly return to the conversion for lead chloride after electrodeposition
It leaches, to realize the closed cycle of flow.
In the present invention, leaching rate >=96.7% of lead, the purity of electric lead as obtained by diaphragm electrodeposition extraction lead >=
99.9%.
Each step is effectively connected in the present invention, and coordinated, inventor is worked by many experiments, obtains this field
Technical staff is difficult to the technique effect expected.It is proved by a large amount of experimental study, " chlorination coordination leaching proposed by the present invention
Go out-decrease temperature crystalline-acetate conversion leaching-diaphragm electrodeposition extraction lead-electrodeposition stripped solution difference reuse " technical combinations can be real
The cleaning of lead, high efficiency extraction in existing sulfuric acid lead skim.Inventor has carried out continuing to optimize improvement to each operation stage of above-mentioned processing, makes
It cooperates, all linked with one another, just obtains the effect of the present invention, consumes a large amount of painstaking effort of inventor.
Specific implementation mode
Following embodiment is intended to further illustrate the present invention, but the present invention is not limited to the following embodiments.
Embodiment 1
The sulfuric acid lead skim that Hunan company provides, through analyzing wherein with PbSO4The lead content of object phase preservation is 26.8% (matter
Measure percentage).
Sulfuric acid lead skim 200g is taken, with CaCl2With NH4The mixed solution of Cl is that coordination leaching agent carries out the sulfuric acid lead skim
Chlorination is coordinated Leach reaction.Wherein, CaCl2Addition be the sulfate radical in sulfuric acid lead skim is entirely formed to needed for calcium sulfate
1.5 times of theoretical amount, NH4Cl and CaCl2The ratio between mole be 1.5:1.It is 85 DEG C that chlorination, which is coordinated extraction temperature, Gu (g) liquid
(ml) than being 1:4, extraction time 90min；Chlorination coordination is immediately separated by filtration Leaching Systems after leaching while hot, obtains
Leaded chlorination coordination leachate and leached mud, analyze lead content in leached mud, calculate to obtain the chlorination coordination leaching of lead in sulfuric acid lead skim
Extracting rate is 96.7%.Obtained leaded chlorination coordination leachate is placed in beaker after cooled to room temperature, solid-liquor separation obtains
Liquid 784ml after to chlorination leading crystal 57.6g and crystallization, this 784ml solution are used for the potassium cloride of next batch sulfuric acid lead skim.It will
The 57.6g chlorination leading crystals that decrease temperature crystalline obtains, which are added in 250ml ammonium acetate solutions, carries out conversion leaching.Ammonium acetate in solution
Amount be convert the Chlorine in Solution lead to theoretical amount needed for lead acetate 1.5 times.Extraction temperature is 50 DEG C when conversion is leached,
Extraction time is 60min.It under similarity condition, then carries out 7 batches and repeats to test as described above, collect conversion leachate altogether
2025ml.Obtained conversion leachate is pumped into the cathode chamber of diaphragm electrodeposition slot.Configuration simultaneously and catholyte same volume concentration
For the ammonium chloride solution of 4mol/L diaphragm electrodeposition extraction lead is carried out as anolyte.Current density is 220A/m when diaphragm electrodeposition2,
30 DEG C of electrodeposition temperature, heteropolar away from 4cm, cathode is Lead initiated plate electrode, and anode is coupled the paliform formed sun by 3 graphite rods through copper folder
Pole, rodlike fence spacing 1cm；The electrodeposition period, diaphragm material was anionic membrane for 24 hours.Pattern is obtained after electrolysis in cathode to cause
The purity of close smooth electric lead, gained electricity lead is 99.93%, current efficiency 98.8%.Tank voltage is tieed up always in electrolytic process
It keeps steady and is set to 2.2~2.4V, anode surface is also precipitated without solid product.
Embodiment 2
The sulfuric acid lead skim that Guangxi company provides, through analyzing wherein with PbSO4The lead content of object phase preservation is 23.9% (matter
Measure percentage).
Sulfuric acid lead skim 2000g is taken, with BaCl2Mixed solution with NaCl is that coordination leaching agent carries out the sulfuric acid lead skim
Chlorination is coordinated Leach reaction.Wherein, BaCl2Addition be the sulfate radical in sulfuric acid lead skim is entirely formed to needed for barium sulfate
3 times of theoretical amount, NaCl and BaCl2The ratio between mole be 4:1.It is 45 DEG C that chlorination, which is coordinated extraction temperature, Gu (g) liquid (ml) compares
It is 1:8, extraction time 160min；Chlorination coordination is immediately separated by filtration Leaching Systems after leaching while hot, obtains leaded
Chlorination is coordinated leachate and leached mud, analyzes lead content in leached mud, calculates to obtain the chlorination coordination leaching rate of lead in sulfuric acid lead skim
It is 98.1%.Obtained leaded chlorination coordination leachate is placed in beaker after cooled to room temperature, solid-liquor separation obtains chlorine
Liquid 15.8L after changing leading crystal 503g and crystallizing.Liquid is used for the potassium cloride of next batch sulfuric acid lead skim after this 15.8L crystallizations.It will
The 503g chlorination leading crystals that decrease temperature crystalline obtains, are added in the sodium acetate solution of 3.5L and carry out conversion leaching.Acetic acid in solution
The amount of sodium is convert the lead chloride of the addition to theoretical amount needed for lead acetate 2.5 times.Extraction temperature is 80 when conversion is leached
DEG C, extraction time 160min.Conversion leachate 3.52L is collected altogether after converting Leach reaction.Liquid pump is leached into the conversion
Enter the cathode chamber of diaphragm electrodeposition slot.Configuration simultaneously is with the ammonium chloride solution of a concentration of 6mol/L of catholyte same volume as anode
Liquid carries out diaphragm electrodeposition and extracts lead.Current density is 350A/m when diaphragm electrodeposition2, electrodeposition temperature 50 C is heteropolar away from 6cm, cathode
To plate ruthenium titanium plate, anode is coupled the paliform anode formed, stud fence spacing 3.5cm by 4 studs through copper folder；The electrodeposition period
For 24 hours, diaphragm material is anionic membrane.After electrolysis the fine and close smooth electric lead of pattern, the purity of gained electricity lead are obtained in cathode
It is 99.95%, current efficiency 98.1%.Tank voltage maintains to stabilize to 2.1~2.3V, anode surface always in electrolytic process
No solid product is precipitated.
Embodiment 3
The sulfuric acid lead skim that Henan company provides, through analyzing wherein with PbSO4The lead content of object phase preservation is 20.2% (matter
Measure percentage).
It takes above-mentioned sulfuric acid lead skim 450g as raw material for standby, liquid after the crystallization of output in embodiment 1 and embodiment 2 is closed
And it obtains containing NaCl, NH4Cl and a small amount of CaCl2And BaCl2Mixed solution 16.58L.From this mixed solution take out 2L with it is upper
It states 450g sulfuric acid lead skims and carries out chlorination coordination and leach, CaCl is added in when leaching2, CaCl2Addition be by the 450g sulfuric acid lead skims
In sulfate radical be entirely formed to 1.5 times of theoretical amount needed for calcium sulfate.Extraction temperature is 90 DEG C, extraction time 150min.
Solid-liquor separation, leached mud dry post analysis wherein PbSO while hot after leaching4Content, calculate the leaching rate of lead is
97.2%.Leachate is separated by filtration the chlorination leading crystal 100.8g being wherein precipitated after being cooled to room temperature, repeat above-mentioned steps 4 batches
It is secondary.It is collected into chlorination leading crystal 510g altogether.The total 9.7L of liquid is used directly for next batch sulfuric acid lead skim after gained crystallization
Potassium cloride.The cathode stripped solution 1800ml obtained in Example 1 wherein converts 510g chlorination leading crystals supplying
It leaches, extraction temperature is 50 DEG C, extraction time 90min.Obtained conversion leachate is pumped into the cathode chamber of diaphragm electrodeposition slot, together
When Example 1 be electrolysed after obtained anode stripped solution 1800ml, ammonium hydroxide is added wherein, adjusts its pH value to its diaphragm
Initial value (pH 5.0) before electrodeposition is used as anolyte afterwards, carries out diaphragm electrodeposition and extracts lead.Current density is when diaphragm electrodeposition
250A/m2, 30 DEG C of electrodeposition temperature is heteropolar away from 5cm, and cathode is stainless steel substrates, and anode, which is coupled by 5 plating ruthenium titanium sticks through copper folder, to be formed
Paliform anode, rodlike fence spacing 1.2cm；The electrodeposition period, diaphragm material was anionic membrane for 24 hours.In the moon after electrolysis
Pole obtains the fine and close smooth electric lead of pattern, and the purity of gained electricity lead is 99.96%, current efficiency 97.5%.In electrolytic process
Tank voltage maintains to stabilize to 2.2~2.5V always, and anode surface is also precipitated without solid product.
Comparative example 1
Other conditions are same as Example 1, and the leachate containing lead source is obtained after chlorination coordination is leached, leaded with this
The leachate of complex configures as catholyte and carries out diaphragm electrodeposition extraction lead as implemented the anolyte described in 1.But it is real
Middle discovery is tested, constantly there is the precipitation of chlorination leading crystal as leachate gradually cools down, in catholyte.Plumbum ion concentration is not in catholyte
It is disconnected to reduce.Product is precipitated in cathode can not be at plate, but loose lead powder, and with the agitation of solution, cathode surface lead powder is not broken
It falls in solution.After electrodeposition 3h, collects lead powder drying and weigh, calculate to obtain cathode efficiency only 33.5%.
Comparative example 2
Other conditions are same as Example 1, only diaphragm electrodeposition when, anodic dissolution is non-to be configured to NH4Cl solution, for example, when with
When being set to NaCl solution, anode releases a large amount of chlorine when electrodeposition, and slot pressure quickly rises to 3.5V or more；When anolyte configures
For (NH4)2SO4When solution, electrolytic deposition process slot pressure is more than 3.0V, and with the extension of electrodeposition time, slot pressure gradually rises to 4.2V.
Comparative example 3
Other conditions are same as Example 1, only diaphragm electrodeposition when, current density is set as 550A/m2.It is electric with this condition
Cathode surface has bubble generation when product, is judged as that liberation of hydrogen side reaction occurs.And anode also has a small amount of chlorine to be precipitated, and slot pressure is rapid
It is increased to 3.5V or more；Cathode generation is not loose porous fine and close, is easy to fall off from cathode surface.After electrodeposition 8h, cathode can not be at
Fine and close plate, current efficiency are determined to 78.1%.
Comparative example 4
Other conditions are same as Example 1, only diaphragm electrodeposition when, the rodlike fence spacing of graphite be 5cm, with this condition every
When film electrodeposition is less than 8h, cathode surface product porous is found, and with the extension of electrodeposition time, cathode surface is precipitated a large amount of
Lead " whisker ", pattern runs down, and can only stop electrodeposition reaction.Cathode product drying analysis is collected, cathode current effect is calculated to obtain
Rate 69.3%.
Comparative example 5
Sulfuric acid lead skim 200g as described in example 1 above is taken, with CaCl2With NH4The mixed solution of Cl is coordination leaching agent pair
The sulfuric acid lead skim carries out chlorination and is coordinated Leach reaction.Wherein, CaCl2Addition be by the sulfate radical whole shape in sulfuric acid lead skim
As 1.5 times of theoretical amount needed for calcium sulfate, NH4Cl and CaCl2The ratio between mole be 1.5:1.Chlorination is coordinated extraction temperature
85 DEG C, Gu (g) liquid (ml) is than being 1:4, extraction time 90min；Chlorination coordination leach after immediately to Leaching Systems while hot
It is separated by filtration, obtains leaded chlorination coordination leachate and leached mud, analyze lead content in leached mud, calculate to obtain lead in sulfuric acid lead skim
Chlorination coordination leaching rate be 96.5%.
Obtained leaded chlorination coordination leachate is placed in beaker after cooled to room temperature, solid-liquor separation obtains chlorination
Leading crystal 57.2g and crystallization after liquid 788ml.This 788ml solution retains spare (the chlorination coordination that can be used for next time is leached).It will
The 57.2g chlorination leading crystals that decrease temperature crystalline obtains, which are added in 250ml ammonium acetate solutions, carries out conversion leaching.Ammonium acetate in solution
Amount be convert the Chlorine in Solution lead to theoretical amount needed for lead acetate 1.5 times.Extraction temperature is 50 when conversion is leached
DEG C, extraction time 60min.It under similarity condition, then carries out 7 batches and repeats to test as described above, collect conversion altogether and leach
Liquid 2010ml.Obtained conversion leachate is pumped into plain electrolysers and carries out electrodeposition extraction lead.Current density is 220A/ when electrodeposition
m2, 30 DEG C of electrodeposition temperature is heteropolar away from 4cm, and cathode is Lead initiated plate electrode, and anode is coupled the fence formed by 3 graphite rods through copper folder
Shape anode, rodlike fence spacing 1cm；But when only electrodeposition is to 3.0h with this condition, since a large amount of brown oils are precipitated in anode surface
Shape insoluble matter causes slot pressure constantly to increase, and the brown insoluble matter is on the increase with the extension of electrodeposition time, and negative and positive are accumulated in
Near extremely so that anode and cathode is short-circuit and causes electrodeposition that can not go on.It collects cathode product drying to weigh, analyzes its ingredient meter
Calculate to obtain cathode efficiency only 51.2%.
Comparative example 5
Other conditions are same as Example 1, only carrying out diaphragm electrodeposition using conventional graphite cake rather than paliform anode.
But when diaphragm electrodeposition is to 8h with this condition, it can obviously be observed in anode plate surface and be covered with one layer of brown insoluble matter, slot
2.2V of the pressure by just when electrodeposition rises to 3.5V.When continuing electrodeposition, slot pressure continues to increase, and anode surface brown insoluble matter increases
Aggravation, cathode surface are precipitated lead pattern and run down, and can only stop electrodeposition reaction.Cathode product drying analysis is collected, is calculated
Cathode efficiency 72.6%.
Claims (10)
1. a kind of method of sulfuric acid lead skim wet clean processes, which is characterized in that include the following steps：
Step 1：The chlorination coordination of sulfuric acid lead skim is leached
It is that coordination leaching agent carries out chlorination coordination leaching to sulfuric acid lead skim with chloride solution, is separated by solid-liquid separation, obtains after leaching
To leachate and leached mud containing lead source；
Step 2：Leachate crystallizes
The leachate crystallization containing lead source that step 1 is obtained, is separated by solid-liquid separation, obtains liquid after chlorination leading crystal and crystallization；
Step 3：The conversion of chlorination leading crystal is leached
Acetate Solution is configured as conversion leaching agent, and the chlorination leading crystal that step 2 is obtained be added in Acetate Solution into
Row conversion, which is leached, obtains conversion leachate；
Step 4：The diaphragm electrodeposition of conversion leachate carries lead
The conversion leachate that step 3 is obtained carries out diaphragm using ammonium chloride solution as anolyte as catholyte
Electrodeposition extracts lead；Electric lead, cathode stripped solution, anode stripped solution are obtained after electrodeposition.
2. a kind of method of sulfuric acid lead skim wet clean processes according to claim 1, it is characterised in that：
In the step one, the solid-liquid mass volume ratio of sulfuric acid lead skim and chloride solution is 1:3~9 (g:Ml),
Include that the chloride A to form precipitation, and and sulphur are reacted with sulfate radical in the step one, in the chloride solution
Acid group reacts not sedimentable chloride B；
In the chloride solution, the amount of chloride A is that the sulfate radical in sulfuric acid lead skim is completely formed needed for sulfate precipitation
1 times or more of theoretical amount；
In the chloride solution, the ratio between mole of chloride B and chloride A >=1.
3. a kind of method of sulfuric acid lead skim wet clean processes according to claim 2, it is characterised in that：
The chloride A is selected from CaCl2、BaCl2At least one of；
The chloride B is selected from NH4At least one of Cl, NaCl.
4. a kind of method of sulfuric acid lead skim wet clean processes according to claim 1, it is characterised in that：
In the step one, extraction temperature is 20~95 DEG C,
In the step one, extraction time is 30~180min,
In the step three, the temperature for converting leaching is 20~90 DEG C；
In the step three, the solid-liquid mass volume ratio for converting leaching is 1:3~7 (g:ml)；
In the step three, the time for converting leaching is 30~180min.
5. a kind of method of sulfuric acid lead skim wet clean processes according to claim 1, it is characterised in that：
In the step three, configures the acetate used in Acetate Solution and be selected from least one of sodium acetate, ammonium acetate；
The addition of acetate is that the Chlorine in Solution lead will be added to be converted into theory needed for lead acetate in the Acetate Solution
1~3 times of amount.
6. a kind of method of sulfuric acid lead skim wet clean processes according to claim 1, it is characterised in that：
When the described step four septation electrodeposition, current density 50A/m2~500A/m2；
When the described step four septation electrodeposition, temperature is 20~80 DEG C；
It is heteropolar away from for 3~12cm when the described step four septation electrodeposition；
When the described step four septation electrodeposition, the electrodeposition period >=20h/ times.
7. a kind of method of sulfuric acid lead skim wet clean processes according to claim 1, it is characterised in that：
In the step four, cathode is one kind in graphite cake, titanium plate, plating ruthenium titanium plate, stainless steel plate, Lead initiated plate electrode；
The anode material is one kind in graphite, titanium, plating ruthenium titanium；
The diaphragm is anionic membrane；
In the step four, anode is paliform anode；
The paliform anode is made of n root fence sticks, n >=2, and the spacing of any adjacent two fence stick is 1~
4cm。
8. a kind of method of sulfuric acid lead skim wet clean processes according to claim 1, it is characterised in that：
In the step four, a concentration of 3~8mol/L of the ammonium chloride solution.
9. a kind of method of sulfuric acid lead skim wet clean processes according to claim 1, it is characterised in that：
Chloride A is filled into after being crystallized obtained by step 3 in liquid and obtains solution return to step one as chlorination coordination leaching agent；Institute
State Chlorine in Solution compound A amount be by the sulfate radical in sulfuric acid lead skim be completely formed theoretical amount needed for sulfate precipitation 1.0~
3.5 again.
10. a kind of method of sulfuric acid lead skim wet clean processes according to claim 1, it is characterised in that：
The cathode stripped solution return to step three is used as conversion leaching agent；
Anolyte when return to step four is for diaphragm electrodeposition after the anode stripped solution addition neutralizer；Anode stripped solution
The neutralizer of addition is ammonium hydroxide；Ammonium hydroxide is added to adjust the pH value of anode stripped solution to step 4 Anodic electrolyte diaphragm electrodeposition
Preceding initial pH value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810618688.8A CN108715935B (en) | 2018-06-15 | 2018-06-15 | A kind of method of sulfuric acid lead skim wet clean processes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810618688.8A CN108715935B (en) | 2018-06-15 | 2018-06-15 | A kind of method of sulfuric acid lead skim wet clean processes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108715935A true CN108715935A (en) | 2018-10-30 |
| CN108715935B CN108715935B (en) | 2019-08-23 |
Family
ID=63913139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810618688.8A Active CN108715935B (en) | 2018-06-15 | 2018-06-15 | A kind of method of sulfuric acid lead skim wet clean processes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108715935B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110468279A (en) * | 2019-09-09 | 2019-11-19 | 赵坤 | A method of recycling lead from the lead plaster material of waste lead storage battery |
| CN110923468A (en) * | 2019-12-02 | 2020-03-27 | 赵坤 | Method for recovering metallic lead from lead-containing materials such as lead sulfate slag |
| CN111575743A (en) * | 2020-05-26 | 2020-08-25 | 中国恩菲工程技术有限公司 | Method for producing metallic lead |
| CN112501451A (en) * | 2020-11-13 | 2021-03-16 | 桐乡市思远环保科技有限公司 | Method for producing metallic lead by adopting solvent extraction electrodeposition process |
| CN112981104A (en) * | 2021-02-05 | 2021-06-18 | 桐乡市思远环保科技有限公司 | Method for treating cadmium-containing waste residues and recovering metal cadmium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194615A (en) * | 2013-03-27 | 2013-07-10 | 云南祥云飞龙有色金属股份有限公司 | Lead hydrometallurgical technology through utilizing lead sulfate |
-
2018
- 2018-06-15 CN CN201810618688.8A patent/CN108715935B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194615A (en) * | 2013-03-27 | 2013-07-10 | 云南祥云飞龙有色金属股份有限公司 | Lead hydrometallurgical technology through utilizing lead sulfate |
Non-Patent Citations (2)
| Title |
|---|
| 付志刚: ""钢铁冶金烧结灰中铅的浸取回收和一氧化铅的制备"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 黎泽仁: ""用含铅氯化渣制取醋酸铅"", 《有色金属(冶炼部分)》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110468279A (en) * | 2019-09-09 | 2019-11-19 | 赵坤 | A method of recycling lead from the lead plaster material of waste lead storage battery |
| CN110923468A (en) * | 2019-12-02 | 2020-03-27 | 赵坤 | Method for recovering metallic lead from lead-containing materials such as lead sulfate slag |
| CN110923468B (en) * | 2019-12-02 | 2022-03-11 | 赵坤 | Method for recovering metallic lead from lead sulfate slag |
| CN111575743A (en) * | 2020-05-26 | 2020-08-25 | 中国恩菲工程技术有限公司 | Method for producing metallic lead |
| CN112501451A (en) * | 2020-11-13 | 2021-03-16 | 桐乡市思远环保科技有限公司 | Method for producing metallic lead by adopting solvent extraction electrodeposition process |
| CN112981104A (en) * | 2021-02-05 | 2021-06-18 | 桐乡市思远环保科技有限公司 | Method for treating cadmium-containing waste residues and recovering metal cadmium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108715935B (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108715935B (en) | A kind of method of sulfuric acid lead skim wet clean processes | |
| CN108470951B (en) | Method for recovering valuable metals in waste nickel-cobalt-manganese ternary lithium ion battery | |
| CN102560535B (en) | Method for recovering lead in waste lead-acid storage battery filler by using wet process | |
| CN107653378A (en) | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery | |
| CN105886767B (en) | A kind of recovery method of copper indium gallium selenide waste material | |
| CN104630826B (en) | Technique for recovering tin from tin anode sludge | |
| CN110423884B (en) | Method for recovering lead from lead plaster of waste lead-acid storage battery | |
| CN102618884A (en) | Lead regeneration method for recovering lead paste from waste lead acid storage battery by wet method | |
| CN102839391B (en) | High purity indium preparation method | |
| CN110468279B (en) | Method for recovering lead from lead plaster material of waste lead storage battery | |
| CN101613803A (en) | A kind of method of recovering lead from lead paste of waste lead-acid battery | |
| CN110387560A (en) | A kind of method that once electrolytic prepares 5N high purity copper | |
| CN102367578B (en) | Combined method for electrolyzing and recovering lead | |
| CN108642522A (en) | A kind of recovery method of the waste material containing indium | |
| CN113862479A (en) | Resource recovery processing method for lead plaster in waste lead storage battery | |
| CN111321302A (en) | Method for recovering lithium and potassium from high lithium potassium anode carbon residue or high lithium potassium electrolyte | |
| CN104152701B (en) | The method that tin is reclaimed from tin refinement slag | |
| TW202000931A (en) | Method for recycling copper-indium-gallium-selenium waste | |
| CN111020194A (en) | Method for synthesizing titanium-aluminum alloy from waste lithium titanate anode and cathode powder | |
| WO2019071642A1 (en) | Method for recovering lead from waste lead-acid battery lead paste in wet process | |
| CN106086414A (en) | A kind of method reclaiming lead from waste lead acid battery lead cream | |
| CN110735155A (en) | Method for producing electrolytic manganese metal and co-producing manganese dioxide | |
| CN112981121B (en) | Method for treating cadmium-containing waste residue and preparing high-purity metal cadmium by precipitation method | |
| CN115367776A (en) | Method for recycling lithium iron phosphate battery | |
| CN114875240A (en) | Method for treating copper-cobalt alloy of waste lithium battery and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |