CN108950600A - A kind of electrolyte and electrolytic method of lead bullion electrorefining - Google Patents
A kind of electrolyte and electrolytic method of lead bullion electrorefining Download PDFInfo
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- CN108950600A CN108950600A CN201810765561.9A CN201810765561A CN108950600A CN 108950600 A CN108950600 A CN 108950600A CN 201810765561 A CN201810765561 A CN 201810765561A CN 108950600 A CN108950600 A CN 108950600A
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- 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
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Abstract
A kind of electrolyte and electrolytic method of lead bullion electrorefining, the electrolyte of the lead bullion electrorefining are lead acetate-acetate system, wherein Pb2+Concentration is 10~200g/L, and the acetate concentration that dissociates is 10~200g/L.The invention also includes a kind of electrolytic methods that lead bullion electrorefining is carried out using the electrolyte, when electrolysis, the paliform pole plate cast using lead bullion is anode, using stainless steel or Lead initiated plate electrode as cathode, lead bullion electrorefining is carried out under certain pulse current, output cathode electricity lead and the earth of positive pole, cathode electricity lead melt and obtain national standard 1# lead pig after casting respectively for lead bullion electrolysis, and noble metal abstraction process is sent to handle after the washed filters pressing of the earth of positive pole.The present invention uses acetic acid-lead acetate solution system to carry out pulse electrolysis refining for electrolyte, has environment-friendly advantage outstanding feature.
Description
Technical field
The invention belongs to field of hydrometallurgy, and in particular to a kind of electrolyte and electrolytic method of lead bullion electrorefining.
Background technique
The industrial electrolysis refining of lead is widely used the cypress that Germany scientist A.G.Betts was proposed in 1901 and hereby refines at present
Method.The technique is mainly characterized by using the pyro-refining removing impurity such as most copper and tin lead bullion as anode, and electro-deposition lead is made
Thin slice be cathode, the mixed aqueous solution of fluosilicic acid (50-100g/L) and lead fluorosilicate (70-90g/L, in terms of lead ion) make electricity
Liquid is solved, control electrolyte temperature is 30-40 DEG C, then with 180-200A/m2Current density be electrolysed in a cell.Electricity
Solution refining the result is that the metallic lead in anode loses electronics and dissolves, while the electricity of cathode output high-purity (Pb > 99.99%)
Solve lead.Since the dissolution potential of the metals such as Cu, Sb, Bi and Ag in anode is higher than the dissolution current potential of lead, thus finally in anode
Also obtain the anode scrap that surface has the earth of positive pole.The technique is currently plumbing electrorefining by development in more than 100 years and perfect
Main technique.
But even to this day, the shortcoming of the technique is also increasingly apparent, especially:
(1) environment is poor.Fluosilicic acid-lead fluorosilicate solution that existing lead bullion electrorefining uses is volatile, and fluosilicic acid, fluorine
Lead silicate itself is more toxic, and the fluosilicic acid and its decomposition volatilized in summer operation from electrolytic cell generates toxic
SiF4Surrounding enviroment are directly endangered with HF gas.
(2) low yield.Since fluosilicic acid is readily volatilized and resolve into toxic HF and SiF when heated4, the technique is general
Diluter silicate fluoride solution can only be used, thus the current density that electrolytic process can bear is relatively low, generally 150-200A/
m2, electrolytic cell unit production capacity, yield are limited.
(3) anode residual anode ratio is high.In traditional refining of lead bullion technique, usually the plate that lead bullion is cast into 2-3cm is made
Electrorefining is carried out for anode.This tabular anode being progressively enriched with surface anode mud in electrodeposition process, leads to electricity
The impedance of solution preocess constantly increases, and often when anode still has about 50% residual, because surface anode mud is more, slot presses through high
Electrolysis can be terminated in advance.Furthermore by the originals such as anode surface remaining anode mud and the incomplete planarization on negative electrode electro-deposition lead surface
Cause, existing electrolysis must also be using wider heteropolar away from exacerbating rising of electrolysis energy consumption etc..
Summary of the invention
The technical problem to be solved by the present invention is to provide one kind for the above-mentioned problems of the prior art and deficiency
The electrolyte and electrolytic method of the performing electrolytic refining on lead bullion of clean and effective.
The technical solution adopted by the present invention to solve the technical problems is:
The electrolyte of the lead bullion electrorefining of the present invention is lead acetate-acetate system (system refers to aqueous solution), wherein Pb2+
Concentration be 10~200g/L (preferably 30~100g/L, more preferable 40-80g/L), dissociate acetate concentration be 10~200g/L (preferably
30~100g/L, more preferable 40-80g/L).
The electrolytic method that lead bullion electrorefining is carried out using the electrolyte of the present invention, comprising the following steps:
The lead bullion after pyro-refining is cast into paliform lead bullion anode plate in the molten state first；Then described in preparing
Electrolyte, and into electrolyte add animal glue, sodium lignin sulfonate and any two kinds of mixtures in cumarin additive,
Electrolyte temperature is adjusted to 10 DEG C~60 DEG C (preferably 30 DEG C~50 DEG C), electrolyte carries out recycle stream by the way of upper entering and lower leaving
Dynamic, rate of circulating flow control is 10~25L/min；Lead bullion anode plate to be refined, cathode plate are put into electrolytic cell again, connect arteries and veins
After rushing power supply, start lead bullion electrorefining.
Further, the lead bullion anode plate is through the preliminary removing impurities of pyrogenic process and the lead bullion anode plate that is cast into, including following matter
Measure percent composition: Pb >=90%, Cu≤1.5%, Sn≤1.5%, As and Sb gross mass≤5%, Bi≤1%.
Further, 1~4cm of rodlike fence spacing of the paliform lead bullion anode plate.
Further, in the electrolyte, the concentration for controlling animal glue is 0.02~2.0g/L (preferably 0.1~1.0g/L),
The concentration for controlling lignosulfonates is 0.02~2.5g/L (preferably 0.1~1.0g/L), and the concentration for controlling cumarin is 0.01
~1.0g/L (preferably 0.1~0.5g/L).
Further, when electrorefining, cathode and anode pole span is 2~5cm；The pulse frequency of pulse current is 50~2000Hz,
Duty ratio is 50%~90%, and average pulse current density is 200~600A/m2；Cathode material is that the lead of Pb >=99.9% begins
Pole piece or stainless steel plate.
The present invention uses lead acetate-acetate system to be electrolysed for electrolyte, significant, the lead solubility with environment-friendly advantage
The feature of high, stability height, gained electricity lead purity is high.
The beneficial effects of the present invention are:
(1) lead acetate-acetate system of the invention and lead bullion electrolytic method are environmental-friendly, and there is no such as existing silicofluoric acid is molten
The problems such as liquid system electrolysis is also easy to produce toxic and harmful gas pollution environment and poisons human health；
(2) present invention carries out lead bullion electrolysis using the lead acetate under specified conditions-acetate system, is more advantageous to inhibition lead bullion
The interference of middle usual impurities element such as Cu, Sn, As, Sb, Bi, the not only higher electric lead product of available purity, but also to electricity
The requirement of solution lead bullion grade can be relaxed to Pb > 90% by existing fluosilicic acid solution electrolysis system Pb > 95%, significantly mitigation lead bullion
The burden that pyro-refining cleans in advance before electrorefining.
(3) present invention by lead bullion be placed in lead acetate under specified conditions-acetate system carry out pulse electrolysis refining, it can be achieved that
200~600A/m of current density2Under the conditions of stablize electrorefining, with existing fluosilicic acid solution electrolysis system lead bullion electrolysis about 150
~200A/m2Current density compare, yield is higher under equal conditions, and production capacity is bigger.
(4) paliform lead bullion anode is used, the electrorefining under Electro-pulsing Field is conducive to the anode surface earth of positive pole
It falls off, slows down anodic passivity, anode residual anode ratio is down to < 35% by 50% or so of existing fluosilicic acid electrolysis system.
Specific embodiment
The invention will be further described with reference to embodiments, but the present invention is not limited to the following embodiments.
Embodiment 1
The coarse-lead alloy that Yunnan company provides, ingredient are as follows: Pb 93.3%, Cu 0.9%, Sn 0.7%, As
1.1%, Sb 2.3%, Bi 0.8%, Ag 0.2%.To be cast into after this alloy molten first paliform anode (long 14cm ×
Wide 16cm, single fence stick diameter 2cm), rodlike fence spacing 1.5cm prepares lead acetate-acetic acid electrolyte, wherein Pb later2+
Concentration 60g/L, acetate concentration 70g/L, and gelatine and sodium lignin sulfonate are added into electrolyte, concentration be respectively 1.0g/L,
0.5g/L.Electrolyte is circulated by the way of upper entering and lower leaving, and rate of circulating flow control is 20L/min, using thermostatical oil
Bath control electrolyte temperature is 40 DEG C.Paliform anode, the stainless steel cathode plate of above-mentioned casting are put into electrolytic cell, yin, yang
Pole pole span is 3cm.After anode and cathode connects the pulse power, starting lead bullion electrorefining, the pulse frequency of pulse current is 1000Hz,
Duty ratio is 80%, and average pulse current density is 400A/m2。
It is electrolysed 2 days under the conditions of above-mentioned technological parameter, when anode residual anode ratio 33% terminates to be electrolysed.Respectively collect cathode lead and
The earth of positive pole obtains the lead that ingredient meets national standard 1# lead standard after cathode lead melting and casting, send after the washed filters pressing of the earth of positive pole
The processing of noble metal abstraction process.The present embodiment lead bullion electrorefining efficiency is calculated as 98.1%.
Embodiment 2
The coarse-lead alloy that Henan company provides, Pb 91.3%, Cu 1.4%, Sn 0.9%, As 0.7%, Sb
3.6%, Bi 1.1%, Ag 0.31%.Paliform anode (long 17cm × wide 16cm, list will be cast into after this alloy molten first
Root fence stick diameter 3cm), rodlike fence spacing 2cm prepares lead acetate-acetic acid electrolyte, wherein Pb later2+Concentration 40g/L,
Acetate concentration 40g/L, and addition gelatine and cumarin, concentration are respectively 0.8g/L, 0.5g/L into electrolyte.Electrolyte uses
The mode of upper entering and lower leaving is circulated, and the control of solution circulation flow speed is 20L/min, controls electrolyte temperature using constant temperature oil bath
Degree is 40 DEG C.The paliform anode of above-mentioned casting, Lead initiated plate electrode (Pb >=99.9%) cathode plate are put into electrolytic cell, yin, yang
Pole pole span is 2.5cm.After anode and cathode connects the pulse power, start lead bullion electrorefining, the pulse frequency of pulse current is
800Hz, duty ratio 70%, average pulse current density are 350A/m2。
It is electrolysed 4 days under the conditions of above-mentioned technological parameter, when anode residual anode ratio 31.5% terminates to be electrolysed.Cathode lead is collected respectively
And the earth of positive pole, the lead that ingredient meets national standard 1# lead standard is obtained after cathode lead melting and casting, after the washed filters pressing of the earth of positive pole
Noble metal abstraction process is sent to handle.The present embodiment lead bullion electrorefining efficiency is calculated as 98.8%.
Comparative example 1 (non-paliform anode)
Using coarse-lead alloy described in above-described embodiment 1 as raw material, plate-shaped anode (14cm × wide is cast into after being melted
16cm × thickness 2cm), lead acetate-acetic acid electrolyte processed is made later, wherein Pb2+Concentration 80g/L, acetate concentration 40g/L, and to electricity
Solving addition gelatine and sodium lignin sulfonate, concentration in liquid is respectively 1.0g/L, 0.5g/L.Electrolyte is by the way of upper entering and lower leaving
It is circulated, the control of solution circulation flow speed is 20L/min, uses constant temperature oil bath control electrolyte temperature for 40 DEG C.It will be upper
State lead bullion plate anode, stainless steel cathode plate is put into electrolytic cell, cathode and anode pole span be 3cm.After anode and cathode connects the pulse power,
Start lead bullion electrorefining, the pulse frequency of pulse current is 1000Hz, duty ratio 80%, and average pulse current density is
400A/m2。
About 13 hours can only be at most electrolysed under the conditions of above-mentioned technological parameter, at this time since anode surface adheres to a large amount of sun
Pole mud, slot pressure increase to 4V or more by 1.1V before, and with the extension of electrolysis time, and anode and cathode is away from being gradually reduced, Ji Hufa
Raw anode and cathode short circuit, can only stop cell reaction, and the weighing of anode residual anode ratio drying is measured as 55.8%.
Comparative example 2 (non-pulse electrolysis)
Using coarse-lead alloy described in above-described embodiment 2 as raw material, it is (long that paliform anode will be cast into after this alloy molten
17cm × wide 16cm, single fence stick diameter 3cm), rodlike fence spacing 2cm.Lead acetate-acetic acid electrolyte is prepared later,
Middle Pb2+Concentration 40g/L, acetate concentration 40g/L, and gelatine and cumarin are added into electrolyte, concentration be respectively 0.8g/L,
0.5g/L.Electrolyte is circulated by the way of upper entering and lower leaving, and the control of solution circulation flow speed is 20L/min, using perseverance
Warm oil bath control electrolyte temperature is 40 DEG C.By the paliform anode of above-mentioned casting, Lead initiated plate electrode (Pb >=99.9%) cathode plate
It is put into electrolytic cell, cathode and anode pole span is 2.5cm.After anode and cathode connects conventional DC power supply, start lead bullion electrorefining.Just
Start to set 350A/m for cathode-current density2, but after only having crossed about 15min, tank voltage is risen to by incipient 1.0v
3.5v, anodic passivity phenomenon are obvious.Therefore, cathode-current density can only be adjusted to 180A/m2。
About 18 hours also can only be at most electrolysed under the conditions of above-mentioned technological parameter, at this time since anode surface adherency is more
The earth of positive pole, slot pressure increases to 4V or more, and with the extension of electrolysis time, away from being gradually reduced anode and cathode almost occurs for anode and cathode
Short circuit, can only stop cell reaction, and the weighing of anode residual anode ratio drying is measured as 53.1%.
Claims (8)
1. a kind of electrolyte of lead bullion electrorefining, it is characterised in that: be lead acetate-acetate system, wherein Pb2+Concentration be 10~
200g/L, the acetate concentration that dissociates are 10~200g/L.
2. the electrolyte of lead bullion electrorefining according to claim 1, it is characterised in that: Pb2+Concentration is 30~100g/L,
Free acetate concentration is 30~100g/L.
3. the electrolyte of lead bullion electrorefining according to claim 2, it is characterised in that: Pb2+Concentration is 40-80g/L, trip
It is 40-80g/L from acetate concentration.
4. a kind of electrolytic method for carrying out lead bullion electrorefining using electrolyte described in claim 1-3, it is characterised in that: including
Following steps:
The lead bullion after pyro-refining is cast into paliform lead bullion anode plate in the molten state first；Then the electrolysis is prepared
Liquid, and into electrolyte add animal glue, sodium lignin sulfonate and any two kinds of mixtures in cumarin additive, adjustment
To 10 DEG C~60 DEG C, electrolyte is circulated electrolyte temperature by the way of upper entering and lower leaving, and rate of circulating flow control is 10
~25L/min；Lead bullion anode plate to be refined, cathode plate are put into electrolytic cell again, after connecting the pulse power, start lead bullion electricity
Solution refining.
5. the electrolytic method of lead bullion electrorefining according to claim 4, it is characterised in that: the lead bullion anode plate is warp
The preliminary removing impurities of pyrogenic process and the lead bullion anode plate being cast into, including following mass percent component: Pb >=90%, Cu≤1.5%, Sn
≤ 1.5%, As and Sb gross mass≤5%, Bi≤1%.
6. the electrolytic method of lead bullion electrorefining according to claim 4 or 5, it is characterised in that: the paliform lead bullion
1~4cm of rodlike fence spacing of anode plate.
7. the electrolytic method of lead bullion electrorefining according to claim 4 or 5, it is characterised in that: in the electrolyte, control
The concentration of animal glue processed is 0.02~2.0g/L, and the concentration for controlling lignosulfonates is 0.02~2.5g/L, controls cumarin
Concentration be 0.01~1.0g/L.
8. the electrolytic method of lead bullion electrorefining according to claim 4 or 5, it is characterised in that: when electrorefining, yin,
Anode pole distance is 2~5cm；The pulse frequency of pulse current is 50~2000Hz, and duty ratio is 50%~90%, average pulse electricity
Current density is 200~600A/m2；Cathode material is the Lead initiated plate electrode or stainless steel plate of Pb >=99.9%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115233033A (en) * | 2022-07-14 | 2022-10-25 | 铅锂智行(北京)科技有限公司 | Lead-based alloy and product thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050222483A1 (en) * | 2004-04-02 | 2005-10-06 | Williams Randall L | Method for treatment of lead-containing surface coatings |
| KR20090002744A (en) * | 2007-07-04 | 2009-01-09 | 강릉대학교산학협력단 | Electrolyte for electrochemical oxygen gas sensor |
| CN102534662A (en) * | 2012-02-13 | 2012-07-04 | 北京化工大学 | Method for performing electrolytic refining on lead bullion |
| CN102618883A (en) * | 2012-02-13 | 2012-08-01 | 北京化工大学 | Method for direct electrolytic refining of crude lead |
| CN103194768A (en) * | 2013-04-16 | 2013-07-10 | 中南大学 | Method for preparing electrolytic manganese metal by using high-iron and high-phosphor manganese ores |
| CN104746098A (en) * | 2015-03-24 | 2015-07-01 | 昆明理工大学 | Electrolyte and method for electrolyzing and refining crude lead |
| CN107268028A (en) * | 2017-06-30 | 2017-10-20 | 湘潭大学 | A kind of method that lead bullion is prepared from waste lead acid battery lead plaster |
-
2018
- 2018-07-12 CN CN201810765561.9A patent/CN108950600B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050222483A1 (en) * | 2004-04-02 | 2005-10-06 | Williams Randall L | Method for treatment of lead-containing surface coatings |
| KR20090002744A (en) * | 2007-07-04 | 2009-01-09 | 강릉대학교산학협력단 | Electrolyte for electrochemical oxygen gas sensor |
| CN102534662A (en) * | 2012-02-13 | 2012-07-04 | 北京化工大学 | Method for performing electrolytic refining on lead bullion |
| CN102618883A (en) * | 2012-02-13 | 2012-08-01 | 北京化工大学 | Method for direct electrolytic refining of crude lead |
| CN103194768A (en) * | 2013-04-16 | 2013-07-10 | 中南大学 | Method for preparing electrolytic manganese metal by using high-iron and high-phosphor manganese ores |
| CN104746098A (en) * | 2015-03-24 | 2015-07-01 | 昆明理工大学 | Electrolyte and method for electrolyzing and refining crude lead |
| CN107268028A (en) * | 2017-06-30 | 2017-10-20 | 湘潭大学 | A kind of method that lead bullion is prepared from waste lead acid battery lead plaster |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115233033A (en) * | 2022-07-14 | 2022-10-25 | 铅锂智行(北京)科技有限公司 | Lead-based alloy and product thereof |
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