CN102534661B - Method for refining crude lead - Google Patents
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- CN102534661B CN102534661B CN201210017247.5A CN201210017247A CN102534661B CN 102534661 B CN102534661 B CN 102534661B CN 201210017247 A CN201210017247 A CN 201210017247A CN 102534661 B CN102534661 B CN 102534661B
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Abstract
The invention relates to a method for refining crude lead, which belongs to the technical field of lead refining. Firstly, crude lead that is obtained through smelting or reducing lead reacts with NaOH containing PbO under a molten state so as to pre-remove As and Sb; then crude lead to be purified is processed through electrolytic refining in NaOH solution containing PbO, auxiliary complexing agents and electrodeposition lead additives so as to obtain electroanalysis lead and anode slime; and finally, electroanalysis lead is melted and poured. The method adopts a nontoxic and non-volatile alkaline medium, and adopts NaOH electrolyte with high conductivity, so that compact and smooth electroanalysis lead can be obtained; in addition, lower electrolytic cell pressure is adopted during the electrolytic process, so that electrolysis energy consumption is reduced, and the electrolysis energy conservation effect is obvious.
Description
Technical field
The invention belongs to plumbous refining techniques field, the present invention relates to a kind of by lead bullion utilization chemistry-electrochemical process carry out refining, purifying obtains the method for high purity electrolytic lead.
Background technology
The lead bullion that tradition pyrometallurgical smelting obtains could use widely conventionally after refining removal of impurities.The object of the refining of lead bullion is to remove the metallic impurity that are wherein mingled with on the one hand, and obtaining purity is 99.99% high purity lead, is that to reclaim in lead bullion be the precious metals such as copper, silver and bismuth on the other hand.
The plumbous refining techniques of industrial extensive employing at present is mainly divided into pyrorefining and electrorefining.There is the shortcomings such as the lower and precious metal losses of lead recovery due to pyrorefining, thereby since 20 beginnings of the century, electrolytic refining process in the world especially China be widely used.
In the research in plumbous electrolysis field, people once studied the acid systems such as fluorine boron salt, muriate and silicofluoric acid, and the method that wherein current industrial electrolytic lead refining generally adopts is Bai Zifa.Cypress hereby purifying method was proposed by A.G.Betts in 1901, and obtained industrial applications in 1902, and its principal character is to make electrolytic solution with the aqueous solution of plumbous silicofluoride and silicofluoric acid composition.First lead bullion is through the preliminary refining of pyrogenic process, and the impurity such as remove portion copper and antimony, then cast anode, and negative electrode adopts galvanic deposit lead to cast starting sheet, is incorporated with PbSiF
6(0.3-0.5mol/L) with free H
2siF
6(0.4-0.6mol/L) in electrolyzer, carry out electrolysis.Because silicofluoric acid easily volatilizees and resolves into poisonous HF and SiF in the time being heated
4, this technique is general adopts rarer silicate fluoride solution, and electrolysis temperature general control is at 30-45 DEG C.Owing to being subject to the restriction of dilute solution specific conductivity and normal temperature lead ion diffusibility, the current density of electrolytic process is generally 180-200A/m
2, electrolyzer is pressed as 0.4-0.5V, and current efficiency is 92-96%, and the electrolysis energy consumption of lead per ton is 120-135KWh.The result of electrorefining is the highly purified electrolytic lead of negative electrode output, obtains the anode scrap of surface with the anode sludge simultaneously.Electrolytic lead is fusing after washing, then carries out oxidation refining and further removes micro-arsenic, antimony, tin, obtains electrolytic lead product by ingot casting, and wherein a part is used for casting starting sheet.Anode scrap is being removed after the surperficial anode sludge refuse and is casting anode.
The advantage of Bai Zifa electrolytic refining process is when can directly obtaining the very high lead bullion of purity, and makes the concentration of precious metal such as copper silver in the anode sludge, thereby is conducive to the comprehensive recovery of the precious metals such as gold and silver.Although through the improvement of more than 100 years, still there is following main drawback in existing cypress hereby purifying method:
1, the H that this process using can only low concentration
2siF
6-PbSiF
6solution carries out electrorefining, conventionally needs the electrolyzer of 0.5V to press, and the Direct Electrolysis energy consumption of refining process is higher, is generally 120-130KWh/t.
2, H
2siF
6easily volatilization, especially more easily produces a large amount of poisonous acid mists summer in job site, the smell is awful.H in addition
2siF
6also can decomposite poisonous HF and SiF
4gas, harmful to human and environment.
The lead bullion that pyrometallurgical smelting obtains not only contains metallic lead, simultaneously owing to being often mingled with other metallic compound in lead ore, these metallic compounds are reduced together along with the reduction of metallic lead in high-temperature reductibility atmosphere, by analysis, in lead bullion, be often mingled with the metals such as Ag, As, Bi, Cu, Sn, Sb, Cd and Fe.The purification process of lead bullion is the process of utilizing the difference of metal or non-metallic element self chemical activity or acid-basicity to carry out gradation separation in essence.The principle reality of electrorefining is also to carry out optionally stripping or electrodeposition process according to the difference of electropotential between element.This electrorefining situation can be divided into three kinds of situations, and the 1st, be mingled with the more negative metal of electropotential; The 2nd, be mingled with electropotential corrigendum metal; The 3rd, be mingled with the close metal of electropotential.
In the time being mingled with the more negative metal of electropotential in lead, Fe, the Cd being for example mingled with in lead or Zn simple substance.We are taking Fe as example, be respectively-0.44V of the current potential of its electropotential in acidity or alkaline medium and-0.877V, and plumbous and+common electric potential of divalent lead compound in acidity or alkalescence be-0.126V and-0.578V, specific as follows:
Fe-2e＝Fe
2+ (E
A 0＝-0.44V)
Fe-2e+2OH
-＝Fe(OH)
2 (E
B 0＝-0.877V)
Pb-2e＝Pb
2+ (E
A 0＝-0.126V)
Pb-2e+2OH
-＝PbO+H
2O (E
B 0＝-0.578V)
Therefore,, for the Fe metal being mingled with in lead, the electrorefining process that we are easy to carry out at acidity or alkaline medium anodic stripping and cathode electrodeposition is separated.For example, when we adopt their two kinds of alloys to carry out refining as anode in acidic medium, now Fe is because current potential is more negative, thereby first anodic stripping reaction occurs.Simultaneously on negative electrode, the Fe in solution
2+because deposition potential is far defeated by pb
2+, when therefore we pass through to control certain electropotential, pb
2+preferentially become metallic lead at negative electrode by galvanic deposit.If we adopt alkaline electrolysis liquid medium, electric stripping-precipitation process is also similar.
In the time being mingled with the metal of electrode corrigendum in lead, two kinds of metal simple-substances of the Cu being for example mingled with in lead bullion and Ag, because their electropotentials in acidity are as follows respectively:
Cu-2e＝Cu
2+ (E
A 0＝0.337V)
Cu-2e+2OH
-＝Cu(OH)
2 (E
B 0＝-0.224V)
Ag-e＝Ag
+ (E
A 0＝0.7996V)
Ag-e+OH
-＝1/2Ag
2O+H
2O (E
B 0＝0.344V)
When we adopt the alloy that contains Pb, Cu and their three kinds of metals of Ag to carry out refining as anode in acidic medium, now the stripping current potential of Cu and Ag is far above Pb, thereby only have Pb that first anodic stripping reaction occurs, two kinds of metals of Cu and Ag do not have stripping, and stay anode surface, form the anode sludge.Same in electrolytic solution due to the Cu that does not have anodic stripping to form
2+and Ag
+, only have pb
2+become metallic lead at negative electrode by galvanic deposit.If we adopt alkaline electrolysis liquid medium, two kinds of metals of Cu and Ag are also stayed anode surface, finally form the anode sludge.
In the time being mingled with the close metal of electropotential in lead, conventionally in 0.1V.Now electrorefining, in the time of anodic stripping, is usually mingled with the common stripping of other metal of certain proportion or carries out co-precipitation at negative electrode, and now we are difficult to obtain highly purified metallic lead by single electrorefining mode.The Sb element being for example mingled with in lead, its electropotential in acid and alkaline medium is as follows respectively:
Sb-3e+3/2H
2O＝1/2Sb
2O
3+3H
+ (E
A 0＝0.152V)
Sb-3e+4OH
-＝SbO
2 -+2H
2O (E
B 0＝-0.66V)
Traditional cypress, hereby in purifying method, Sb has than the electrode of Pb corrigendum, and now Sb preferentially stays in the anode sludge with the form of simple substance.In basic solution, the SbO of high density
2 -likely be accompanied by lead ion generation cathode codeposition process.
For this simple substance of As, its electropotential in acidity or basic solution is as follows respectively:
As-3e+3/2H
2O＝1/2H
3AsO
3 (E
A 0＝0.247V)
As-3e+4OH-＝AsO
2 -+2H2O (E
B 0＝-0.68V)
We find, its electropotential situation in basic solution is similar with Sb.In existing acid refining, they are mainly stayed anode with anode sludge form and show, and in basic refining method of the present invention, it will be stayed in electrolytic solution with the form of preferential anodic stripping, causes in electrolytic process, AsO in electrolytic solution
2 -the enrichment gradually of concentration.
For Sn simple substance, its electropotential in acidity or basic solution is as follows respectively:
Sn-2e＝Sn
2+ (E
A 0＝-0.14V)
Sn-2e+4OH-＝SnO
2 2-+2H
2O (E
B 0＝-0.91V)
Hereby in purifying method, due to the electropotential that the electrode of Sn (0.14V) is defeated by Pb (0.126V) slightly, in electrolytic solution, very easily easily there is the enrichment of Sn existing acid cypress.Add electropotential between them very approaching, therefore Sn is very easy to negative electrode co-precipitation occurs together with Pb, and therefore, for the electrorefining of Pb, Sn is the metal of very difficult removal of impurities in acidity.The conventional method of people is to separate fully in ore dressing process, and then the characteristic of smelting process recycling Sn metallicity ripple slightly alive, utilizes oxygen to be oxidized, and makes the Sn being mingled with in lead become SnO
2or scum silica frost is removed.We find that the electropotential of Sn is far defeated by Pb in alkaline electrolyte, although this situation is difficult to occur the electrolytic codeposition of nickel of Sn at negative electrode, SnO in electrolytic solution can occur
2 2-enrichment.
Regrettably, the research of current performing electrolytic refining on lead bullion both domestic and external and production are still mostly limited to Betts method.The electrolytic lead smelting method (CN200810232653.7) of the people such as such as Gao Wenjie invention reported silicofluoric acid concentration adjusted to 110-149g/L, and lead content is 70-110g/L, adopts forward and reverse DC electrolysis method to smelt plumbous method.The method has been eliminated lead dendritic crystal to a certain extent, but in the reversible circulation stage, the lead of just galvanic deposit is dissolved in electrolytic solution again, causes this part electricity loss of energy.In the production method (CN200810097208.4) of the high purity lead of Ma Shengjun invention, reported from lead sulfide ore and waste lead acid battery, smelt obtain in silicofluoric acid and plumbous silicofluoride electrolytic solution, carry out electrorefining and obtain the method for high purity lead (99.99%) containing stibium crude lead.This invention is that the distance by controlling electrolyzer Anodic and negative electrode is installed, and has obtained more than 99.996% pure lead, and regrettably, electrolytic process still needs the electrolyzer of 0.45-0.48V to press, and causes electrolysis energy consumption higher.Also there is people from environmental, once used and in alkaline system, carry out plumbous electrolysis.For example Chen Wei flat (Hunan University's journal, 1996,23 (6): 111-116) utilizes NaOH and KNaC
4h
4o
6under the help of gelatin additive, carry out the electrolysis of lead plaster and reclaim the lead in lead plaster, regrettably, this galvanic deposit can only obtain spongiform lead powder.And relevant people utilize alkaline NaOH solution to carry out the method rarely seen report always of lead bullion electrorefining.Because the dissolving power of plumbous oxide in simple NaOH solution is limited, add and do not find that effective galvanic deposit additive gets off to control plumbous electrodeposition process, mostly what obtain is loose porous electrolytic lead, the lead of this high-ratio surface is easy in melting process and airborne oxygen generation oxidizing reaction, these are all unfavorable for the industrial application of NaOH system electrolysis, cause plumbous alkaline system electrolysis to be failed developed always, also do not realize so far industrial applications.
Summary of the invention
A kind of method that the object of the invention is to overcome above-mentioned the deficiencies in the prior art and provide clean energy-conservation electrolysis refined lead.First the present invention adopts the NaOH fused solution that contains PbO to carry out pre-dearsenification, antimony and tin to lead bullion, makes it to be more suitable for the needs of alkaline electrolysis refining.Content of impurities in the lead bullion that pyrometallurgical smelting obtains is conventionally in 1%, therefore the content of every kind of impurity simple substance is very low, but in refining process, need in order to reduce electrolytic solution the pressure often upgrading, the present invention provides a kind of method that significantly reduces the refined lead of electrolytic solution consumption by the pre-removal of impurities of alkalescence simultaneously.
One of key point of the present invention is to find that novel complexing agent has increased substantially the solubleness of plumbous oxide in NaOH, two of key point is to find that the plumbous additive of novel galvanic deposit has overcome a plumbous difficult problem that easily generates dendrite arm in alkaline medium, thereby can obtain purity up to more than 99.99% fine and close galvanic deposit lead.Due to the use of high conductivity and high density NaOH electrolytic solution, the present invention has lower electrolyzer and presses in electrolytic process, has significantly reduced electrolysis energy consumption, and Electrolytic Energy Saving effect is remarkable.The present invention presses at the electrolyzer that the laboratory lab scale stage has obtained the low 0.07-0.15V of reaching, and makes electrolysis energy consumption be reduced to 26-50KWh/t (Pb).These energy-saving and emission-reduction of studying as further excavating electrolytic lead refining process provide a kind of new important channel.
For achieving the above object, the technical solution used in the present invention is as follows.A kind of electrolytic smelting method of lead bullion, be first smelting to be obtained to lead bullion or the plumbous reaction that pre-de-As, Sb and Sn occur at molten state and the NaOH that contains PbO of reduction, then the lead bullion of purifying in advance carried out to electrorefining in the NaOH solution that contains the plumbous additive of PbO, complexing-aid agent and galvanic deposit and obtain the method for electrolytic lead and the anode sludge.
A method for refining crude lead, is characterized in that, comprises the following steps:
(1) lead bullion under molten state and be dissolved with in the NaOH fused solution of PbO and carry out redox reaction, makes As, Sb and Sn in lead bullion first be converted into Na
3asO
3, Na
3sbO
3and Na
2snO
2remove as scum silica frost, thereby obtain the lead bullion of pre-removal of impurities;
(2) lead bullion of the pre-removal of impurities of step (1) is cast to positive plate, electrolytic lead or stainless steel are made to negative electrode starting sheet simultaneously, be placed in the NaOH solution that contains PbO, complexing-aid agent and galvanic deposit additive and carry out electrolysis;
(3) make in the lead dissolving galvanic deposit negative electrode starting sheet in lead bullion anode by electrolysis, anode surface has the mud shape metal of indissoluble to generate gradually simultaneously, mud shape metal is the anode sludge, and wherein segment anode mud becomes groove mud because bottom of electrolytic tank is sunk in stirring;
(4) electrolytic lead cathode electrodeposition being obtained carries out obtaining pure lead pig after melting and casting.
In aforesaid method, in step (1) NaOH, the mass content of PbO is 1-20%, and NaOH molten state is at 400-550 DEG C.In step (2), in electrolyzer, the concentration of electrolytic solution NaOH is 3-11mol/L, and PbO concentration is 0.05-0.55mol/L.In step (3), the electrolysis temperature of electrolyzer is 30-110 DEG C, current density 100-1500A/m
2.
In above-mentioned steps (1), NaOH has not only played dissolving As
2o
3, Sb
2o
3effect with SnO; also play a part protecting the lead of fusing to avoid dioxygen oxidation in air simultaneously; although therefore calculating the weight of NaOH in theory according to the amount of As, Sb and Sn in impurity in lead bullion is only the 0.1-0.4% of lead bullion weight; but NaOH dosage in fact of the present invention is the 1.5-30% of lead bullion weight, these excessive NaOH form a liquid level and play a part to protect these lead to avoid oxidation on the lead of fusing.
The lead bullion of the pre-removal of impurities of above-mentioned steps (2) is through being cast into after anode, is placed on and in above-mentioned electrolytic solution, carries out electrorefining.Because PbO is the epicene meta-alkalescence metal oxide of a kind of tool, therefore NaOH has limited dissolving power to PbO.The lysate of PbO in NaOH is expressed as NaPb (OH) conventionally
3, NaHPbO
2, Na
2pb (OH)
4or Na
2pbO
2, more scientific expression is in recent years generally NaPb (OH)
3, in fact it can regard PbO+H as
2o or Pb (OH)
2and complexing lysate between NaOH.,
Pb (OH)
2+ NaOH=NaPb (OH)
3(formula 1-1)
From above-mentioned reaction formula (1-1), can find out, the NaOH solution of high density and comparatively high temps is conducive to the dissolving of PbO, the present invention is in order to reduce the impedance of electrolytic solution of electrolytic process in addition, through a large amount of optimization experiment, find that the NaOH of higher concentration can be used as the complexing agent of PbO, doubles as the conductive agent of solution simultaneously.Experiment shows, in electrolytic solution, comparatively ideal NaOH concentration is 3-11mol/L, and PbO concentration is 0.05-0.55mol/L simultaneously, and correspondingly the temperature of electrolytic solution is controlled at 30 to 110 DEG C, preferably at the temperature of 35 to 75 DEG C, carries out.The present invention, in order to improve the dissolution rate of PbO and the stability of electrolytic solution, adds a small amount of complexing-aid agent to improve the dissolving power of electrolytic solution to PbO in NaOH-PbO solution.The present invention adopts a kind of or two kinds of complexing-aid agents that mixture is dissolution process in ethylene glycol, glycerol, sorbyl alcohol or Xylitol, and wherein the concentration of each complexing-aid agent is 0.1-50g/L.
Existing research discovery, in the alkaline PbO solution of high density, galvanic deposit lead is easy to grow into the lead with dendrite arm or powdery, and the metallic lead of this high-ratio surface, because have very high specific surface, is therefore easy to occur oxidizing reaction in melting process.The present invention finds through great many of experiments, some materials can be used as the galvanic deposit additive of electrodeposition process lead, they are one or both mixtures in gum resin, trolamine, thionamic acid sodium, methylsulphonic acid lead, sodium lignosulfonate or Dodecyl Dimethyl Amine, and wherein the concentration of each galvanic deposit additive materials is 0.1-10g/L.In electrolytic process, can effectively improve the compactness of galvanic deposit lead by adding above-mentioned galvanic deposit additive mixture a kind of or two kinds, thereby reduce oxidation plumbous in follow-up melting process.
Usually, in the starting stage of electrolysis, the chloride plate forming due to casting shows smoother, its specific surface is relatively little, therefore it can bear Anodic Stripping Currents and also reduces thereupon, if now adopt higher current density to carry out electrolysis, must bring very high anodic polarization current potential.Correspondingly, in negative electrode one side, same ganoid lead electrode, because its true specific surface is less, also can only be born less electric current and carry out galvanic deposit.Existing cypress hereby in purifying method, the rising that single constant current mode has not only caused electrolysis initial stage groove to press, and also this too high current density is easy to cause the generation of the dendritic lead of negative electrode.In fact single electrolysis mode is difficult to the plumbous stripping-electrodeposition process in electrorefining process of real embodiment and corresponding electrochemistry rule thereof in itself, thereby is difficult to fully excavate plumbous energy saving way from darker angle.
The present invention finds by the polarization scan of a large amount of anodes or negative electrode, at the initial stage of electrolysis, adopt constant-potential electrolysis pattern stage by stage, not only can effectively control the groove of electrolytic process and press, and can react more truly the electric current ability to bear of lead electrode self.Along with the carrying out of electrolytic process, now anode becomes more coarse because of plumbous stripping, negative electrode, also because tiny plumbous galvanic deposit makes the lead on its surface have certain increase, can progressively be heightened the groove of constant-potential electrolysis process and press simultaneously, progressively increases the current density of electrolytic process.Usually, when electrolysis is carried out after 3-30h, now lead bullion anode and galvanic deposit lead electrode can be born certain constant current mode and carry out electrolysis, and now the present invention proceeds to conventional constant-current electrolysis process, until electrorefining finishes.The electrolytic process of reality of the present invention is to adopt continuous constant-potential electrolysis process and constant-current electrolysis process of multistage.Preferably: the starting stage of electrolysis adopts the constant potential electrolysis pattern of 0.04-0.06V, electrolysis time 1-3h; Adopt the constant potential electrolysis pattern of 0.07-0.08V in the subordinate phase of electrolysis, electrolysis time 1-3h; Further heighten the magnitude of voltage of constant potential electrolysis in the phase III of electrolysis, the voltage of controlling constant potential electrolysis is 0.09-0.11V, electrolysis time 1-3h; Proceed to constant-current electrolysis pattern in the fourth stage of electrolysis, now according to the height of the temperature of electrolytic solution in electrolyzer, control the current density of lead bullion anode.In implementation process of the present invention, owing to having adopted the NaOH of high density and higher electrolysis temperature, these two factors can significantly promote the raising of electrolytic conductivity, and therefore constant-current electrolysis of the present invention can be than carrying out under current density higher in existing silicofluoric acid medium.When electrolyte temperature is during in 30-45 DEG C, constant-current electrolysis adopts 100-300A/m
2current density.When electrolyte temperature is during in 45-60 DEG C, electrolytic solution can adopt 300-750A/m
2current density.When electrolyte temperature is during in 60-110 DEG C, the current density of electrorefining process can adopt 750-1500A/m
2level.
In implementation process of the present invention, find, in fourth stage constant-current electrolysis process, the electrolyzer of electrorefining process is pressed in the 10-50h of beginning, still there will be certain decline phenomenon, this phenomenon derives from anode lead progressively dissolve after, its surface becomes coarse, causes actual real current density to decrease.Similarly, also there is thickening of stereotype and process of growth in the lead of galvanic deposit negative electrode, also causes the real current density of negative electrode to decrease, and these two factors are pressed electrolyzer can be low between 0.077-0.095V.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 and be elevated to 0.2-0.3V when above when electrolyzer, now stop electrolysis, and take out residual lead bullion anode and galvanic deposit lead electrode, electrorefining end of processing.Electrolysis obtains cathode electrodeposition lead and carries out melting operation, after casting, obtains pure lead pig.
In sum, method of the present invention has following features:
(1) in implementation process of the present invention, the present invention is by the mode of the pre-removal of impurities of alkalescence for the first time, farthest remove the soluble impurity such as As, Sb and Sn being mingled with in former lead bullion cream, thereby provide help for improving the purity of follow-up electrorefining lead and reducing the pressure of regeneration of electrolyte;
(2) in electrorefining process of the present invention, the present invention utilizes the alkaline NaOH solution of high density and the assist in dissolving effect of complexing-aid agent, obtained the PbO solution of high density, the NaOH solution of this high density and the PbO of high density provide favourable condition for the polarization and the corresponding electrolysis energy consumption that reduce in electrolytic process.
(3) the present invention adopts electrolysis mode stage by stage in electrolytic process, and this electrolysis mode can effectively be controlled the electrolyzer of electrolytic process and press, thereby obtains lower electrolysis energy consumption.
(4) the present invention adopts the NaOH solution of non-volatility, can greatly eliminate the poisonous acid mist problem of existing refining plant because adopting silicofluoric acid medium to produce, thereby increases substantially labor's Production environment quality.
(5) the present invention adopts the electrolytic solution of high conductivity NaOH solution as refining process, can obtain densification, smooth electrolytic lead under galvanic deposit Additive, (200-300A/m under with the identical current density of existing industrial electrolysis
2) batch experiment in, the electrolyzer that can obtain the low 0.10-0.15V of reaching is pressed, directly save the electrolyzer of 0.3-0.4V both at home and abroad presses than the existing silicofluoric acid method extensively adopting, the refining process of lead per ton is saved 80-90KWh/t, this can save every year 3200-3600 ten thousand degree electricity for the Qian Ye company of 400,000 tons of annual outputs, this,, for reducing plumbous production cost, promotes the energy-saving and emission-reduction of plumbous industry industry to have important realistic price.
Brief description of the drawings
Fig. 1 is the FB(flow block) of the inventive method;
Fig. 2 is the voltage-time curve in embodiments of the invention 4.
Embodiment
Hereinafter carry out with reference to the accompanying drawings to describe in more detail illustrative embodiments.Described accompanying drawing is used for illustrating the present invention, but not is limited.
The present invention adopts alkali-chloride improving, now Sb (0.66V) has the more negative electropotential than Pb (0.578V), but only have-0.082V of potential difference between the two, therefore the impurity Sb being mingled with in lead is in anodic stripping process, to be accompanied by the stripping of Pb and preferential stripping, the SbO of these strippings
2 -ion will be enriched in electrolytic solution gradually, cause the SbO in electrolytic solution
2 -raise gradually.Although rare SbO
2 -be difficult to again cathode electrodeposition and become Sb, but the rear SbO that these solubility raise gradually
2 -follow and separate out at negative electrode by slowly starting, thereby reduced the purity of cathode electrodeposition lead.
It should be noted that, content of impurities in the lead bullion that pyrometallurgical smelting obtains is conventionally in 1% left and right, therefore the content of every kind of impurity simple substance is very low, but in refining process, need in order to reduce electrolytic solution the pressure often upgrading, the present invention provides a kind of method of the refined lead that can significantly reduce electrolytic solution consumption simultaneously.Fig. 1 is the schema of an embodiment of the inventive method.With reference to Fig. 1, lead bullion forms plumbous liquid after heating and melting in advance, then adds the NaOH of melting and the mixture of PbO, and stirs fully.The electropotential that the present invention utilizes the electrode of As, Sb in lead bullion now and tri-kinds of simple substance of Sn to be defeated by Pb, makes the redox reaction between their three kinds of simple substance and excessive PbO, and these reactions are simultaneously accelerated because of the high temperature of melting NaOH and plumbous liquid.Another advantage of molten lead liquid is that plumbous surface can be upgraded rapidly in stirring in addition, thereby ensures that As, the Sb of plumbous liquid inside and Sn obtain sufficient removal of impurities.Above-mentioned reaction is as follows:
2As+3PbO＝3Pb+As
2O
3
As
2O
3+6NaOH＝2Na
3AsO
3+3H
2O
2Sb+3PbO＝3Pb+Sb
2O
3
Sb
2O
3+6NaOH＝2Na
3SbO
3+3H
2O
Sn+PbO＝Pb+SnO
SnO+2NaOH＝Na
2SnO
2+H
2O
Salt-forming reaction between above-mentioned redox and oxide compound and NaOH subsequently finally obtains containing Na
3asO
3, Na
3sbO
3and Na
2snO
2the scum silica frost of impurity and with purify after metallic lead.
In alkalescence provided by the invention removes lead bullion in the method for As, Sb and Sn, in aforesaid method, the NaOH gross weight of controlling this step is the 1.5-30% of metal lead bullion (preferably 5-30%), and the weight of wherein adding PbO is the 1.5-10% of lead bullion content.In order to ensure that reactant carries out removing impurities qualitative response quickly and efficiently, need the temperature of NaOH melting to be controlled on plumbous fusing point, again in order to reduce plumbous volatilization at high temperature, we are controlled at the reaction of this process between 400-550 DEG C simultaneously, and the simultaneous reactions time is 10-120min.The too short reaction times is difficult to above-mentioned three kinds of impurity in effective elimination lead bullion, and the long time has increased the oxidational losses of lead bullion.
Great many of experiments shows, through above-mentioned basic removing foreign matter process, As, Sb in lead bullion and the impurity weight percent content of Sn can be reduced to respectively 0.0004-0.001%, 0.0005-0.002% and the 0.0004-0.001% of plumbous weight, and the single index of these simple substance can reach trade mark Pb99.990 or above standard.In an embodiment of the invention, 10kg lead bullion is in advance through after 420 DEG C of fusings, drop into the melting NaOH of 0.5kg and the PbO of 0.2kg, the reaction of process 60min under fully stirring, As, Sb in lead bullion and the impurity weight percent content of Sn can be reduced to respectively 0.0006%, 0.0007% and 0.0004% of plumbous weight, this index except As be Pb99.994 than the trade mark 0.0005% slightly higher, all the other two kinds of metals content impurities have reached the standard of Pb99.994.The pre-removal of impurities process of this alkalescence, provides the raw material of high-quality for alkaline electrolysis refinery practice below reduces the pollution of As, Sb and tri-kinds of impurity of Sn in electrolytic solution.
The electrolytic process of following examples is the preferred version in the present invention preferably, and in electrolytic process, the electrochemical reaction formula of anode and negative electrode is expressed as follows:
Anode: Pb-2e+3OH
-=Pb (OH)
3 -
Negative electrode: Pb (OH)
3 -+ 2e=Pb+3OH
-
In this electrolytic process, the Pb that can see anode loses electronics and dissolves, simultaneously Pb (OH)
3 -obtain electronics generation electrodeposition process at negative electrode.Although in theory, the theoretical electromotive force of this process depends on the Pb (OH) between anode and negative electrode
3 -the concentration potential that concentration difference forms.In the time that anode is identical with near plumbum ion concentration negative electrode, now the electromotive force between two electrodes is almost equal.But in actual electrolytic process, anode is due to the continuous stripping of lead, cause plumbum ion concentration higher, negative electrode is lead ion galvanic deposit constantly to occur become plumbous consumption reaction, cause near the plumbum ion concentration of negative electrode slightly lower than solution bulk concentration, therefore this process need promotes the carrying out of electrolytic process by external power supply.
Embodiment 1
(1) get the lead bullion of the last decopper(ing) of selling on market, wherein lead content is about 99%.By 1kg lead bullion first at 450 DEG C and the 100g NaOH fused solution that is dissolved with 20g PbO react 45min, make to be separately converted to Na after the impurity such as As, Sb and Sn wherein and above-mentioned excessive PbO and NaOH reaction
3asO
3, Na
3sbO
3, Na
2snO
2process with metallic lead;
(2) lead bullion obtaining through above-mentioned pre-purification is cast 8*11*1 (wide * is high, and * is thick) cm
3positive plate, adopt and be of a size of 8*11*0.05 (wide * is high, and * is thick) cm simultaneously
3stainless steel make negative electrode starting sheet, the interpole gap of controlling anode and negative electrode is 2.6-3.0cm, and they are placed in electrolyzer abreast;
(3) configuration concentration 300ml is the PbO mixing solutions of 7M NaOH and 0.3M, then adding 1g sorbyl alcohol to make the concentration of complexing-aid agent is 3g/L, in order to keep the planarization on the plumbous surface of electrodeposition process galvanic deposit, we add the trolamine of 0.5g/L gum resin and 0.5g/L in above-mentioned solution simultaneously;
(4) (3) process is obtained to mixed electrolytic solution and be injected in electrolyzer, stablize after 50 DEG C until electrolyte temperature, connect with the mains and start to carry out electrolysis.In order effectively to prevent the generation of electrolytic process lead dendritic crystal and to save the electric energy of electrorefining process, experimentation adopts electrorefining pattern stage by stage.
In the initial 0-3h stage of electrolysis, first adopt the constant potential electrolysis pattern of 0.05V; At the subordinate phase 4-6h of electrolysis, adopt the constant potential electrolysis pattern of 0.075V; At the phase III of electrolysis 7-10h, the present invention further heightens constant potential electrolysis magnitude of voltage, and controlling constant potential electrolysis voltage is 0.1V.In the fourth stage of electrolysis, keep electrolysis temperature constant, the present invention proceeds to constant-current electrolysis pattern, and the current density of controlling lead bullion anode is 300A/m
2, the current density on corresponding negative electrode starting sheet is 300A/m
2.Now the electrolyzer of electrorefining process is pressed and is generally between 0.079-0.152V.Along with the carrying out of anode electrolysis process in leaching, its surface has accumulated the anode sludge of more indissolubles, has hindered the carrying out of anodic stripping, the rising that causes electrolyzer to be pressed.In the time that the high 0.2V of electrolyzer voltage rise is above, now we stop electrorefining, take out lead bullion anode and cathode electrodeposition lead.Electrolysis is obtained to cathode electrodeposition lead to be carried out obtaining pure lead pig after melting and casting.
Through ICP quantitative analysis, the metals content impurity in this lead pig is as shown in table 1.
The Chemical Analysis of Wire Rod of table 1 lead pig
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.As calculated, the power consumption of electrolytic process ton lead is 27.9 degree electricity.
Embodiment 2
(1) get on the market common pyrogenic process lead bullion, wherein lead bullion content is about 99%.By 5kg lead bullion first at 450 DEG C and the 400g NaOH fused solution that is dissolved with 70g PbO carry out stirring reaction 60min, make to reduce after impurity Sb, Sn in lead and As impurity and above-mentioned excessive PbO and NaOH reaction and be separately converted to Na
3sbO
3, Na
2snO
2, Na
3asO
3process with metallic lead;
(2) lead bullion obtaining through above-mentioned pre-purification is cast 18*20*1.2 (wide * is high, and * is thick) cm
3positive plate, adopt and be of a size of 8*11*0.05 (wide * is high, and * is thick) cm simultaneously
3the pure plumbous negative electrode starting sheet of making, they are placed in electrolyzer abreast, the interpole gap of its Anodic and negative electrode is 2.9-3.0cm.
(3) configuration concentration 1.5L is the PbO mixing solutions of 8M NaOH and 0.35M, then adding 30g ethylene glycol to make the concentration of complexing-aid agent is 20g/L, in order to keep the planarization on the plumbous surface of electrodeposition process galvanic deposit, we add the sodium lignosulfonate of 0.5g/L methylsulphonic acid lead and 2g/L in above-mentioned solution simultaneously.
(4) (3) process is obtained to mixed electrolytic solution and be injected in electrolyzer, be stabilized in after 60 DEG C until electrolyte temperature, connect with the mains and start to carry out electrolysis.In order effectively to prevent the generation of electrolytic process lead dendritic crystal and to save the electric energy of electrorefining process, experimentation adopts electrorefining pattern stage by stage.
In the initial 0-3h stage of electrolysis, first adopt the constant potential electrolysis pattern of 0.05V; At the subordinate phase 4-6h of electrolysis, adopt the constant potential electrolysis pattern of 0.075V; At the phase III of electrolysis 7-10h, the present invention further heightens constant potential electrolysis magnitude of voltage, and controlling constant potential electrolysis voltage is 0.1V.In the fourth stage of electrolysis, keeping electrolysis temperature is 60 DEG C, and the present invention proceeds to constant-current electrolysis pattern, and the current density of controlling lead bullion anode is 500A/m
2, the current density on corresponding negative electrode starting sheet is also 500A/m
2.Now the electrolyzer of electrorefining process is pressed and is generally between 0.087-0.135V.Along with the carrying out of anode electrolysis process in leaching, its surface has accumulated the anode sludge of more indissolubles, has hindered the carrying out of anodic stripping, the rising that causes electrolyzer to be pressed.In the time that the high 0.3V of electrolyzer voltage rise is above, now we stop electrorefining, take out lead bullion anode and cathode electrodeposition lead.Electrolysis is obtained to cathode electrodeposition lead to be carried out obtaining pure lead pig after melting and casting.
Through ICP quantitative analysis, the metals content impurity in this lead pig is as shown in table 2.
The Chemical Analysis of Wire Rod of table 2 lead pig
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.As calculated, the power consumption of electrolytic process ton lead is 31.9 degree electricity.
Embodiment 3
(1) get waste lead acid battery common on market and reclaim the reduction lead obtaining, wherein lead bullion content is about 98.7%.By 1kg lead bullion first at 500 DEG C and the 100g NaOH fused solution that is dissolved with 30g PbO carry out stirring reaction 45min, make to reduce after major impurity Sb, Sn in lead and As impurity and above-mentioned excessive PbO and NaOH reaction and be separately converted to Na
3sbO
3, Na
2snO
2, Na
3asO
3process with metallic lead;
(2) lead bullion obtaining through above-mentioned pre-purification is cast 8*11*1 (wide * is high, and * is thick) cm
3positive plate, adopt and be of a size of 8*11*0.05 (wide * is high, and * is thick) cm simultaneously
3stainless steel make negative electrode starting sheet, they are placed in electrolyzer abreast, the interpole gap of its Anodic and negative electrode is 2.5-2.8cm.
(3) configuration concentration 300ml is the PbO mixing solutions of 7.5M NaOH and 0.33M, then adding 3.33g Xylitol to make the concentration of complexing-aid agent is 10g/L, in order to keep the planarization on the plumbous surface of electrodeposition process galvanic deposit, we add the Dodecyl Dimethyl Amine of 0.5g/L gum resin and 0.1g/L in above-mentioned solution simultaneously.
(4) (3) process is obtained to mixed electrolytic solution and be injected in electrolyzer, be stabilized in after 55 DEG C until electrolyte temperature, connect with the mains and start to carry out electrolysis.In order effectively to prevent the generation of electrolytic process lead dendritic crystal and to save the electric energy of electrorefining process, experimentation adopts electrorefining pattern stage by stage.
In the initial 0-3h stage of electrolysis, first adopt the constant potential electrolysis pattern of 0.05V; At the subordinate phase 4-6h of electrolysis, adopt the constant potential electrolysis pattern of 0.075V; At the phase III of electrolysis 7-10h, the present invention further heightens constant potential electrolysis magnitude of voltage, and controlling constant potential electrolysis voltage is 0.1V.In the fourth stage of electrolysis, the present invention proceeds to constant-current electrolysis pattern, and the current density of controlling lead bullion anode is 350A/m
2, the current density on corresponding negative electrode starting sheet is also 350A/m
2.Now the electrolyzer of electrorefining process is pressed and is generally between 0.079-0.116V.Along with the carrying out of anode electrolysis process in leaching, its surface has accumulated the anode sludge of more indissolubles, has hindered the carrying out of anodic stripping, the rising that causes electrolyzer to be pressed.In the time that the high 0.3V of electrolyzer voltage rise is above, now we stop electrorefining, take out lead bullion anode and cathode electrodeposition lead.Electrolysis is obtained to cathode electrodeposition lead to be carried out obtaining pure lead pig after melting and casting.
Through ICP quantitative analysis, the metals content impurity in this lead pig is as shown in table 3.
The Chemical Analysis of Wire Rod of table 3 lead pig
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.As calculated, the power consumption of electrolytic process ton lead is 27.6 degree electricity.
Embodiment 4
In electrolytic process, adopt the NaOH solution of 8M, the PbO that this solution contains 70g/L has simultaneously added the ethylene glycol of 3g/L as complexing-aid agent simultaneously, has added the gum resin of 0.2g/L and the sodium lignosulfonate of 0.9g/L as galvanic deposit additive.Adopt lead bullion anode and lead electrode that lead content is 99%, at 60 DEG C, carry out electrolysis.In the starting stage of electrolysis, we first adopt respectively the constant voltage mode of 0.05V, 0.075V and 0.10V to carry out triphasic continuous electrolysis, and wherein the time of each constant-voltage phase is 1h.This electrolysis is carried out constant-current electrolysis pattern since 3h, and accompanying drawing 2 has shown the groove pressure change curve of this constant-current electrolysis process.Now the current density of lead bullion anode and lead electrode is 300A/m
2.Now the electrolyzer of electrorefining process is pressed and is generally between 0.079-0.152V.We see in electrorefining process, and along with the carrying out of anode electrolysis process in leaching, its surface has accumulated the anode sludge of more indissolubles, has hindered gradually the carrying out of anodic stripping, and the rising that causes electrolyzer to be pressed finally stops in the time that bath voltage is elevated to 0.2-0.3V.Other are with embodiment 2.
Claims (4)
1. a method for refining crude lead, is characterized in that, comprises the following steps:
(1) lead bullion under molten state and be dissolved with in the NaOH fused solution of PbO and carry out redox reaction, makes As, Sb and Sn in lead bullion first be converted into Na
3asO
3, Na
3sbO
3and Na
2snO
2remove as scum silica frost, thereby obtain the lead bullion of pre-removal of impurities;
(2) lead bullion of the pre-removal of impurities of step (1) is cast to positive plate, electrolytic lead or stainless steel are made to negative electrode starting sheet simultaneously, be placed in the NaOH solution that contains PbO, complexing-aid agent and galvanic deposit additive and carry out electrolysis;
(3) make in the lead dissolving galvanic deposit negative electrode starting sheet in lead bullion anode by electrolysis, anode surface has the mud shape metal of indissoluble to generate gradually simultaneously, mud shape metal is the anode sludge, and wherein segment anode mud becomes groove mud because bottom of electrolytic tank is sunk in stirring;
(4) electrolytic lead cathode electrodeposition being obtained carries out obtaining pure lead pig after melting and casting;
In step (2), in electrolyzer, the concentration of electrolytic solution NaOH is 3-11mol/L, and PbO concentration is 0.05-0.55mol/L; In step (3), the electrolysis temperature of electrolyzer is 30-110 DEG C, and the current density of controlling lead bullion anode is 100-1500A/m
2, the current density on corresponding negative electrode starting sheet is 100-1500A/m
2;
The electrolytic process of step (3) adopts multistage continuous constant pressure electrolytic process and constant-current electrolysis process;
The starting stage of electrolysis adopts the constant potential electrolysis pattern of 0.04-0.06V, electrolysis time 1-3h; Adopt the constant potential electrolysis pattern of 0.07-0.08V in the subordinate phase of electrolysis, electrolysis time 1-3h; Phase III in electrolysis is further heightened constant potential electrolysis magnitude of voltage, and controlling constant potential electrolysis voltage is 0.09-0.11V, electrolysis time 1-3h; Proceed to constant-current electrolysis pattern in the fourth stage of electrolysis;
When electrolyte temperature is during in 30-45 DEG C, constant-current electrolysis process adopts 100-300A/m
2current density;
When electrolyte temperature is during in 45-60 DEG C, constant-current electrolysis process adopts 300-750A/m
2current density;
When electrolyte temperature is during in 60-110 DEG C, constant-current electrolysis process adopts 750-1500A/m
2current density.
2. according to the method for claim 1, it is characterized in that, step (1) NaOH dosage is the 1.5-30% of lead bullion weight, and in NaOH, the mass content of PbO is 1-20%, and NaOH molten state is at 400-550 DEG C.
3. according to the method for claim 1, it is characterized in that, the complexing-aid agent in step (2) is a kind of or two kinds of mixtures in ethylene glycol, glycerol, sorbyl alcohol or Xylitol, and the concentration of each complexing-aid agent is 0.1-50g/L.
4. according to the method for claim 1, it is characterized in that, in step (2), each galvanic deposit additive is one or both mixtures in gum resin, trolamine, thionamic acid sodium, methylsulphonic acid lead, sodium lignosulfonate or Dodecyl Dimethyl Amine, and the concentration of each material is 0.1-10g/L.
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| CN103540954B (en) * | 2012-07-13 | 2016-06-08 | 张超 | A kind of electrolytic etching of metal method in basic solution |
| CN103205577A (en) * | 2013-04-12 | 2013-07-17 | 杭州电子科技大学 | Method for extracting and separating lead from waste lead-containing glass |
| WO2015003537A1 (en) * | 2013-07-12 | 2015-01-15 | Zhang Chao | Metal electrolytic method in alkaline solutions |
| CN103510109B (en) * | 2013-10-24 | 2016-03-02 | 北京化工大学 | The method of the leaded grid of waste lead acid battery is reclaimed from gravity contact electricity solution |
| CN105274565A (en) * | 2014-07-18 | 2016-01-27 | 张超 | Method for electrolyzing metals through wet method |
| CN105887138B (en) * | 2016-06-16 | 2018-03-06 | 郴州市金贵银业股份有限公司 | A kind of method of electrorefining processing lead bullion |
| CN108441888A (en) * | 2018-05-15 | 2018-08-24 | 江西理工大学 | A kind of tin electrorefining electrolyte compound additive |
| CN114069060A (en) * | 2021-10-28 | 2022-02-18 | 天能电池集团股份有限公司 | Negative lead paste of valve-regulated lead storage battery, preparation method of negative lead paste and valve-regulated lead storage battery |
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