CN1274885C - Technique for electrolyzing slurry of fluosilicic acid in bismuth mine - Google Patents
Technique for electrolyzing slurry of fluosilicic acid in bismuth mine Download PDFInfo
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Abstract
The present invention relates to a technique for electrolyzing slurry of fluosilicic acid in bismuth ore. Bismuth ore concentrate serves as an ore slurry raw material and enters a pulp tank; after the bismuth ore concentrate is pulped, hydrochloric acid is added, and acidity is regulated; then, the slurry continuously enters an ore slurry electrolytic tank, and under the function of a direct current energized to the electrolytic tank, the leaching and the electrolysis of bismuth are completed. After electrolysis, bismuth powder is separated at the cathode and falls into the bottom of a membrane bag. The bismuth powder is pressed in a sponge bismuth filter press by a powder drawing device, and a sponge bismuth pressing block is dewatered and smelted to metal coarse bismuth. The high purity bismuth with the finally content of 99.999% is obtained through the passing of chlorine gas and sodium hydroxide for removing impurities and refining. The technology is mainly used for bismuth smelting from inferior bismuth raw materials, such as a material containing bismuth sulfide or bismuth trioxide or low grade secondary bismuth, etc. Compared with the existing methods of melting bismuth in a pyrogenic method, an ore slurry electrolytic technology of a hydrochloric acid system, etc., the technique has the advantages of low cost, low energy consumption, high production quality, simple process, less pollution and very obvious economical and social benefit.
Description
Technical field
The present invention relates to the method for refining of bismuth; Relate in particular to a kind of bismuth mineral silicofluoric acid in-pulp electrolysis technology.
Background technology
Bismuth is in the 5th family of the periodic table of elements, and its chemical atomic weight is 208.9804, and out-shell electron is 6S
26P
3, being usually expressed as+3 valencys and+5 valencys, a few cases shows as+divalent ,+1 valency ,-3 valencys and-1 valency; Bismuth metal be the glossy solid of silver gray, property crisp, easily broken, matter is hard.Proportion is 9.78, is dissolved in rare HNO
3, hot H
2SO
4And concentrated hydrochloric acid.Scientist Georgius Agricoq has noticed the existence of bismuth at first from the melt of ore.But,, confirm that just bismuth is a kind of element up to the smelting that bismuth was arranged in 18th century.In a last century, people have found that first bismuth compound has analgesic activity to stomach trouble.So far, bismuth compound still is widely used in treating stomach trouble.
Bismuth normally with the symbiotic a kind of elements in ore deposit such as zinc, silver, lead, tin, belong to rare elements, itself does not have extraction value.China is bismuth big producing country in the world, mainly reclaims from the byproduct of plumbous zinc ore and copper mine, also can be recovered to bismuth in the tin ore.The geographic secret mineral amount in Chenzhou, China Hunan is good, of high grade only in the world, and itself has extraction value.Bismuth is few in the nature storage, and the about mean value of the concentration in the earth's crust is 0.1ppm, has only the higher 0.5-24ppm of bismuth-containing amount in the manganese ore orbicule of ocean, and tool is silicite, content 0.2-0.9ppm.At present, the year of world market bismuth ingot in large supplyly is about 7000 tons.Wherein, 3000 tons of Asia supplys, 1000 tons in Mexico, 2000 tons in Britain, 1000 tons in Canada.About 7.5 ten thousand yuan/ton of the bismuth prices of content 99.99%.About 2000 tons of China's annual production, our province output accounts for more than 1000 ton, wherein: more than 300 ton of persimmon bamboo plantation, more than 300 ton of Zixing, more than 500 ton in Chenzhou, exhausted most product deep processing for export, high value added product is less.
Bismuth has four kinds of forms: bulk, needle-like, coccoid, powdery.Bulk is generally the 4.5-13.6kg/ piece, mainly is used as alloy addition.Needle-like diameter 0.16cm, long 2.54cm is mainly used in and produces bismuth class medicine and make catalyzer.Powdery has various sieve mesh, is mainly used in electronic industry.The common 4.5-60 gram/ball of spherical bismuth is used for metallurgical addition agent.The U.S. is the main body entrance state of bismuth, and more than 1600 ton of annual import is mainly from Peru, Belgium, France and Britain's import.Secondly also have from Britain, China, Canada, French import.Since the seventies, the price of world market bismuth is from minimum fluctuation 4.4 dollars/kilogram to the highest 44 dollars/kilogram.The bismuth of the U.S. 90% is used for medicine before the thirties, opens up many new purposes after the seventies.As industrial, manufacturing compound, metallurgical addition agent, alloy etc.Pharmaceutical bismuth only accounts for about 50%.The beginning of the nineties, the alloy bismuth accounted for 10%, and the pharmaceutical purpose bismuth drops to 20%.
The main application of China's bismuth metal is to do the Western medicine product, occupancy 60-70%.Next is alloy, electronic product etc.In recent years, the research and development to the bismuth series products have abroad given to show great attention to, and the article of delivering every year reaches hundred pieces, and content relates to manufacturing, production, deep processing and application etc.Inorganic and the bismuth organic compound of some novel types, new texture is synthesized out, and beginning puts it in every field.Especially technical popularization makes bismuth become the focus of research, has obtained important breakthrough.The application of estimating bismuth compound will make the use value of bismuth rise to a new high degree.
The production technology comparative maturity of external bismuth metal, bismuth compounds kind is more, and Application Areas is wider, and use value is higher.Wherein the main production method of bismuth metal has three kinds:
A, Bettertan-Kroll method
Calcium metal and magnesium are added in the lead of fusing, form quaternary compound, this quaternary compound fusing point is higher than the temperature of plumbous fusing point.The higher metal mixture bismuth magnesium calcium of bi content just is cured, and is suspended in can take out above plumbous.Also contain lead in the bismuth magnesium calcium emersion thing, must remove, its way is with emersion thing reheat, the lead that dissociates, and then separate, this part lead circulates again and is used for the separation of bismuth.The bismuth magnesium calcium cpd that obtains is handled with chlorine or lead chloride, removes bismuth, lead alloy that calcium magnesium generates again; Bi content is the highest in bismuth, the lead alloy, treated again generation finishing metal bismuth.
In United States Patent (USP) NO5041160, narrated the above-mentioned bismuth method of taking off.It's a pity that this takes off bismuth emersion thing and comprises a large amount of lead,, all must from the emersion thing, reclaim lead and bismuth for environmental protection and consideration economically.Calculate by weight, typical emersion thing contains the 3-6% bismuth of having an appointment, 0.4-1.5% calcium and 1-2% magnesium, and all the other are plumbous basically.By a series of deleading operations, can realize bismuth and plumbous separating and recovery basically, and can to increase the bi content that is retained in the emersion material be pure bismuth up to obtaining basically with the slag form.
Pointed out a kind of method that reclaims bismuth from take off the bismuth scum silica frost in United States Patent (USP) NO4039322, it is to make solid-state alkalescence take off bismuthide by vacuum filtration directly to separate with fusion of lead.This method can increase the bismuthide concentration in the emersion thing, and can reduce the quantity of the lead that must remove in refining procedure subsequently.
A kind of commercial run of handling the emersion thing is at first to remove calcium and magnesium (being commonly referred to concentrated scum silica frost), then to the capable halogenation of this concentrated emersion thing to generate PbCl
2Slag.Continuing above-mentioned processing is pure bismuth up to obtaining basically.Remove before calcium and the magnesium carrying out halogenation, usually PbCl
2Slag will carry out the processing that recirculation participates in the emersion thing, this molten slag be used to handle in the skimming operation, obtain take off bismuth lead.
Pointed out that in United States Patent (USP) NO2955931 a kind of refining takes off the method for bismuth scum silica frost.Usually, this basic skills is an emersion thing concentrated and that fusing obtains according to currently known methods, and to produce the product of a kind of 25-40% of containing (weight) bismuth, calcium and magnesium are removed with emersion thing form simultaneously.Then this product being carried out cupellation (cupelled) handles so that the bi content of emersion thing is increased to about 50-60% (weight) scope.If bi content surpasses above-mentioned level, then use this emersion thing of chlorine halogenation to remove left lead, and stay purer bismuth product relatively with the form of lead chloride.
In the improving one's methods of people such as Ftores, keep finishing halogenation in the melt more than 85% by bi content wherein and improve the halogenation rate.Said process is finished by the following method, promptly uses the high lead alloy molten bath of bismuth-containing amount, and add emersion thing (50-65%) that bismuth-containing amount and ratio are lower level during the halogenating reaction so that all the bi content of melts remain on more than 85%.
Though the method for above-mentioned refining bismuth can be produced a kind of high purity bismuth product, but still need from original feed, reclaim the rate of recovery of bismuth and the output of bismuth product with raising by quickening separating reaction and making the bismuth amount of taking away in the deslagging operation reduce to minimum.And above-mentioned method is not suitable for the bismuth concentrate and directly smelts.
B, thermal process
By the thick bismuth that extracts in the copper metallurgy flue dust, adopt thermal process to purify and produce smart bismuth, its technology is summarized as follows: copper metallurgy flue dust leached mud, make the pelletizing melting, extract lead bullion. lead bullion is made the electrolysis lead bullion through electrolysis, in the anode sludge that stays in the electrolytic process enrichment bismuth element.After anode sludge water cleaned, adding temperature was 400 ℃, and molten sodium hydroxide is pulled alkaline residue subsequently out, makes the thick bismuth of bismuth-containing more than 70%.Thick bismuth fusing also is warming up to 680～720 ℃, adds sulphur, removes and gets copper; Be cooled to 500～550 ℃ of hydro-oxidation sodium, remove and get arsenic, tellurium element; Be cooled to 350-400 ℃ again, feed the chlorine deleading, after be warmed up to 450-520 ℃, pull the chlorination lead skim out; Continue to be warmed up to 680-720 ℃, the chlorine in the solution is overflowed; Be cooled to 480-550 ℃ again, the zincification desilver; Continue to be cooled to 320-940 ℃, feed chlorine, remove entrapped zinc, condensation makes the smart bismuth of solid then.
Pyrogenic process is produced smart bismuth complex process, and service temperature lifting repeatedly, and power consumption is high, and technology divides folding frequent.Particularly need secondary to feed chlorine, contaminate environment, operational condition is abominable.
C, electrolytic purification technology
The design that Chinese patent publication number CN1031117A discloses " a kind of technology of thick bismuth refining " its invention is: bi content is that the thick bismuth of 70-95% is removed antimony element through the sodium hydroxide melt compounded, the thick bismuth ingot that is cast into definite shape is as electrolytic anode, negative electrode adopts graphite, and perhaps smart bismuth is a material.Electrolytic anode, negative electrode are positioned over electrolyzer by certain position and interval. electrolytic solution is the acid bismuth-containing aqueous solution, and wherein the concentration of bismuth is 3.0～7.2 mol, and the concentration of acid is 3.6～6 mol.Electrolytic process parameter is: volts DS 0.10～0.26V, current density 150～250A/m
2, strength of current 15～45A.
To regularly measure the bi content of bismuth in the electrolytic solution during above-mentioned technology electrolysis, stir electrolytic solution, in time regulate strength of current, otherwise be difficult to control electrolysis process.Must do thick bismuth ingot earlier before the electrolysis, so complicated operation, efficient is not high.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, propose a kind of easy and simple to handlely, it is low, free of contamination to consume energy, and can directly use the bismuth mineral silicofluoric acid in-pulp electrolysis technology of bismuth concentrate as raw material.
To achieve these goals, a kind of bismuth mineral in-pulp electrolysis technology of the present invention's design, it is characterized in that: the bismuth concentrate that contains bismuth sulfide or oxidation bismuth mineral or low-quality secondary bismuth material enters the pulp groove as raw material of ore, after pulp adds the hydrochloric acid acid adjustment, guarantee that bi content is 1.8～16.8 mol in the slurries, acid content is 3.5～9 mol, and above-mentioned slurries are entered the in-pulp electrolysis groove continuously, and ionogen is plumbous silicofluoride solution PbSiF
6With silicofluoric acid H
2SiF
6, make negative electrode with the pure stereotype that diaphragm bag is housed, more than 90%, the casting stereotype of stanniferous below 0.001% made anode with leaded, and feeding voltage at electrolyzer is 3.10～4.25V, and current density is 130～250A/m
2The direct current effect under finish the leaching and the electrolysis of bismuth simultaneously, and stir on electrolysis limit in limit in the electrolytic process, negative electrode after the electrolysis is separated out bismuth meal and is the spongy diaphragm bag bottom that falls into, dependence is taken out the powder device and is pressed into the sponge bismuth pressure filter, pressure filter is dehydrated into filter cake briquetting dehydration back retailoring with sponge bismuth briquetting and becomes the thick bismuth of the high metal of bismuth-containing, through logical chlorine, it is 99.999% high purity bismuth that the sodium hydroxide impurity removing refining becomes final content, ore pulp after above-mentioned electrolyzer leaches injects the filtration washing pond through acid proof pump and filters, the leached mud that washing and filtering goes out is stored up with special-purpose place and is done comprehensive reclaimed materials processing, leach liquor returns the pulp groove and recycles, sedimentary a small amount of spongy bismuth meal also is pressed into the sponge bismuth pressure filter with taking out the powder device in the filtration washing pond simultaneously, the a spot of leach liquor of regular discharge in the above-mentioned electrolytic process forms calcium scum and discharge of wastewater after the lime neutralizing treatment is up to standard.
Methods such as the present invention and existing pyrogenic process refining bismuth and hydrochloric acid system in-pulp electrolysis technology relatively have following advantage:
A, the invention solves adaptability problem to bismuth mineral material (as leaded bismuth raw material), especially make unmanageable complicated bismuth mineral raw material, the electrolysis treatment of low-grade bismuth-containing material becomes possibility, thereby made full use of resource, reduce cost greatly and energy consumption, increase substantially metal recovery rate, the quality product height is for condition has been created in the production of high purity bismuth.So putting forward the bismuth novel process, the in-pulp electrolysis of silicofluoric acid system belongs to initiative both at home and abroad.
B, the present invention have finished type approval test, compare with the domestic and international existing bismuth technology of smelting, and it is simple to have flow process, and this device structure is simplified, and it is reliable to turn round, and the technico-economical comparison advanced person pollutes and lacks, and overall technology is on the leading domestic level, and reaches advanced world standards.
C, practicality of the present invention are very strong, are fit to handle unmanageable low-grade bismuth mineral raw material and bismuth-containing material, and pollute fewly, and economic benefit and social benefit are very remarkable.
D, flow process closed cycle of the present invention, three waste discharge seldom belong to the clean environment firendly production technique.
E, the present invention are with a wide range of applications, can handle bismuth raw material inferior on the one hand, subsequent process can be produced high-purity smart bismuth on the other hand, provides reliable high-quality technology basic substance for developing high-tech industries such as high-grade medicine industry, space industry, superconductor technology, electronic material.
Description of drawings
Accompanying drawing 1 is process flow sheet of the present invention.
Embodiment
Following embodiment will be done further the present invention and describe in detail:
Present embodiment is an example with plump smeltery, Xu Jia hole, factory that this project is total and power supply chamber floor area of building 1000m
2, power supply is a 500KVA transformer.
The major equipment that present embodiment is used is chosen as:
1, in-pulp electrolysis pulp groove
Select Φ 1500 * 2000mm (V
Liquid=3.5m
3) 2 of pulp grooves, power of motor 2.2kw * 2=4.4kw, material is the steel acid resisting brick.
2, in-pulp electrolysis groove
The in-pulp electrolysis groove is of a size of 2000 * 1500 * 1750mm, and direct current strength of current 2700A, electrolysis time are 1.25 times of the theoretical electrolysis time of bismuth, so handle concentrate amount 2700 * 2.6 ÷ 100 * 22 ÷ 1.25 ÷ 20%=618kg/d grooves single groove day; In-pulp electrolysis groove platform number: 7.41 * 2252 ÷ 618=18 platforms, divide three rows, 9 electrolyzer series connection of every row.Every in-pulp electrolysis groove power of agitator is got 2.2kw, totally 2.2 * 18=39.6kw, and the cell body material is a Steel Concrete lining acid resisting brick.
3, rectifier
Rated current-2700 ÷ 90%=3000A, bath voltage=(3.5+0.5) * and 12=48V, select one of silicon-controlled rectifier GHS-3000A/60V.
4, sponge bismuth pressure filter
Filter cake volume: 7.41 ÷ 3=2.47L/ time (3 times/d), select 6 of XA20/800-U chamber-type press filters, F=20m
3/ platform, power of motor 1.5kw * 2=3kw, material PP.
5, middle steel basin
The residence time got 4 hours, then: V slurry: 1.28 * 2 * 4=10.24m
3/ groove.Select Φ 2500X2500mm
3Platform, power of motor 5.5kw. material is the steel lining acid resisting brick.
6, water consumption and water supply standard
The water of productive use water quality requirement is not high, and domestic water is by 30L/ people class, and shower water is by 60L/ people class.Water supply pressure requires 0.3Mpa.Project water consumption 40.2m
3/ d.
7, draining
The water yield of production draining deduction in-pulp electrolysis evaporation, project are produced water displacement 10.5m every day
3, maximum hour water displacement 8.1m
3/ h, metallic impurity such as Bi, Pb, Cu in the waste water of discharging, qualified discharge in lime and after the sedimentation.Living drainage 3.0m
3/ d can directly discharge.
8, heat supply and fuel oil storage tank
This project factory long-term temperature in location is higher, and slurry electrolysis process of complex antimony self can be kept electrolyte temperature 50-60 ℃ in the production, does not need outer heating.Select the worker's shower of holding office of one of 0.2t/h hot water boiler to use.
Produce consumption coal 1000Kg/tBi, be mainly used in the refining heating, the rotary furnace smelting burning heavy oil, total year expendable weight oil mass of project is 360t, selects 15m
3Two in oil tank is used the toothed gear pump fuel feeding.
9, ventilation and air compressor machine
The in-pulp electrolysis factory building is provided with windproof skylight, adopts natural ventilation system to get rid of factory building interior steam and acid mist.The rotary furnace smelting flue gas adopts wet dust collection, dedusting cooling back discharging.The width of cloth for rotary furnace smelting and refining generation is penetrated heat, adopts the local forced ventilation heat radiation of factory building natural ventilation and exhaust fan.The a small amount of chlorine contained exhaust gas that produces during refining adopts the dechlorination back discharging of alkali lye absorption tower.
Leached mud filters and sponge bismuth is filtered and need be dried up filter cake by pressurized air, and tolerance is little, selects 3 of ZW-3/8 type air compressor machines, should build the pneumatics machine room and carry out the insulating noise processing.
The technical scheme of present embodiment
Raw material bismuth concentrate mainly is made up of bismuthinite and pyrite, according to mineralogical property, by commerical test and draw thick bismuth rendering industry knowhow and use for reference lead bullion rotary furnace smelting technology, determine the technical process of this project, embodiment is: the pulp groove that the bismuth concentrate is entered Φ 1500X2000mm as raw material of ore, after pulp adds the hydrochloric acid acid adjustment, guarantee that bi content is 1.8～16.8 mol in the slurries, acid content is 3.5～9 mol, above-mentioned slurries are entered continuously the in-pulp electrolysis groove of 2000 * 1500 * 1750mm, ionogen is plumbous silicofluoride solution PbSiF6 and silicofluoric acid H2SiF6, make negative electrode with the pure stereotype that diaphragm bag is housed, more than 90%, the casting stereotype of stanniferous below 0.001% made anode with leaded.Adjust silicon-controlled rectifier GHS-3000A/60V, making it feed voltage at electrolyzer is 3.5-4.0vV, and current density is 150A/m
2The direct current effect under finish the leaching and the electrolysis of bismuth simultaneously, and use the middle agitator of power of motor 5.5kw in the electrolytic process, stir on electrolysis limit, limit, negative electrode after the electrolysis is separated out bismuth meal and is the spongy diaphragm bag bottom that falls into, be pressed into the XA20/800-U chamber-type press filter by taking out the powder device, pressure filter is dehydrated into filter cake briquetting dehydration back retailoring with sponge bismuth briquetting and becomes the thick bismuth of the high metal of bismuth-containing, and becoming final content through logical chlorine, sodium hydroxide impurity removing refining is 99.999% high purity bismuth.Ore pulp after above-mentioned electrolyzer leaches injects the filtration washing pond through acid proof pump and filters, the leached mud that washing and filtering goes out is stored up with special-purpose place and is done comprehensive reclaimed materials processing, leach liquor returns the pulp groove and recycles, sedimentary a small amount of spongy bismuth meal also is pressed into the sponge bismuth pressure filter with taking out the powder device in the filtration washing pond simultaneously, the a spot of leach liquor of regular discharge in the above-mentioned electrolytic process forms calcium scum and discharge of wastewater after the lime neutralizing treatment is up to standard.
The present embodiment main economic and technical indices:
Bismuth total yield 95%, total direct yield 90%;
Power consumption 3500kwh/tBi, acid consumption (HCl31%) 800kg/tBi;
Coal consumption 1000kg/tBi, heavy oil 200kg/fBi;
Zinc ingot metal 50kg/tBi, chlorine 90kg/tBi;
Soda ash 150kg/tBi, caustic soda 50kg/tBi;
Present embodiment technological operation condition
Electrolyte temperature 50-60 ℃, liquid-solid ratio 4-8: 1;
Current density 150A/m
2, electrolysis time 22h/d;
Bath voltage 3.5-4.0v, ore deposit treatment capacity 2t/d;
Electrolytic solution major ingredient (g/l), Bi
2+20-30, Cl 110-130.
Present embodiment process calculation master data
The bismuth concentrate is formed (butt): Bi20%, Fe15.56%, SiO
216.47%, CsO4.0%, MgO0.17%, Ag74g/t, concentrate contains H2O13%.
Leaching yield: Bi98%, Ag95%Fe6%.
Slag rate: 70%.
Leached mud is moisture: 20%.
The sponge bismuth filter cake: moisture 25%, bismuth-containing 87%.
Circulation of elecrolyte amount: Cs=6666.6 ÷ 300=22.22t/dL=22.22X8 ÷ 22-6.21m
3/ h=59.3m
3/ d, L/S=8: 1.
In-pulp electrolysis evaporated water: 4m3/d.
Concentrate is brought the water yield into: 7.41 ÷, 82% * 18%=1.63m
3/ d.
Liquid waste disposal amount: L=800 * 400 ÷, 300 * 31% * (35.5/36.5) ÷ 120=2.7m
3/ d.
Sponge bismuth meal: G
Gu=7.41 * 20% * 97% ÷ 87%=1.66t/d, V=1.66 ÷ 9+1.66 ÷ 75% * 25%=0.184+0.553=0.74m
3/ d.
Leached mud: Gs=7.41 * 70%=5.2t/d.
Claims (2)
1, a kind of bismuth mineral silicofluoric acid in-pulp electrolysis technology, it is characterized in that: the bismuth concentrate that contains bismuth sulfide or oxidation bismuth mineral or low-quality secondary bismuth material enters the pulp groove as raw material of ore, after pulp adds the hydrochloric acid acid adjustment, guarantee that bi content is 1.8～16.8 mol in the slurries, acid content is 3.5～9 mol, above-mentioned slurries are entered the in-pulp electrolysis groove continuously, and ionogen is plumbous silicofluoride solution PbSiF6 and silicofluoric acid H2SiF
6, make negative electrode with the pure stereotype that diaphragm bag is housed, more than 90%, the casting stereotype of stanniferous below 0.001% made anode with leaded, and feeding voltage at electrolyzer is 3.10～4.25V, and current density is 130～250A/m
2The direct current effect under finish the leaching and the electrolysis of bismuth simultaneously, negative electrode after the electrolysis is separated out bismuth meal and is the spongy diaphragm bag bottom that falls into, dependence is taken out the powder device and is pressed into the sponge bismuth pressure filter, pressure filter is dehydrated into filter cake briquetting dehydration back retailoring with sponge bismuth briquetting and becomes the thick bismuth of the high metal of bismuth-containing, through logical chlorine, it is 99.999% high purity bismuth that the sodium hydroxide impurity removing refining becomes final content, ore pulp after above-mentioned electrolyzer leaches injects the filtration washing pond through acid proof pump and filters, the leached mud that washing and filtering goes out is stored up with special-purpose place and is done comprehensive reclaimed materials processing, leach liquor returns the pulp groove and recycles, sedimentary a small amount of spongy bismuth meal also is pressed into the sponge bismuth pressure filter with taking out the powder device in the filtration washing pond simultaneously, the a spot of leach liquor of regular discharge in the above-mentioned electrolytic process forms calcium scum and discharge of wastewater after the lime neutralizing treatment is up to standard.
2, a kind of bismuth mineral silicofluoric acid in-pulp electrolysis technology according to claim 1 is characterized in that: stir on electrolysis limit in limit in the electrolytic process.
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| CNB021397031A CN1274885C (en) | 2002-10-22 | 2002-10-22 | Technique for electrolyzing slurry of fluosilicic acid in bismuth mine |
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|---|---|---|---|
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| CN103014779B (en) * | 2012-03-18 | 2015-07-29 | 英德佳纳金属科技有限公司 | A kind of multistage ore pulp decomposes Winning cell and decomposes electrodeposition process integration |
| CN104099480B (en) * | 2014-08-09 | 2016-03-30 | 江西龙天勇有色金属有限公司 | A kind of slag bismuth oxide prepares the method for bismuth electrolytic solution |
| CN105506728B (en) * | 2014-09-29 | 2019-10-15 | 盛美半导体设备（上海）有限公司 | The device of precipitating metal ion from electrochemical polish liquid |
| CN106811768A (en) * | 2017-02-24 | 2017-06-09 | 中南大学 | A kind of method for processing bismuth sulfide ore |
| CN108677031B (en) * | 2018-06-15 | 2019-09-27 | 昆明理工大学 | A method of recycling lead from lead sponge |
| CN111252770A (en) * | 2020-04-26 | 2020-06-09 | 贵州瓮福蓝天氟化工股份有限公司 | Method for removing chlorine from fluosilicic acid |
| CN112575192A (en) * | 2020-11-10 | 2021-03-30 | 湖南柿竹园有色金属有限责任公司 | Method for extracting valuable metals by electrolytic separation of bismuth silver zinc slag |
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