CN107059053A - A kind of method that electrolyte being electrolysed for lead and its molten lead mend lead - Google Patents
A kind of method that electrolyte being electrolysed for lead and its molten lead mend lead Download PDFInfo
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- CN107059053A CN107059053A CN201710014315.5A CN201710014315A CN107059053A CN 107059053 A CN107059053 A CN 107059053A CN 201710014315 A CN201710014315 A CN 201710014315A CN 107059053 A CN107059053 A CN 107059053A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
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Abstract
Lead method is mended the invention provides a kind of molten lead for the electrolyte being electrolysed for lead, methods described comprises the steps：Molten lead step：Oxidant is added in the silicate fluoride solution equipped with metallic lead, while launching ultrasonic wave, dissolves metallic lead, lead is with Pb2+Form enter silicate fluoride solution；Mend lead step：Pb will be contained again2+Silicate fluoride solution is filled into electrolyte, makes Pb in electrolyte2+Concentration reaches target Pb2+The requirement of concentration.Present invention also offers mend the electrolyte that lead method mend lead using this molten lead.The molten lead of the present invention mend lead method have a wide range of application and molten lead is mended that lead effect is notable, low cost and environmental protection, had no toxic side effect, with extensive commercial value and promotional value.
Description
Technical field
The side of lead is mended the present invention relates to a kind of electrolyte, more particularly to a kind of electrolyte being electrolysed for lead and its molten lead
Method.
Background technology
The technical staff of lead electrolysis industry knows：
1st, newly-built lead electrolysis enterprise or lead electrolysis enterprise increase electrolyte volume newly, it is necessary to newly match somebody with somebody fixture using silicate fluoride solution
There is certain Pb2+The electrolyte of concentration, to meet fluting or increase groove electrolyte use requirement.
2nd, in high miscellaneous chloride plate electrolytic process, because the leaded main grade of positive plate is low, the main grade lead of anode is more 90%
Hereinafter, and the impurity element such as arsenic, antimony, bismuth is too high, electrolysis anode sludge yield is very big, and quality is hard.With the progress of electrolysis, sun
Pole mud layer is gradually thickening and densification, Pb2+Spread difficulty increase so that anodic current efficiency is less than cathode efficiency, causes electricity
Solve the Pb in liquid2+With the progress of electrolysis, Pb2+The continuous dilution of concentration, the rate of dilution is up to more than 3%.
3rd, at higher current densities, when the main grade lead of anode enters quadrat electrolysis less than 98%, because current density is high, anode
Main grade is low so that anodic current efficiency is less than cathode efficiency, causes the Pb in electrolyte2+Concentration is with the progress of electrolysis
Continuous dilution.
Above-mentioned (1), (2) and (3) situation by the external world, it is necessary to fill into Pb into electrolyte2+, it is ensured that Pb in electrolyte2+It is dense
Degree reaches target Pb2+Concentration requirement, makes Pb2+Concentration be in control range in, be ensure cathode lead quality important measures it
One.
At present, the method for lead electrolyte benefit lead has addition oxidant mode in yellow lead benefit lead and electrolyte to mend lead.
When the first, mending lead using yellow lead, yellow lead main component is PbO, and PbO can react with fluosilicic acid, generates PbSiF6,
Its chemical equation is：PbO+H2SiF6=PbSiF6+H2O.Using the method supplement electrolyte Pb2+, mend lead speed fast but yellow
Red reparation technology is complicated, and reparation technology is as shown in Figure 1：
Splicer's skill is mended using yellow lead, there are following five big defects：
1st, producing yellow lead needs very big investment in fixed assets, and operating cost is high, causes electrolyte to mend lead cost high.
2nd, produce yellow lead to carry out at high temperature, lead and lead oxide are volatile, there is environmental pollution in producing process and seriously ask
Topic.
3rd, yellow lead belongs to dangerous waste material, and formality of deals is handled cumbersome.
4th, yellow lead belongs to dangerous waste material, it is necessary to which using the vehicle transport that qualification is transported with dangerous waste, cost of transportation is high and transports
It is defeated to have difficulties；
5th, itself smeltery can not produce yellow lead, it is impossible to reach self-sufficiency, and be made troubles to lead is mended.
CN101906643A discloses a kind of high lead bismuth silver alloy electrolysis deleading process.First to high lead bismuth in anode pot
Silver alloy is pre-processed, and then the high lead bismuth silver alloy of liquation shape is pumped into anode mould and casts positive plate, by preparing
After the electrowinning process of electrolyte and positive plate, cathode sheets in a cell, then it can obtain high-grade precipitation lead and be easy to
The lead anode slurry of processing.The process and condition of supplement silicofluoric acid and yellow lead are disclosed in this article, but uses silicofluoric acid
Carry out carrying out benefit lead to electrolyte with yellow lead, there is the deficiency as above analyzed.
CN103374728A discloses the method that lead electrolytic solution is produced using industrial wastes, is related to chemical technology field.Behaviour
Make step：(1) waste liquid using generations such as the high calcareous fertilisers of industrial production, phosphate fertilizer and anhydrous hydrofluoric acids is raw material；(2) waste liquid raw material enters
Various composition content is chemically examined after factory first, and adds water and is diluted according to hydrofluoric acid in raw material and fluosilicic acid content；(3) basis
Fluohydric acid content adds Cab-O-sil in raw material, while being stirred about 24 hours with 50-100 revs/min of rotating speed；(4) according to original
The harmful element such as sulphur, phosphorus content adds yellow lead powder and carries out stir about 48 hours in material, removes sulfate radical and phosphate radical；(5) such as
There are the complete hydrofluoric acid of unreacted, sulfate radical and phosphate radical etc. in fruit solution, then appropriate quick lime and grass are added according to content
Wood ash is neutralized thoroughly to remove, and is eventually fabricated qualified lead electrolytic solution mother liquor.The present invention solves prior art production lead
There is production cost height in electrolyte, energy resource consumption is high, the problems such as being unfavorable for environmental protection.This utilization industrial wastes production lead electricity
The method of solution liquid is used to make lead electrolytic solution mother liquor, is not directed to molten lead in electrolytic process and mends lead, and using yellow lead powder come
Lead electrolytic solution is made, there is the deficiency as above analyzed.
2nd, lead is mended using addition oxidant mode in electrolyte, then there is oxidant and arsenic, antimony and bismuth etc. in the earth of positive pole are miscellaneous
Qualitative response, causes the concentration impurity ions such as arsenic in electrolyte, antimony and bismuth to raise, and will influence cathode lead quality.
In addition, CN102031383A discloses a kind of lead smelting gas wet processing process, key step includes：Lead smelting gas is broken
Leached after broken, ball milling with watery hydrochloric acid, leachate hydrogenation sodium oxide molybdena hydrolytic precipitation is chlorine oxygen bismuth, and chlorine oxygen bismuth returns bismuth smelting system, water
Liquid waste solution Returning utilization after processing；Leached mud is made the transition with sodium carbonate, and make the transition Mother liquor Returning utilization, and transition slag is molten with silicofluoric acid
Solution, the slag after filtering is the silver-colored slag of richness for being enriched silver, returns silver-colored smelting system, and the silicofluoric acid lead solution of gained returns lead electrolysis and matched somebody with somebody
Liquid.Flow of the present invention is simple, non-environmental-pollution；Fluosilicic lead plumbate is made in lead in lead smelting gas and is used as electrolyte, lead electricity is reduced
The input amount of yellow lead in solution system；Argentiferous can be directly obtained up to more than the 60% silver-colored slag of richness by being dissolved with silicofluoric acid after lead, silver is straight
High income；Whole system solution is recycled, and synthetical recovery degree is high；Processing time is short, and integrated cost is low.This method can
Fluosilicic lead plumbate is made in lead in lead smelting gas and is used as electrolyte, the input amount of yellow lead in lead electrolysis system is reduced, but produce
Fluosilicic lead plumbate is the one of which addition product of this lead smelting gas wet processing process, thus is needed under given conditions
(in the case of having lead smelting gas) makes in this way, and technique is also complex.
The content of the invention
The present invention mends the technological deficiency that the method for lead is present to solve the electrolyte of above-mentioned lead electrolysis of the prior art,
A kind of molten lead for the electrolyte being electrolysed for lead is provided and mends lead method, the simple and environmentally-friendly safety of technique, and mends lead effect significantly, no
Undesired impurities can be produced.
Obtained by a kind of molten lead benefit lead method of electrolyte being electrolysed for lead
The electrolyte being electrolysed for lead.
Lead method is mended the invention provides a kind of molten lead for the electrolyte being electrolysed for lead, methods described includes following steps
Suddenly：Molten lead step：Oxidant is added in the silicate fluoride solution equipped with metallic lead, while launching ultrasonic wave, makes metallic lead
Dissolving, lead is with Pb2+Form enter silicate fluoride solution；Mend lead step：Pb will be contained again2+Silicate fluoride solution is filled into electrolyte, is made
Pb in electrolyte2+Concentration reaches target Pb2+The requirement of concentration.
Invention further provides a kind of electrolyte being electrolysed for lead, using as above any one in the electrolyte
Method described in carries out molten lead and mends lead so that the concentration of the lead ion in electrolyte reaches more than target plumbum ion concentration.
Lead method is mended using the molten lead for the electrolyte being electrolysed provided by the present invention for lead, compared with prior art, had
Following advantage：First, the present invention adds oxidant (oxygen, hydrogen peroxide, air etc.) in the silicate fluoride solution equipped with metallic lead,
Metallic lead is dissolved, belongs to hydrometallurgy, it is environmentally friendly；And metallic lead, investment, operation are dissolved under the conditions of wet method
Cost is low, can reduce the molten lead of electrolyte and mend lead cost；Secondly, oxidant is not directly added into what is be electrolysed for lead by the present invention
Electrolyte, but be first used to oxidant aoxidize the silicate fluoride solution equipped with metallic lead, obtain containing Pb2+Silicate fluoride solution is filled into again
In electrolyte, thus final product quality is had no side effect；Again, using the invigoration effect of ultrasonic wave, produced with oxidant
Synergy, occurs dissolving to metallic lead and obtains Pb2+Course of reaction strengthened, improve reaction efficiency, and metal
The Pb of lead formation2+Ion it is more efficient, after testing, oxidant is added compared to simple, containing Pb2+Pb in silicate fluoride solution2+From
The concentration of son is higher.In addition, metallic lead can just be dissolved in enterprise itself factory building so that the molten lead of electrolyte mends the life of lead
Production. art is simple, tissue is flexible；And this cost that the raw material that molten lead is mended the method for lead and used is carried out to electrolyte is low,
Wide material sources of raw material and reliable, can reduce molten lead and mend lead cost；In a word, molten lead of the invention mends the application of lead method
Wide and molten lead is mended notable lead effect, low cost and environmental protection, had no toxic side effect, with extensive commercial value and promotion price
Value.
Brief description of the drawings
Fig. 1 is the schematic diagram for showing related reparation technology of the prior art.
Embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
It will be apparent to one skilled in the art that needing to fill into Pb into electrolyte by the external world in the case of following three kinds2+, protect
Demonstrate,prove Pb in electrolyte2+Concentration reaches target Pb2+Concentration requirement, makes Pb2+Concentration is in control range：
First, newly-built lead electrolysis enterprise or lead electrolysis enterprise increase electrolyte volume newly, it is necessary to newly be prepared using silicate fluoride solution
With certain Pb2+The electrolyte of concentration, to meet fluting or increase groove electrolyte use requirement.
2nd, in high miscellaneous chloride plate electrolytic process, because the leaded main grade of positive plate is low, the main grade lead of anode is more 90%
Hereinafter, and the impurity element such as arsenic, antimony, bismuth is too high, electrolysis anode sludge yield is very big, and quality is hard.With the progress of electrolysis, sun
Pole mud layer is gradually thickening and densification, Pb2+Spread difficulty increase so that anodic current efficiency is less than cathode efficiency, causes electricity
Solve the Pb in liquid2+With the progress of electrolysis, Pb2+The continuous dilution of concentration, the rate of dilution is up to more than 3%.
3rd, at higher current densities, when the main grade lead of anode enters quadrat electrolysis less than 98%, because current density is high, sun
Extremely main grade is low so that anodic current efficiency is less than cathode efficiency, causes the Pb in electrolyte2+Concentration is entered with electrolysis
The continuous dilution of row.
It is dense when lead ion in above process, it is necessary to detect the content of the lead ion in the electrolyte being electrolysed for lead
When degree is less than the plumbum ion concentration of technological requirement, then need to carry out benefit lead to electrolyte；The purpose of the present invention is that offer one
Planting is used for the molten lead benefit lead method for the electrolyte that lead is electrolysed, and this molten lead mends the simple and environmentally-friendly safety of technique of lead method, and benefit lead
Effect is notable, in the absence of undesired impurities.
The present invention be used for lead be electrolysed electrolyte molten lead mend lead method through the following steps that realize：
Step 1：Molten lead step：Oxidant (oxygen, hydrogen peroxide, air are added in the silicate fluoride solution equipped with metallic lead
Deng), while launching ultrasonic wave, dissolve metallic lead, lead is with lead ion (Pb2+) form enter silicate fluoride solution；
In this step, the silicate fluoride solution can use various silicate fluoride solutions known to those skilled in the art,
In situations where it is preferred, using fluosilicic acid ortho acid, fluorine silicon acid electrolyte, fluorine silicic acid aqueous solution, leaded fluorine-containing silicate aqueous solution
In one or more.
In this step, the metallic lead can use various metallic leads known to those skilled in the art, in order that metal
The cost of lead is lower, cyclic utilization rate is higher, in situations where it is preferred, using the scrap lead in lead smelting process, be electrolysed pure lead,
One or more in the secondary resource of lead.
In this step, the oxidant, which can be used, can be oxidized to metallic lead lead ion (Pb2+) various oxidations
Agent, it is worth mentioning at this point that, the undesirable metal impurities of lead electrolysis system, the meeting such as conventional solid oxidizer such as potassium permanganate
Metal impurities, thus it is not recommended that using, it is preferred to use the not gaseous state or liquid oxidizer of metal ion.In preferred situation
Under, one or more of the oxidant in oxygen, hydrogen peroxide, air are raw after these oxidizing metallic leads
Into H2O, it is ensured that resulting contains Pb2+The purity of silicate fluoride solution is high, impurity is few.
In this step, the process of oxidant is added in the silicate fluoride solution equipped with metallic lead, is specially equipped with gold
Gaseous oxidant is blasted in the silicate fluoride solution for belonging to lead, it is preferred to use oxygen or air；Or add hydrogen peroxide；Wherein, using oxygen
Gas, air are as oxidant, and the mol ratio of oxygen, the addition of air (oxygen-containing tolerance) and metallic lead is 0.5~5:1, it is more excellent
Selection of land, the mol ratio of oxygen, the addition of air (oxygen-containing tolerance) and metallic lead is 1~2:1；Oxidation is used as according to hydrogen peroxide
Agent, then H in hydrogen peroxide2O2Addition and metallic lead mol ratio be 1~2:1.Using preferred oxidant and its in preferred model
Interior content is enclosed, the solute effect of lead oxide is enabled to more preferably so that can be with Pb after metallic lead dissolving2+Form enter fluorine
Silicate solution.Then, metallic lead dissolves, and lead is with Pb2+Form enter silicate fluoride solution.
In this step, oxidant is added in the silicate fluoride solution equipped with metallic lead, while launch ultrasonic wave, compared to
It is simple to add oxidant, being capable of the efficiency that dissolves of reinforced metal lead by the synergy of oxidant and ultrasonic wave so that
Metallic lead generation lead ion Pb2+It is more efficient, reaction speed is faster.For from principle, ultrasound-enhanced heterogeneous reaction is first
It is its mechanism.The pressure of change is produced when ultrasonic wave is propagated in a liquid with strong agitation solution, so as to significantly reduce
External diffusion resistance；And at heterogeneity (solid phase particle surface), there is fracture in hole or bubble in liquid.Because external pressure with
Acoustic pressure is acted in the same direction, and microbubble will be compressed into several kilo-atmospheric pressures, subsequent rapid expansion and produce huge impact
Ripple.The latter not only triggers strong vortex flow and eliminates diffusional resistance, also produces destruction to solid phase particle, that is, removes its table
Facial mask, the micro-porosity and degree of grinding for increasing superficial layer, and substantially reduce inside diffusional resistance.Powerful shock wave can also be destroyed
Change superficial layer crystal structure, generation and accumulation fault of construction, so as to improve reaction equilibrium constant and reduction reaction activity.This
Outside, the phonolysis of aqueous medium can also occur in the hole in ultrasound field, thus some oxidation-reduction reactions can be influenceed.
In a word, ultrasound has huge invigoration effect to the hydrometallurgy heterogeneous reaction of external diffusion, interior diffusion control；To in power school district
Heterogeneous reaction also have certain facilitation effect, so as to promote metallic lead be oxidized dissolving, generate Pb2+, and with Pb2+'s
Form enters silicate fluoride solution.In the present invention, transmitting ultrasonic wave can be using the supersonic generator bought on the market, at this
In invention, control the frequency of ultrasonic wave between 20kHz~105kHz, the application time of ultrasonic wave is between 30min~3h.Control
The frequency and application time of ultrasonic wave processed can keep metallic lead to generate lead ion Pb in the range of2+The carry out speed of reaction and
Efficiency.
Step 2：Mend lead step：Pb will be contained again2+Silicate fluoride solution is filled into electrolyte, makes Pb in electrolyte2+Concentration reaches
Target Pb2+Concentration requirement, so as to ensure fluting work, increase groove work, high miscellaneous chloride plate electrolysis and the electrolysis of high current density lead
Be smoothed out.
In this step, because lead electrolysis is normal temperature electrolysis, general electrolyte system temperature control is between 20~35 DEG C
Carry out, thus Pb will be contained2+Silicate fluoride solution fills into electrolyte, and solution temperature control when noting filling into is normal temperature, and normal temperature is also named
General temperature or room temperature, are commonly defined as 25 DEG C；In the present invention, the temperature range of normal temperature allows between 10~35 DEG C,
Between preferably 20~35 DEG C.Make Pb in electrolyte2+Concentration reaches target Pb2+Concentration requirement, it is ensured that fluting work, increasing groove work
What work, high miscellaneous chloride plate electrolysis and high current density lead were electrolysed is smoothed out.
Prepare electrolyte first to newly-built lead electrolysis enterprise or lead electrolysis enterprise increases electrolyte volume newly, it is necessary to which new prepare
Target Pb2+The electrolyte of concentration；Using the method for the present invention, Pb will be contained2+Silicate fluoride solution is filled into electrolyte, reaches preparation
Target Pb2+The purpose of the electrolyte of concentration.Mending lead method using this molten lead replaces traditional use yellow lead to prepare electrolyte side
Formula, the simple and environmentally-friendly safety of technique, and mend lead effect significantly, with good economic value.
In the method for the invention, it is necessary to according to Pb in the lead electrolytic solution (mended before implementation before lead)2+Concentration, electrolytic process are poor
The Pb of rate, target electrolyte2+The factors such as concentration, electrolyte volume, determine the addition of high lead silicate fluoride solution, then determine to need
The amount of metallic lead is dissolved, to ensure Pb in electrolyte2+Concentration and electrolyte cumulative volume keep balance.Using the molten lead of the present invention
Mend lead method and replace Pb in traditional use yellow lead supplement electrolyte2+Method, be simple and convenient to operate with technique, effect show
The advantages of work.
In summary, using technical scheme, compared with prior art, have the following advantages that：First, it is of the invention
Oxidant (oxygen, hydrogen peroxide, air etc.) is added in the silicate fluoride solution equipped with metallic lead, metallic lead is dissolved, belonged to
It is environmentally friendly in hydrometallurgy；And metallic lead is dissolved under the conditions of wet method, investment, operating cost are low, can reduce electrolysis
The molten lead of liquid mends lead cost；Secondly, oxidant is not directly added into the electrolyte being electrolysed for lead by the present invention, but first will oxidation
Agent is used to aoxidize the silicate fluoride solution equipped with metallic lead, obtains containing Pb2+Silicate fluoride solution is filled into electrolyte again, thus to final
Product quality have no side effect；In addition, metallic lead can just be dissolved in enterprise itself factory building so that the molten lead of electrolyte is mended
The simple production process of lead, tissue are flexible；And it is this that molten the lead method for mending lead and the raw material used are carried out to electrolyte
Cost is low, wide material sources of raw material and reliable, can reduce molten lead and mend lead cost；In a word, it is of the invention to have a wide range of application and molten
Lead is mended notable lead effect, low cost and environmental protection, had no toxic side effect, thus with extensive commercial value and promotional value.
The present invention will be described in further detail by embodiment below.
Embodiment 1：
Embodiment 1 is used to illustrate that newly-built lead electrolysis enterprise is used containing Pb2+Silicate fluoride solution newly prepare have certain Pb2+
The electrolyte of concentration, to meet the requirement of fluting, specific implementation process is：
Certain newly-built lead smeltery, electrolysis is slotted, it is necessary to newly configure electrolyte volume 1000m first3, bath composition is
H2SiF6 88g/L、Pb2+90g/L, total fluosilicic acid 150g/L；
Oxidant is added in the silicate fluoride solution equipped with metallic lead, metallic lead is dissolved, lead is with Pb2+Form enter
Enter silicate fluoride solution；Wherein,
Silicate fluoride solution composition is fluosilicic acid 550g/L, then preparing electrolyte needs fluosilicic acid volume to be 273m3(1000m3
In total fluosilicic acid 150g/L, then fluosilicic acid amount is that fluosilicic acid content is 550g/L in 150t, fluosilicic acid ortho acid in this solution, then needs
It is 150t/0.55=272.7 ≈ 273m to want fluosilicic acid volume3)。
Pb in electrolyte2+Concentration is 90g/L, electrolyte volume 1000m3Metallic lead 90t is needed, then oxidant dissolving metal
Lead weight is 90t.According to air or oxygen as oxidant, oxygen content and the mol ratio of metallic lead are in oxygen or air
0.5~5:1, thus need to add in air or oxygen containing O2Measure as 6.95t~34.75t；It is oxidant according to hydrogen peroxide,
H in hydrogen peroxide2O2Addition and metallic lead mol ratio be 1~2:1, then contain H in hydrogen peroxide2O2Addition be 0.16t~
0.32t。
Ultrasound is launched to (silicate fluoride solution of the reaction vessel built with metallic lead) in reaction vessel simultaneously in implementation process
Ripple, the FREQUENCY CONTROL of ultrasonic wave is between 20kHz~105kHz, and the application time of ultrasonic wave is controlled between 30min~3h.
Embodiment 2：
Embodiment 2 is for illustrating in high miscellaneous chloride plate electrolytic process, the Pb in electrolyte2+With the progress of electrolysis, Pb2 +The continuous dilution of concentration, thus need to carry out electrolyte in molten lead benefit lead, specific implementation process is：
In certain lead smeltery, high miscellaneous chloride plate electrolysis output electricity lead 3000t/a (ton/year), electrolytic process, electrolyte lead
The rate of dilution is 3%, and fluosilicic acid consumption is the electric lead of 20kg/t-；
Oxidant is added in the silicate fluoride solution equipped with metallic lead, metallic lead is dissolved, lead is with Pb2+Form enter
Enter silicate fluoride solution, then Pb will be contained2+Silicate fluoride solution is filled into electrolyte, makes Pb in electrolyte2+Concentration reaches target Pb2+It is dense
The requirement of degree；Wherein,
Silicate fluoride solution composition is fluosilicic acid 550g/L, density 1.41kg/L, then consumes fluosilicic acid weight and volume difference
For 60t/a (ton/year) and 42.55m3/ a (cubic meter/year)；(3000t/a electricity lead yield, the electric lead of fluosilicic acid consumption 20kg/t-,
Then consumption fluosilicic acid weight is 3000*0.02=60t/a；Volume=60/1.41=42.55m3/a).
Electrolyte needs metallic lead 90t, then oxidant dissolving metallic lead weight is 90t/a (ton/year).According to air or
Oxygen is as oxidant, and oxygen content and the mol ratio of metallic lead are 0.5~5 in oxygen or air:1, it is necessary to add air or oxygen
Contain O in gas2Measure as 6.95t~34.75t；It is oxidant according to hydrogen peroxide, H in hydrogen peroxide2O2Addition and metallic lead
Mol ratio is 1~2:1, then contain H in hydrogen peroxide2O2Addition is 0.16t~0.32t.
Ultrasound is launched to (silicate fluoride solution of the reaction vessel built with metallic lead) in reaction vessel simultaneously in implementation process
Ripple, the FREQUENCY CONTROL of ultrasonic wave is between 20kHz~105kHz, and the application time of ultrasonic wave is controlled between 30min~3h.
Embodiment 3：
Embodiment 3 is used to illustrate that lead electrolysis enterprise increases electrolyte volume newly and used containing Pb2+Silicate fluoride solution newly match somebody with somebody fixture
There is certain Pb2+The electrolyte of concentration, to meet the requirement for increasing groove, specific implementation process is：
Certain lead smeltery, electrolysis system needs to increase electrolysis slot number, it is necessary to newly configure electrolyte volume 500m3, electrolyte
Composition is H2SiF6 88g/L、Pb2+90g/L, total fluosilicic acid 150g/L；
Oxidant is added in the silicate fluoride solution equipped with metallic lead, metallic lead is dissolved, lead is with Pb2+Form enter
Enter silicate fluoride solution；Wherein,
Silicate fluoride solution composition is fluosilicic acid 550g/L, then preparing electrolyte needs fluosilicic acid volume to be 136m3；
Pb in electrolyte2+Concentration is 90g/L, electrolyte volume 500m3Metallic lead 45t is needed, then oxidant dissolving metal
Lead weight is 45t.According to air or oxygen as oxidant, oxygen content and the mol ratio of metallic lead are in oxygen or air
0.5~5:1, thus need to add in air or oxygen containing O2Measure as 3.48t~17.38t；It is oxidant according to hydrogen peroxide,
H in hydrogen peroxide2O2Addition and metallic lead mol ratio be 1~2:1, then contain H in hydrogen peroxide2O2Addition be 0.08t~
0.16t。
Ultrasound is launched to (silicate fluoride solution of the reaction vessel built with metallic lead) in reaction vessel simultaneously in implementation process
Ripple, the FREQUENCY CONTROL of ultrasonic wave is between 20kHz~105kHz, and the application time of ultrasonic wave is controlled between 30min~3h.
The evaluation of above-described embodiment 1~3：
Embodiments of the invention 1~3 add oxidant (oxygen, hydrogen peroxide, sky in the silicate fluoride solution equipped with metallic lead
Gas etc.), dissolve metallic lead, so as to supplement lead ion, implementation result has：
First, it is environmentally friendly the invention belongs to hydrometallurgy；And metallic lead, reduced investment, fortune are dissolved under the conditions of wet method
Row cost is low, and the molten lead of reduction electrolyte mends lead cost；
2nd, metallic lead can just be dissolved in enterprise itself factory building so that the molten lead of electrolyte mends the production technology of lead
Simply, organize flexible；And this cost that the raw material that molten lead is mended the method for lead and used is carried out to electrolyte is low, raw material
Wide material sources and reliable, can reduce molten lead and mend lead cost；
The 3rd, oxidant is not directly added into the electrolyte being electrolysed for lead, but is first used to oxidant aoxidize equipped with gold
Belong to the silicate fluoride solution of lead, obtain containing Pb2+Silicate fluoride solution is filled into electrolyte again, thus product quality is had no side effect, production
Go out product and can reach GB/T 469-2013《Lead pig》The trade mark is the quality requirements of 99.994% lead pig in standard；Molten lead mends lead effect
Fruit is notable, with higher practical value.
4th, using the invigoration effect of ultrasonic wave, synergy is produced with oxidant, occurring dissolving to metallic lead obtains Pb2+
Course of reaction strengthened, improve reaction efficiency, and the Pb of metallic lead formation2+Ion it is more efficient, after testing,
Oxidant is added compared to simple, containing Pb2+Pb in silicate fluoride solution2+The concentration of ion is higher.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (9)
1. a kind of molten lead for the electrolyte being electrolysed for lead mends lead method, it is characterised in that methods described comprises the steps：
Molten lead step：Oxidant is added in the silicate fluoride solution equipped with metallic lead, while launching ultrasonic wave, makes metallic lead
Dissolving, lead is with Pb2+Form enter silicate fluoride solution；
Mend lead step：Pb will be contained again2+Silicate fluoride solution is filled into electrolyte, makes Pb in electrolyte2+Concentration reaches target Pb2+It is dense
The requirement of degree.
2. according to the method described in claim 1, it is characterised in that the oxidant in oxygen, hydrogen peroxide, air one
Plant or several.
3. method according to claim 1 or 2, it is characterised in that oxygen is added in the silicate fluoride solution equipped with metallic lead
The process of agent is：Gaseous oxidant is blasted in the silicate fluoride solution equipped with metallic lead or hydrogen peroxide is added.
4. method according to claim 3, it is characterised in that the gaseous oxidant uses oxygen or air, oxygen or
Oxygen content and the mol ratio of metallic lead are 0.5~5 in air:1；The oxidant uses H in hydrogen peroxide, hydrogen peroxide2O2Addition
Amount and the mol ratio of metallic lead are 1~2:1.
5. according to the method described in claim 1, it is characterised in that the frequency of the ultrasonic wave between 20kHz~105kHz,
The application time of ultrasonic wave is between 30min~3h.
6. according to the method described in claim 1, it is characterised in that the silicate fluoride solution uses fluosilicic acid ortho acid, fluorine silicon
One or more in acid electrolyte, fluorine silicic acid aqueous solution, leaded fluorine-containing silicate aqueous solution.
7. according to the method described in claim 1, it is characterised in that the metallic lead use scrap lead in lead smelting process,
It is electrolysed the one or more in the secondary resource of pure lead, lead.
8. according to the method described in claim 1, it is characterised in that Pb will be contained2+Silicate fluoride solution is filled into electrolyte, described to contain
Pb2+The temperature of silicate fluoride solution is 20~35 DEG C.
9. a kind of electrolyte being electrolysed for lead, it is characterised in that used in the electrolyte as claim 1~8 is any
Method described in one carries out molten lead and mends lead so that the concentration of the lead ion in electrolyte reaches more than target plumbum ion concentration.
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| CN116443884A (en) * | 2023-06-07 | 2023-07-18 | 内蒙古星汉新材料有限公司 | Byproduct fluosilicic acid impurity removal process and potassium fluoride preparation method |
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