CN102618883A - Method for direct electrolytic refining of crude lead - Google Patents
Method for direct electrolytic refining of crude lead Download PDFInfo
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- CN102618883A CN102618883A CN2012100317690A CN201210031769A CN102618883A CN 102618883 A CN102618883 A CN 102618883A CN 2012100317690 A CN2012100317690 A CN 2012100317690A CN 201210031769 A CN201210031769 A CN 201210031769A CN 102618883 A CN102618883 A CN 102618883A
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Abstract
The invention relates to a method for direct electrolytic refining of crude lead, and belongs to the technical field of lead refining. According to the method, the crude lead prepared by pyrometallurgy is casted into a crude lead anode, wherein the crude lead anode is sleeved inside an anode bag; and electrolysis is performed in an additive-containing perchloric acid-lead perchlorate solution electrolyte to electrically deposit the lead in the anode on the cathode, such that the high purity electrolyzed lead and the anode mud are respectively obtained from the cathode and the anode. With the present invention, the lead without a pre-refining treatment can be directly subjected to electrolytic refining to obtain the pure lead with the purity more than 99.99% and the anode mud doped with noble metals, such that the recovery rate of the noble metals can be substantially improved so as to provide greater economic benefits.
Description
Technical field
The invention belongs to plumbous refining techniques field; The direct electrolysis process that relates to a kind of lead bullion specifically will have the lead bullion that pyrometallurgical smelting process obtains now and directly utilize electrochemical method to carry out the method that electrorefining obtains high purity electrolytic lead and residual valuable metal.
Background technology
Along with developing rapidly of the vehicles such as automobile, lead-acid cell also obtains swift and violent development as the indispensable chemical power source of these vehicles.According to statistics, China has reached more than 3,500,000 tons plumbous output in 2010, and wherein nearly 80% lead is used to the manufacturing field of lead-acid cell.Because the valve-controlled type maintenance-free lead-acid cell is in order to reduce the self-discharge coefficient of battery, very high requirement has been proposed for the foreign matter content of leady raw materials.Usually, for quality and the work-ing life that guarantees lead-acid cell, the main raw material that producer mainly uses purity to produce as lead-acid cell at the metallic lead more than 99.99%.Regrettably, traditional lead ore or waste lead acid battery are generally 95-99% through the purity of the metallic lead that pyrometallurgical smelting obtains, and the lead bullion of these low-purity must could be accepted by fields such as lead-acid celies through refining repeatedly.At present plumbous in the world refining techniques mainly contains two kinds of pyrorefining and electrorefinings; Because the valuable metals such as copper, silver and bismuth that electrorefining can more effectively reclaim in the lead to be mingled with, thus electrolytic refining process in the world especially China obtained using widely.
Existing electrolytic refining process is called cypress purifying method now again.It is to be proposed by A.G.Betts in 1901, and begins to obtain industrial applications in 1902, and its principal character is to make electrolytic solution with the aqueous solution that plumbous silicofluoride and silicofluoric acid are formed.This electrolysis process need adopt the lead bullion of preliminary refining, especially needs the lead bullion of preparatory decopper(ing) and tin just can cast anode, and thin pure lead flake is a negative electrode, is filling 0.3-0.5mol/L PbSiF
6(with 0.4-0.6mol/L H
2SiF
6Carry out electrorefining in the electrolyzer of () mixed solution and obtain the plumbous and surperficial anode anode scrap that has the anode sludge of highly purified catholyte.The silicofluoric acid purifying method has become the classics of our times electrolytic lead refining through this 100 years of development.Its advantage is stably to obtain purity up to the pure lead more than 99.99%, and its shortcoming is also paid close attention to by people day by day simultaneously.Main drawback is following:
1; Because metals such as copper and tin are easy to pollute silicofluoric acid-plumbous silicofluoride electrolytic solution, so the 95-98% lead bullion that traditional pyrometallurgical smelting obtains just can be used to existing electrorefining technology through the lead bullion that obtains 99% purity after the pyrogenic process preliminary refining removal of impurities more than the 1-2 road usually.We find now, in the lead bullion of the 95-98% process through 2 road pyrorefining copper removal tin, usually are being mingled with the loss of rare precious metals such as a large amount of Ag and Bi.For example the silver content of 98% lead bullion of plumbous certain batch of Henan light gold is 0.51%; Yet after 2 road pyrogenic process preliminary refining technologies; Its purity is that the silver content of 99% lead bullion is reduced to 0.17%, and this directly causes having in the lead bullion per ton 3400g silver because of in pyrogenic process preliminary refining technology, being run off.
2, silicofluoric acid volatilizees easily when being heated and resolves into deleterious HF and SiF
4This technology generally can only adopt rarer silicate fluoride solution; And electrolysis temperature generally is controlled at lower temperature (30-45 ℃), and this rarer electrolytic solution and lower working temperature make that the specific conductivity of electrolytic solution is lower, and ion diffusion speed is slower simultaneously; Thereby the current density that electrolytic process can bear is also lower, is generally 180-200A/m
2, produce up to the groove of 0.4-0.5V simultaneously and press at electrolytic process, make the electrolysis energy consumption of lead per ton up to 120-135KWh.
3, the toxicity of silicofluoric acid-plumbous silicofluoride solution is bigger, adds easily volatilization of this solution itself, and this situation is more outstanding when the summer operation, the silicofluoric acid that volatilizes from electrolyzer and decompose the deleterious SiF that produces
4Not only the smell is awful with HF gas, and directly endanger the healthy of operative employee.
4, in traditional refining of lead bullion technology, people directly carry out electrorefining with the fluid origin stereotype of lead bullion 2-3cm as anode.We find that under study for action the anode of this simple shape is difficult to realize anodic stripping completely, and major cause is that one is that annode area is less, is difficult to bear very high current density; The 2nd, this tabular anode causes the impedance of electrolytic process constantly to raise in the enrichment gradually of electrodeposition process along with the surperficial anode sludge, and anode only still has 50% when residual often, because of the more premature termination electrolysis of the surperficial anode sludge.The 3rd, because the incomplete planarization on the plumbous surface of cathode electrodeposition; Cause the interpole gap of this tabular anode and lead electrode to shorten gradually along with electrolytic carrying out; Therefore people's interpole gap of having to leave in advance 4-5cm prevents interelectrode short circuit, and this long interpole gap has been aggravated the rising of electrolysis energy consumption again.
Though in recent years; People once studied systems such as perchlorhydria and NaOH in the research in the electrolysis field of lead; But because lead chloride is less at hydrochloric acid or the solubleness of plumbous oxide in NaOH solution; Or not having effective galvanic deposit additive to cause galvanic deposit lead to present a kind of loose dendrite, very easily reoxidation and fail industriallization in melting process, thereby industry is at present gone up the method that electrolytic lead refining generally adopts and still is the Bai Zifa based on the silicofluoric acid medium.
For example the electrolytic lead smelting method (CN200810232653.7) of people such as Gao Wenjie invention has been reported silicofluoric acid concentration has been adjusted to 110-149g/L, and lead content is 70-110g/L, adopts forward and reverse dc electrolysis method to smelt plumbous method.This method has been eliminated lead dendritic crystal to a certain extent, but in the reversible circulation stage, the lead of galvanic deposit just is dissolved in the electrolytic solution again, causes the loss of this part electric energy.Reported that the stibium crude lead that contains that smelting obtains from lead sulfide ore and waste lead acid battery carries out the method that electrorefining obtains high purity lead (99.99%) in silicofluoric acid and plumbous silicofluoride electrolytic solution in the working method (CN200810097208.4) of the high purity lead of Ma Shengjun invention.This invention is to install through the distance of anode and negative electrode in the control electrolyzer, has obtained the pure lead more than 99.996%, and regrettably, electrolytic process still needs the electrolyzer of 0.45-0.48V to press, and causes electrolysis energy consumption higher.The people is also arranged from environmental, once used and carry out plumbous electrolysis in the alkaline system.For example Chen Wei puts down (Hunan University's journal, 1996,23 (6): 111-116) utilize NaOH and KNaC
4H
4O
6Under the help of gelatin additive, carry out the electrolysis of lead plaster and reclaim the lead in the lead plaster, regrettably, this galvanic deposit can only obtain spongiform lead powder.And relevant people utilize alkaline NaOH solution to carry out the rarely seen always report of method of lead bullion electrorefining.Because the dissolving power of plumbous oxide in simple NaOH solution is limited; Add and find that not effective galvanic deposit additive gets off to control plumbous electrodeposition process; The loose porous electrolytic lead that obtains very much, the lead of this high-ratio surface are easy in melting process and airborne oxygen generation oxidizing reaction, and these all are unfavorable for the electrolytic industrial application of NaOH system; To cause plumbous alkaline system electrolysis to be failed developed always, do not realize industrial applications so far.
The inventor finds; The lead bullion that pyrometallurgical smelting directly obtains is except the metallic lead that contains 95-98% purity; The alloy that also contains the alloy grid of associated metal in the lead ore or lead-acid cell directly is mixed in the high melt process in the lead bullion, for example metals such as Ag, As, Bi, Cu, Sn, Sb, Cd and Fe.As a rule, mainly contain the Cu that weight percent is 0.3-0.7%, the Ag of 0.1-0.5%, the Sb of 0.1-2.0%, the As of 0.1-0.4% and the simple substance such as Bi of 0.1-0.4% in the 95-98% lead bullion, and impurity such as the Sn of trace and Fe.
The principle of electrorefining is actual to be to carry out optionally stripping and electrodeposition process according to the difference of electropotential between the element.Owing to be mingled with the foreign metal of its electropotential corrigendum in the lead, for example Bi, Cu, Sb and Ag4 kind metal simple-substance and nonmetal As, because their electropotentials in acidity are respectively as follows:
Cu-2e＝Cu
2+ (E
A 0＝0.337V)
Ag-e＝Ag
+ (E
A 0＝0.7996V)
Sb-3e+3/2H
2O＝1/2Sb
2O
3+3H
+ (E
A 0＝0.152V)
As-3e+3/2H
2O＝1/2H
3AsO
3 (E
A 0＝0.247V)
When employing contains Pb and above-mentioned at least 5 kinds of alloys than stable metal or nonmetal formation and in acidic medium, carries out refining as anode; Because the stripping current potential of simple substance such as Sb, Cu, Ag and Bi is far above Pb; Thereby have only Pb that the anodic stripping reaction at first takes place; These impurity will form the anode sludge because of staying anode surface after the plumbous stripping.Same in electrolytic solution because the Sb that does not have anodic stripping to form
3+, Cu
2+, Ag
+And Bi
3+Plasma, thereby Pb is only arranged
2+Become metallic lead at negative electrode by galvanic deposit.Find by analysis; In the lead bullion of 95-98%; Because the total content of various impurity is up to 2-5% in this lead; Be 99% purity lead bullion total impurities behind the pre existing decopper(ing) 2-5 doubly, thereby more thicker earth of positive pole very easily take place and cover in the lead bullion of this high impurity content in the electrorefining process, even seriously hinder the phenomenon of its inner follow-up stripping of lead bullion.
Hinder electrolysis process in order to overcome the anode sludge that occurs in the existing electrorefining process; People adopt the purpose of pyrogenic process preliminary refining to come to reduce significantly the content of impurity in the lead bullion on the one hand; Adopt after the anode sludge is accumulated to certain thickness the electrolytic method of premature termination on the other hand.In addition; The anodic stripping current potential of metallic copper is higher than metallic lead in the lead bullion; But being easy under the oxygenizement of oxygen in air, it is dissolved in the electrolytic solution; These dissolved trace coppers are because high electropotential is easy to be accompanied by plumbous electrodeposition process and separate out at negative electrode; Cause the index of copper in the galvanic deposit lead higher, this also has to impel people also to utilize the process of pyrogenic process preliminary refining can reduce the content of impurity such as copper tin in the lead bullion significantly, for existing electrorefining provides high quality raw material.
How to study and invent a kind of new electrolytic solution and electrorefining splicer thereof skill; Promptly develop a kind of novel nontoxic no evaporable electrolytic solution and directly the lead bullion that pyrogenic process obtains 95-98% is carried out electrorefining; Reduce the loss of precious metals such as Ag in the existing necessary preliminary refining technology of refining significantly; Increase substantially labour productivity, improve employee's production environment and healthy, become the problem of needing solution badly.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; A kind of novel plumbous method of electrorefining is provided; Promptly adopting the perchloric acid-lead perchlorate solution that contains 3 kinds of additives is novel electrolyte; And adopting the novel anode construction that has anode, the lead bullion that can directly obtain pyrometallurgical smelting carries out electrorefining, directly obtains purity up to the pure lead more than 99.99% and the anode sludge that is mingled with precious metal.
One skilled in the art will appreciate that perchloric acid is a kind of very strong mineral acid, it has the acidity stronger than mineral acids such as sulfuric acid and silicofluoric acid, so it has very high dissolving power to metal.But regrettably; Because its chlorine atom is in+7 valencys; Thereby the perchloric acid of higher concentration often embodies stronger oxidisability, and this oxidisability not only causes lead to be easy to autolyze reaction in acidic solution, thereby reduces the current efficiency of electrolytic lead refining process; And the redox reaction between perchloric acid and the lead, cause the deadness consumption of electrorefining procedure division perchloric acid.We find that under study for action the perchloric acid of high density has the intensive oxidation capacity after being heated, yet when we were controlled at certain limit to the concentration of perchloric acid and temperature, this moment, perchloric acid had stability preferably.Further discover; After containing certain density lead ion in the perchloric acid solution; The plumbous ability in its oxidized metal also decreases; Therefore contain certain density lead ion or lead perchlorate at perchloric acid solution, also can increase substantially the stability of perchloric acid in the plumbous process of electrorefining.We also find under study for action in addition, and the additive 1 that in perchloric acid solution, adds minute quantity can further improve the electrodeposition efficiency of lead ion in perchloric acid solution, reduce perchloric acid certainly in the consumption of cathodic reduction property.Through comprehensively effective control of the influence factor of above-mentioned 4 aspects, can possibility be provided for opening up the application of perchloric acid in electrolytic lead refining.On this basis; The present invention finds that a kind of lead bullion dissolved additive 2 that can promote to accelerate significantly the dissolving of lead bullion in perchloric acid solution; Thereby greatly alleviate high-content impurity is produced in the lead bullion the anode sludge to the dissolved restraining effect, this discovery can make the direct electrorefining of the lead bullion of the existing low-purity 95-98% that handles through preliminary refining provide maybe.At last; The present invention has found that also some can be used in the galvanic deposit additive 3 in the high density perchloric acid electrolytic solution; These additives or combination in twos have scale resistance and stability preferably; Can be applied in the perchloric acid electrolytic solution and do not decompose, have the plumbous effect of outstanding galvanic deposit simultaneously, make lead ion become fine and close galvanic deposit lead layer at cathode electrodeposition.
The technical scheme that the present invention adopts is following.
The direct electrolytic smelting method of a kind of lead bullion; It is characterized in that; Be pyrometallurgical smelting to be obtained lead bullion be cast as the lead bullion anode jacket in anode; In containing the perchloric acid of additive-lead perchlorate electrolysis of solutions liquid, carry out electrolysis with the plumbous galvanic deposit in the anode to negative electrode, thereby obtain the highly purified electrolytic lead and the anode sludge respectively at negative electrode and anode.
Further, above-mentioned pyrometallurgical smelting obtains lead bullion or reduces plumbous fluid origin lead bullion anode is the lead bullion anode that contains the space, and its apparent density is controlled at 9.9-11.0g/cm
3Between.
Further, above-mentioned pyrometallurgical smelting obtains lead bullion or reduces plumbous fluid origin lead bullion anode being contained in the anode, and the anode sludge was stayed anode after electrolysis was accomplished, and the anode sludge in the separate bag obtains rare metal contained in the lead bullion.
Specifically; First importance of the present invention has provided the perchloric acid-lead perchlorate solution of the high density of high stripping capacity, and wherein the concentration of perchloric acid is 0.3-3.5mol/L, preferred 1.5-3.0mol/L; The concentration of lead perchlorate is 0.05-1.0mol/L, preferred 0.25-0.55mol/L.Wherein the working temperature of electrolytic solution is 15-75 ℃, preferred 40-60 ℃.The anode of electrolytic process and cathode current density are 20-1200A/m
2, preferred 100-600A/m
2In order to overcome or to alleviate in the anodic stripping process because the anode passivation phenomenon that high-load impurity causes; And high density and high-temperature perchloric acid solution are from the problem in cathodic reduction; Also have 3 kinds of effective additives in the electrolytic solution of the present invention, promptly suppress additive 1, promotion lead bullion dissolved additive 2 and the novel galvanic deposit plumbous additive 3 of perchloric acid in cathodic reduction.
3 kinds of additives that are used for perchloric acid-lead perchlorate electrolytic solution provided by the invention specifically comprise:
1); Suppress a kind of or two kinds of mixtures that perchloric acid reductive additive 1 is meant in tripoly phosphate sodium STPP, trisodium phosphate, boric acid or the 3-methoxybenzoic acid, their independent effective concentration is respectively between 0.01-2.5g/L, 0.05-6.0g/L, 0.01-10.0g/L and the 0.01-5.0g/L.
2), promote lead bullion dissolved additive 2 to be meant the mixture of Monochloro Acetic Acid and acetate, their effective concentration is respectively 0.02-10g/L and 0.01-5.0g/L.
3); The plumbous additive 3 of novel galvanic deposit is meant a kind of or two kinds of mixtures in naphthols, gelatine, sodium lignosulfonate or the tonka bean camphor, and the concentration of wherein above-mentioned four kinds of additive materials is corresponding 0.002-0.035g/L, 0.05-5.0g/L, 0.05-2.5g/L and 0.01-0.5g/L respectively.
Electrolytic solution of the present invention adopts the perchloric acid solution of high density; Contain simultaneously and suppress additive 1, promotion lead bullion dissolved additive 2 and the novel galvanic deposit plumbous additive 3 of perchloric acid in cathodic reduction; These three kinds of additives have effectively overcome perchloric acid from the difficult problem in cathodic reduction and lead easy generation dendrite arm in the perchloric acid medium, thereby it is plumbous up to the fine and close galvanic deposit more than 99.99% to obtain purity.Adopt lower electrolyzer to press in the electrolytic process of the present invention, electrolysis energy consumption is reduced, the electrolysis energy-saving effect is remarkable, has obtained the low electrolyzer that reaches 0.1-0.15V like the laboratory lab scale stage and has pressed, and makes electrolysis energy consumption be reduced to 30-50KWh/t (Pb).These researchs provide a kind of new important channel for the energy-saving and emission-reduction of further excavating the electrolytic lead refining process.
Second importance of the present invention provided a kind of lead bullion anodic method of manufacture of synchronous dissolving-galvanic deposit (being that the interpole gap between anode and the negative electrode is constant before the electrolysis and after the electrolysis) of novel suitable perchloric acid medium's electrorefining needs.One skilled in the art will appreciate that in the existing refining of lead bullion technology, is to adopt thick lead bullion plate of 2-3cm and the refining of the plumbous thin slice catholyte of galvanic deposit.Though additive can greatly promote the plumbous compactness of cathode electrodeposition, in actual production, the metallic lead surface that this galvanic deposit obtains is actual under electron microscope to be still a kind of metallic lead that forms of being piled up by crystal grain.Because the space between crystal grain is piled up, cause the real density of this lead to be slightly less than the 11.3g/cm of fine and close plumbous (being equal to the lead bullion anode for preparing after the prior art fusion) after the fusion usually
3, generally at 9.9-11.0g/cm
3Between.The existence of this phenomenon causes in the electrolytic process interpole gap between the anode and negative electrode constantly to be dwindled, and the interpole gap that makes people have to leave in advance at tabular anode and lead electrode 4-5cm prevents interelectrode short circuit.Novel anode provided by the invention is actually based on above-mentioned asynchronous dissolving-electro-deposition method and realizes.
The invention provides a kind of lead bullion anode that leaves the space in advance, this lead bullion anodic apparent density is controlled at 9.9-11.0g/cm
3Between, with the plumbous density basically identical of cathode electrodeposition.It can be through leaving the space on lead bullion surface or inside in advance; Reduce plumbous apparent density; Can make the plumbous and anode lead bullion of cathode electrodeposition that electrolysis obtains have close apparent density, thereby prevent the phenomenon that the interpole gap between the anode and negative electrode is constantly dwindled in the electrolytic process.In other words; Adopt the lead bullion anode of this low bulk density; Can prevent that electrolytic process from dwindling the phenomenon that possibly cause short circuit between two electrodes because of interpole gap; Thereby can just can adopt the low interpole gap that reaches 1-3cm at the electrolysis initial stage, even lowly reach the 0.2-1.0cm interpole gap and come to reduce significantly the energy consumption phenomenon that the impedance of electrolytic solution causes in the electrolytic process.This lead bullion anode that leaves the space in advance, generally can to adopt conventional method be may command with reduce plumbous apparent density, has the lead bullion anode of thin trace or leave method such as air in inside and realize like casting.
The 3rd importance of the present invention provided a kind of suitable lead bullion anode and dissolved needed anode fully, this anode adopt can acid corrosion-resistant dense membrane paper process, it be at the electrorefining protheca on anode and bring into play its effect.This anode provides three kinds of significant effects, 1) be to reduce the oxidation of airborne oxygen antianode lead bullion and alloy thereof significantly and the oxidation stripping of copper in the dissolving, the especially lead bullion that cause.2) be that the anode of this densification can prevent that metal flows because of the stirring of electrolytic solution in some fine mud shape anode things that anodic dissolution processes produces and deposits to cathode surface, thus the reduction problem of the plumbous purity of the negative electrode that causes.3) be that this anode can be contained in the whole anode sludge that stay after the stripping of anode lead bullion in the sack, for the refinement of precious metal in the later stage anode sludge provides convenience.Experiment shows that this anode can adopt a kind of or two kinds of fiber production in vinylon, viscose fiber, SE barrier film, Vestolen PP 7052 or the polycthylene grafted mould material to form, and the gauge control of anode is at 0.03-0.8mm.
Generally speaking, the technical scheme that preferably adopts of the present invention is following.The direct electrolytic smelting method of a kind of lead bullion; Be earlier pyrometallurgical smelting to be obtained lead bullion or the plumbous lead bullion anode that contains the space that is cast as of reduction; Be contained in then in the anode jacket, under the effect of perchloric acid-lead perchlorate and additive, through electrolysis with plumbous galvanic deposit in the anode to negative electrode; Thereby obtain the highly purified electrolytic lead and the anode sludge at negative electrode and anode, the anode sludge that separates at last in the anode jacket obtains rare metal contained in the lead bullion.
In an implementation process of the present invention, we need be according to the height of the temperature of electrolytic solution in the electrolyzer, control lead bullion anodic current density.Though the present invention is owing to adopted the perchloric acid of high density and higher electrolysis temperature, these two factors can increase substantially the specific conductivity of electrolytic solution, and therefore constant-current electrolysis of the present invention can be carried out under higher current density.According to experiment, different temperature can be selected different current densities, and when the temperature of electrolytic solution was in 30-45 ℃, 20-300A/m was adopted in constant-current electrolysis
2Current density be advisable.When electrolyte temperature was in 45-60 ℃, electrolytic solution can adopt 300-600A/m
2Current density.When electrolyte temperature was in 60-75 ℃, the current density of electrorefining process can adopt 600-1200A/m
2Level.
Find that in implementation process of the present invention at the incipient 1-50h of electrorefining process, electrolyzer is pressed and certain decline phenomenon can be occurred, this phenomenon derives from anode lead progressively dissolve after, its surface becomes coarse, causes actual real current density to decrease.Similarly, thickening of stereotype and process of growth have also appearred in the lead of galvanic deposit negative electrode, also cause the real current density of negative electrode to decrease, and these two factors can be hanged down between the 0.077-0.095V electrolyzer pressure.Along with proceeding of electrorefining process, because anode surface accumulates the mud shape metal cladding of more indissolubles gradually, the rising that causes electrolyzer to be pressed.Press when electrolyzer to be elevated to 0.2-0.4V when above, show that the lead bullion in the anode almost completely dissolves this moment, the anode sludge of the lead bullion anode scrap of residual minute quantity and electrolytic process formation only in the anode.Stop electrolysis, and take out the content in galvanic deposit lead electrode, lead bullion anode scrap and the anode thereof, electrorefining end of processing.Electrolysis obtains cathode electrodeposition lead and carries out the fusion operation, after casting, obtains pure lead pig.The anode sludge can be used as the important source material of rare metal simultaneously, gets into the corresponding operation of refining.
In sum, method of the present invention has following characteristics:
(1) in implementation process of the present invention, the perchloric acid of high density of the present invention-lead perchlorate solution has increased substantially the dissolving power and the specific conductivity of solution, thereby is that the direct electrorefining lead that improves the low-purity lead bullion provides precondition;
(2) in electrorefining process of the present invention; The present invention utilizes 3 kinds of novel additives to come to suppress respectively perchloric acid in cathodic reduction; Promote lead bullion dissolving and the plumbous electrodeposition process of control; The use of these three kinds of new additives effectively overcome perchloric acid from the difficult problem in cathodic reduction and lead easy generation dendrite arm in the perchloric acid medium, thereby it is plumbous up to the fine and close galvanic deposit more than 99.99% to obtain purity.
(3) the present invention adopts the new texture lead bullion anode that has the space in electrolytic process; Thereby realized that plumbous anode dissolves-synchronous electrodeposition process synchronously; This new anode and method thereof are for reduce the interpole gap between anode and the negative electrode significantly; Theoretical basis is provided, thereby this ultrashort interpole gap can reduce the resistance of solution self significantly, obtains lower electrolysis energy consumption.
(4) the present invention adopts the perchloric acid-lead perchlorate solution of non-volatility, can greatly eliminate the poisonous acid mist problem of existing refining plant because of adopting the silicofluoric acid medium to be produced, thereby increases substantially labor's production environment quality.
(5) the present invention adopts the anode that novel acid resisting material is processed, and has almost completely realized the whole dissolvings of high-level efficiency of lead bullion and the high efficiente callback of the anode sludge.This employing anode is realized whole dissolution mode of lead bullion, has changed significantly on the one hand and only can dissolve half anodic shortcoming in the existing electrorefining technology, thereby increased substantially production efficiency.Effectively reduce the pollution of the anode sludge on the other hand, thereby favourable condition is provided for obtaining more highly purified galvanic deposit lead to the galvanic deposit lead electrode.
(6) the present invention proposes scanning of employing electrokinetic potential and continuous current bonded electrolysis mode stage by stage, optimize the electrolytic process curve, thereby in electrolytic process, can obtain lower electrolysis energy consumption.
A large amount of experiments show, the electrorefining technology of this new lead, and the present three aspect advantages of final body:
(1) less energy-consumption.
The present invention is (200-300A/m under the identical current density of together existing industrial electrolysis
2) in batches in the experiment; Can obtain the low electrolyzer that reaches 0.07-0.13V presses; Bai Zifa than existing domestic and international extensive employing directly saves the above electrolyzer pressure of 0.3-0.4V; Realize more than the refining process economize on electricity 60-80% of lead per ton that can save 3200-3600 ten thousand degree this every year for the plumbous company already of 400,000 tons of annual outputs.
(2) high efficiency
Novel process adopts high-solvency electrolytic solution, band space anode and three kinds of modes of anode directly to realize plumbous synchronous dissolving-electrodeposition process; Cutting down the consumption of energy simultaneously; The anodic residual anode ratio is reduced to 1-10% from existing 40-60%; When this reduces the plumbous production cycle significantly, improved plumbous purified production efficiency
(3) high rare metal yield
Analyses such as ICP experiment shows; Novel process can be saved existing 1-2 road pyrogenic process decopper(ing) preliminary refining operation; Thereby reduce the rare metal loss of pyrogenic process preliminary refining process significantly, wherein the yield of precious metal silver can be increased to the 2200-5600 gram of the inventive method from the 1100-2000 gram of existing lead per ton.
Thereby the present invention is technological as a kind of novel electrolytic lead refining, and it not only can promote the energy-saving and emission-reduction of plumbous industry, and can promote noble metal recovery significantly, thereby creates higher economic benefit.
Embodiment
Hereinafter illustrative embodiments will be described in more detail.Said but not limit it.
Embodiment 1
(1) get the lead bullion of selling on the market (its composition is seen table 1), wherein lead content is about 98%.With the fusion of 1kg lead bullion and cast the lead bullion anode that the surface has striped, be of a size of 8*10*1.25 (wide * is high, and * is thick) cm
3, its anodic apparent density is 10.0g/cm
3, anode is packed in the anode that the SE diaphragm material processes simultaneously, and bag is thick to be 0.3mm.
(2) employing is of a size of 8*10*0.05 (wide * is high, and * is thick) cm
3The plumbous negative electrode starting sheet of making of galvanic deposit, the interpole gap of control anode and negative electrode is 2.0-2.2cm, makes them be placed in the electrolyzer abreast;
(3) configuration concentration is 2.0mol/L HClO
4Pb (ClO with 0.33mol/L
4)
2Mixing solutions 300ml adds additive then, makes the boric acid that contains 0.55g/L in the electrolytic solution, the 0.3g/L Mono Chloro Acetic Acid, and 0.2g/L acetate behind 2.0g/L gelatine and the 2.0g/L sodium lignosulfonate and make electrolyte temperature progressively be elevated to 55 ℃, and is stabilized on this temperature;
(4) (3) process is obtained mixed electrolytic solution and is injected in the electrolyzer, treat that electrolyte temperature is stabilized in 55 ℃ after, the beginning constant-current electrolysis of connecting with the mains.Current density on control lead bullion anode and the negative electrode starting sheet is 350A/m
2This moment, the electrolyzer pressure of electrorefining process was generally between the 0.091-0.133V.Along with the carrying out of anode electrolysis process in leaching, its cumulative the anode sludge of more indissolubles, hindered the carrying out of anodic stripping, the rising that causes electrolyzer to be pressed.Press when electrolyzer to be elevated to 0.25V when above, this moment, we stopped electrorefining, took out the content in galvanic deposit lead electrode, lead bullion anode scrap and the anode thereof, the electrorefining end of processing.Electrolysis is obtained obtaining pure lead pig after cathode electrodeposition lead carries out fusion and casts.The anode sludge in the anode is used to refine rare metal.Because there is slight crystal protrusion phenomenon on the plumbous surface of electrolytic deposition, and the slight void between the crystal, its apparent density is 10.1g/cm
3, the mean pole spacing between two electrodes remains unchanged basically.
Through the ICP quantitative analysis, the metals content impurity in this lead pig is as shown in table 1.
Table 1
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.Through calculating, the plumbous power consumption of electrolytic process ton is 27.9 degree.
Embodiment 2
(1) get the lead bullion of selling on the market (its composition is seen table 2), wherein lead content is about 98%.With the fusion of 1kg lead bullion and cast the lead bullion anode that has striped, be of a size of 8*10*1.25 (wide * is high, and * is thick) cm
3, its anodic apparent density is 10.0g/cm
3, anode is packed in the anode that polycthylene grafted mould material processes simultaneously, and bag is thick to be 0.05mm.
(2) employing is of a size of 8*10*0.05 (wide * is high, and * is thick) cm
3The plumbous negative electrode starting sheet of making of galvanic deposit, the interpole gap of control anode and negative electrode is 2.0-2.2cm, makes them be placed in the electrolyzer abreast;
(3) configuration concentration is 2.2mol/L HClO
4Pb (ClO with 0.32mol/L
4)
2Mixing solutions 300ml adds additive then, makes the tripoly phosphate sodium STPP that contains 0.05g/L in the electrolytic solution; 0.2g/L Mono Chloro Acetic Acid; 0.2g/L acetate behind 1.5g/L gelatine and the 2.5g/L sodium lignosulfonate and make electrolyte temperature progressively be elevated to 50 ℃, and is stabilized on this temperature;
(4) (3) process is obtained mixed electrolytic solution and is injected in the electrolyzer, treat that electrolyte temperature is stablized 50 ℃ after, the beginning constant-current electrolysis of connecting with the mains.Current density on control lead bullion anode and the negative electrode starting sheet is 300A/m
2This moment, the electrolyzer pressure of electrorefining process was generally between the 0.095-0.155V.Along with the carrying out of anode electrolysis process in leaching, its cumulative the anode sludge of more indissolubles, hindered the carrying out of anodic stripping, the rising that causes electrolyzer to be pressed.Press when electrolyzer to be elevated to 0.25V when above, this moment, we stopped electrorefining, took out the content in galvanic deposit lead electrode, lead bullion anode scrap and the anode thereof, the electrorefining end of processing.Electrolysis is obtained obtaining pure lead pig after cathode electrodeposition lead carries out fusion and casts.The anode sludge in the anode is used to refine rare metal.Because there is slight crystal protrusion phenomenon on the plumbous surface of electrolytic deposition, and the slight void between the crystal, its apparent density is 10.1g/cm
3, the mean pole spacing between two electrodes remains unchanged basically.
Through the ICP quantitative analysis, the metals content impurity in this lead pig is as shown in table 2.
Table 2
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.Through calculating, the plumbous power consumption of electrolytic process ton is 28.6 degree.
Embodiment 3
(1) get the lead bullion of selling on the market (its composition is seen table 3), wherein lead content is about 98%.With the fusion of 1kg lead bullion and cast the lead bullion anode that has striped, be of a size of 8*10*1.15 (wide * is high, and * is thick) cm
3, its anodic apparent density is 10.9g/cm
3, anode is packed in the anode that polycthylene grafted mould material processes simultaneously, and bag is thick to be 0.05mm.
(2) employing is of a size of 8*10*0.05 (wide * is high, and * is thick) cm
3The plumbous negative electrode starting sheet of making of galvanic deposit, the interpole gap of control anode and negative electrode is 0.9-1.1cm, makes them be placed in the electrolyzer abreast;
(3) configuration concentration is 2.2mol/L HClO
4Pb (ClO with 0.3mol/L
4)
2Mixing solutions 300ml adds additive then, makes the trisodium phosphate that contains 0.10g/L in the electrolytic solution; 0.2g/L Mono Chloro Acetic Acid; 0.2g/L acetate behind 2.0g/L gelatine and the 2.5g/L sodium lignosulfonate and make electrolyte temperature progressively be elevated to 40 ℃, and is stabilized on this temperature;
(4) (3) process is obtained mixed electrolytic solution and is injected in the electrolyzer, treat that electrolyte temperature is stablized 40 ℃ after, the beginning constant-current electrolysis of connecting with the mains.Current density on control lead bullion anode and the negative electrode starting sheet is 100A/m
2This moment, the electrolyzer pressure of electrorefining process was generally between the 0.075-0.135V.Along with the carrying out of anode electrolysis process in leaching, its cumulative the anode sludge of more indissolubles, hindered the carrying out of anodic stripping, the rising that causes electrolyzer to be pressed.Press when electrolyzer to be elevated to 0.30V when above, stop electrorefining this moment, take out the content in galvanic deposit lead electrode, lead bullion anode scrap and the anode thereof, the electrorefining end of processing.Electrolysis is obtained obtaining pure lead pig after cathode electrodeposition lead carries out fusion and casts.The anode sludge in the anode is used to refine rare metal.Only there is very small crystal protrusion phenomenon on the plumbous surface of this electrolytic deposition, the comparatively smooth densification of integral body, and its apparent density is 10.9g/cm
3, the mean pole spacing kept stable between two electrodes.
Through the ICP quantitative analysis, the metals content impurity in this lead pig is as shown in table 3.
Table 3
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.Through calculating, the plumbous power consumption of electrolytic process ton is 20.9 degree.
Embodiment 4
(1) get the lead bullion of selling on the market (its composition is with seeing table 4), wherein lead content is about 98%.With the fusion of 1kg lead bullion and cast the lead bullion anode that has striped, be of a size of 8*10*1.23 (wide * is high, and * is thick) cm
3, its anodic apparent density is 10.2g/cm
3, anode is packed in the anode that polycthylene grafted mould material processes simultaneously, and bag is thick to be 0.05mm.
(2) employing is of a size of 8*10*0.05 (wide * is high, and * is thick) cm
3The plumbous negative electrode starting sheet of making of galvanic deposit, the interpole gap of control anode and negative electrode is 2.0-2.2cm, makes them be placed in the electrolyzer abreast;
(3) configuration concentration is 2.5mol/L HClO
4Pb (ClO with 0.3mol/L
4)
2Mixing solutions 300ml adds additive then, makes the boric acid that contains 0.25g/L in the electrolytic solution; 0.2g/L Mono Chloro Acetic Acid; 0.2g/L acetate behind 0.02g/L naphthols and the 2.5g/L sodium lignosulfonate and make electrolyte temperature progressively be elevated to 63 ℃, and is stabilized on this temperature; And make electrolyte temperature progressively be elevated to 63 ℃, and be stabilized on this temperature.
(4) (3) process is obtained mixed electrolytic solution and is injected in the electrolyzer, treat that electrolyte temperature is stablized 63 ℃ after, the beginning constant-current electrolysis of connecting with the mains.Current density on control lead bullion anode and the negative electrode starting sheet is 600A/m
2This moment, the electrolyzer pressure of electrorefining process was generally between the 0.133-0.189V.Along with the carrying out of anode electrolysis process in leaching, its cumulative the anode sludge of more indissolubles, hindered the carrying out of anodic stripping, the rising that causes electrolyzer to be pressed.Press when electrolyzer to be elevated to 0.30V when above, stop electrorefining this moment, take out the content in galvanic deposit lead electrode, lead bullion anode scrap and the anode thereof, the electrorefining end of processing.Electrolysis is obtained obtaining pure lead pig after cathode electrodeposition lead carries out fusion and casts.The anode sludge in the anode is used to refine rare metal.Because there is small crystal protrusion phenomenon on the plumbous surface of electrolytic deposition, adds the slight void of the plumbous intergranule of galvanic deposit, its apparent density is 10.2g/cm
3, the mean pole spacing kept stable between two electrodes.
Through the ICP quantitative analysis, the metals content impurity in this lead pig is as shown in table 4.
Table 4
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.Through calculating, the plumbous power consumption of electrolytic process ton is 35.9 degree.
Claims (9)
1. direct electrolytic smelting method of lead bullion; It is characterized in that; Be pyrometallurgical smelting to be obtained lead bullion be cast as the lead bullion anode jacket in anode; In containing the perchloric acid of additive-lead perchlorate electrolysis of solutions liquid, carry out electrolysis with the plumbous galvanic deposit in the anode to negative electrode, thereby obtain the highly purified electrolytic lead and the anode sludge respectively at negative electrode and anode.
2. according to the method for claim 1, it is characterized in that the lead bullion anode is meant the lead bullion anode that contains a fixed gap, its apparent density is controlled at 9.9-11.0g/cm
3Between, the anode sludge was stayed in the anode after electrolysis was accomplished, and the anode sludge in the separate bag obtains rare metal contained in the lead bullion.
3. according to the method for claim 1; It is characterized in that; Anode is to adopt a kind of or two kinds of fiber production in vinylon, viscose fiber, SE barrier film, Vestolen PP 7052 or the polycthylene grafted mould material to form, and its gauge control is at 0.03-0.8mm.
4. according to the method for claim 1, it is characterized in that additive is meant the mixture that suppresses perchloric acid cathodic reduction additive 1, promotion lead bullion anode dissolution additive 2 and be used in perchloric acid medium's galvanic deposit additive 3.
5. according to the method for claim 4; It is characterized in that; Additive 1 is meant a kind of or two kinds of mixtures in tripoly phosphate sodium STPP, trisodium phosphate, boric acid or the 3-methoxybenzoic acid, and their separately effective concentration is respectively 0.01-2.5g/L, 0.05-6.0g/L, 0.01-10.0g/L and 0.01-5.0g/L.
6. according to the method for claim 4, it is characterized in that additive 2 is meant the mixture of Monochloro Acetic Acid and acetate, their effective concentration is respectively 0.02-10g/L and 0.01-5.0g/L.
7. according to the method for claim 4; It is characterized in that; The plumbous additive 3 of galvanic deposit is meant a kind of or two kinds of mixtures in naphthols, gelatine, sodium lignosulfonate or the tonka bean camphor, and the concentration of wherein above-mentioned four kinds of additive materials is corresponding 0.002-0.035g/L, 0.05-5.0g/L, 0.05-2.5g/L and 0.01-0.5g/L respectively.
8. according to the method for claims 1, it is characterized in that the concentration of perchloric acid is 0.3-3.5mol/L in described perchloric acid-lead perchlorate electrolytic solution, the concentration of lead perchlorate is 0.05-1.0mol/L, and the working temperature of electrolytic solution is 0-75 ℃.
9. according to arbitrary method of claims 1-8, it is characterized in that, described electrolysis, different temperature is selected different constant current density, and when the temperature of electrolytic solution was in 30-45 ℃, 20-300A/m was adopted in constant-current electrolysis
2Current density be advisable; When electrolyte temperature was in 45-60 ℃, 300-600A/m was adopted in constant-current electrolysis
2Current density; When electrolyte temperature was in 60-75 ℃, 600-1200A/m was adopted in constant-current electrolysis
2Current density.
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| CN104562093A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Method for preparing cathode used in refining of lead bullion |
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| CN110791802A (en) * | 2019-10-21 | 2020-02-14 | 北京曙光航空电气有限责任公司 | Electrochemical treatment method based on polar plate sheath |
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| CN108950600A (en) * | 2018-07-12 | 2018-12-07 | 益阳生力材料科技股份有限公司 | A kind of electrolyte and electrolytic method of lead bullion electrorefining |
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| CN113293409A (en) * | 2021-05-28 | 2021-08-24 | 中南大学 | Method for preparing compact and flat bismuth metal through electrolysis |
| US11913128B2 (en) | 2021-05-28 | 2024-02-27 | Central South University | Compact and flat bismuth metal preparation by electrolysis method |
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