CN103938228B - Lead electrolytic solution and the purification method of earth of positive pole wash water foreign metal ion - Google Patents
Lead electrolytic solution and the purification method of earth of positive pole wash water foreign metal ion Download PDFInfo
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Abstract
Lead electrolytic solution and the purification method of earth of positive pole wash water foreign metal ion, comprise the following steps: lead electrolytic solution foreign metal ion cleaning, positive plate and minus plate is installed in electrolysis bath, the electrolyte circulation rate controlled in electrolysis bath is 8～10L/min, sampling detection in every 6 ~ 12 hours is once, until after electrolyte foreign metal ion is up to standard, then energising normally produces；Earth of positive pole wash water foreign metal ion cleaning, take earth of positive pole wash water is transported to wash water purification tank, load stereotype in groove, control the ratio of stereotype surface area and the volume of earth of positive pole wash water, reaction clarification 24 ~ 48 hours, allocates electrolyte into after earth of positive pole wash water foreign metal ion is up to standard.The present invention solve high miscellaneous lead bullion electrorefining and lead electrolysis reproduce the initial stage because of in electrolyte foreign metal ion exceed standard and the technical barrier of output defective precipitation lead, the precipitation lead of output is up-to-standard, there is advantage simple to operate, that production efficiency is high, recovery rate of valuable metals is high, remarkable in economical benefits.
Description
Technical field
The present invention relates to electrolytic lead refining field, particularly to a kind of lead electrolytic solution and earth of positive pole wash water foreign metal ion
Purification method.
Background technology
In recent years, lead smelting in China ability and yield increase substantially, and lead industrial structure contradiction is further exacerbated by, and industry is competing
Strive more and more fierce.Along with the exhaustion day by day of mineral resources, lead smelts being continuously increased of production cost, and many lead smelting enterprises change
Become idea, leady raw materials based on the plumba material of the high added values such as Gao Yin, high antimony, high bismuth, the main grade of output relatively low (about 90%),
Containing the miscellaneous lead bullion of the height that arsenic, antimony, bismuth, copper and gold silver are higher, then carry out electrorefining, with synthetical recovery valuable metal therein, carry
The synthetical recovery benefit of high enterprise.
Use high miscellaneous lead bullion to carry out electrorefining, enter electrolyte for reducing foreign metal ion, the most commonly used
Low current density (≤140A/m2), production efficiency is low, and high current density (>=170A/m in using2), the most inevitably make
Become foreign metal ion in earth of positive pole wash water and electrolyte significantly to exceed standard, meanwhile, reproduce the initial stage because of groove inner anode mud in lead electrolysis
Metal impurities return and molten will also result in foreign metal ion in electrolyte and significantly exceed standard, and domestic and international common practice is to utilize for 1～3 week
Phase high current density allows foreign metal elemental release, and the precipitation lead that foreign metal ion exceeds standard to return anode casting mold be anode
Plate, causes metal to repeat to smelt, and production cost increases.
Summary of the invention
The technical problem to be solved is, overcomes the drawbacks described above that prior art exists, it is provided that a kind of lead electrolysis
Liquid and the new purification method of earth of positive pole wash water foreign metal ion, it can be on the basis of not increasing equipment investment and production cost
Realize electrolyte and the purification of earth of positive pole wash water foreign metal ion, solve high miscellaneous lead bullion electrorefining and lead electrolysis reproduces the initial stage
Because in electrolyte, foreign metal ion exceeds standard and the technical barrier of output defective precipitation lead, the precipitation lead of output is up-to-standard,
There is advantage simple to operate, that production efficiency is high, recovery rate of valuable metals is high, remarkable in economical benefits.
The technical solution adopted for the present invention to solve the technical problems is: a kind of lead electrolytic solution and earth of positive pole wash water impurity gold
Belong to the purification method of ion, comprise the following steps: in electrolysis bath, install positive plate and minus plate, control the electrolysis in electrolysis bath
Liquid circulation rate is 8～10L/min, and sampling in every 6 ~ 12 hours detects once, until after electrolyte foreign metal ion is up to standard, then
Energising normally produces；Earth of positive pole wash water foreign metal ion cleaning step: earth of positive pole wash water is transported to wash water purification tank,
Loading stereotype in groove, control the ratio of stereotype surface area and the volume of earth of positive pole wash water, reaction clarification 24 ~ 48 hours, the earth of positive pole is washed
Electrolyte is allocated into after water impurity metal ion is up to standard.
Further, described foreign metal ion includes bismuth, copper, silver and antimony four metal ion species.
Further, described electrolyte foreign metal ion cleaning is the displacement of lead bismuth, i.e. positive plate and the gold of cathode plate surface
Belonging to lead and be oxidized to lead ion entrance electrolyte, electrolyte foreign metal ion is reduced to metal and precipitates.
Further, described earth of positive pole wash water foreign metal ion cleaning is the displacement of lead bismuth, i.e. controls stereotype surface area and sun
The ratio of the volume of pole mud wash water, carries out displacement reaction, and metallic lead is oxidized to lead ion, and foreign metal ion is reduced to metal
And precipitate.
Further, described stereotype surface area is 25～30m with the ratio of earth of positive pole wash water volume2/m3, react 24 hours desirable
Obtain Expected Results.
Further, described electrolyte foreign metal ion concentration up to standard is Bi≤0.004g/L, Cu≤0.002g/L, Ag
≤ 0.0008g/L, Sb≤0.5 g/L.
Further, described earth of positive pole wash water foreign metal ion concentration up to standard is Bi≤0.03g/L, Cu≤0.004g/
L, Ag≤0.002g/L, Sb≤1.2 g/L.
Further, the width of described wash water purification tank is consistent with normal electrolysis bath with the degree of depth, the 1 of a length of normal electrolysis bath
～3 times, internal employing lining moulds anticorrosion, and material is polrvinyl chloride.
Foreign metal ion in electrolyte and earth of positive pole wash water is purified by the present invention, controls electrolyte and the earth of positive pole
Wash water foreign metal ion concentration, within correlation standard scope, solves high miscellaneous lead bullion electrorefining and lead electrolysis reproduces
Initial stage because of in electrolyte foreign metal ion exceed standard the defective lead of output and repeat to smelt, the technology that production cost is significantly increased is difficult
Topic, separates out lead quality and meets the Pb99.994 standard-required in GB/T469-2005.
Compared with prior art, the present invention have a characteristic that 1, high miscellaneous lead bullion electrorefining can use normal in high
Electric current density, it is up-to-standard that output separates out lead, and production efficiency is greatly improved；2, solve lead electrolysis and reproduce the initial stage because of in electrolyte
Foreign metal ion exceeds standard output defective precipitation lead and repeats to smelt, the technical barrier that production cost is significantly increased；3, do not increase
Oil (gas) filling device investment and production cost, simple to operate, automaticity is high；4, remarkable in economical benefits, uses the present invention through inventor
Result over 2 years shows, lead electrolysis reproduces the precipitation lead qualification rate 100% of output, and high miscellaneous lead bullion uses middle and high electric current density electricity
The precipitation lead qualification rate solving refine output is more than 99%, and the lead factory producing 100000 tons of electric lead per year can reclaim antimony, bismuth 2000 tons every year
Above.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
It is as follows to the Concentration Testing of electrolyte foreign metal ion that lead electrolysis reproduces the initial stage: Bi 0.024g/L, Cu
0.006g/L, Ag 0.0085g/L, Sb 0.85g/L, Qi Zhongtong, silver, bismuth exceed standard more than 3～10 times respectively.To electrolyte impurity
Metal ion purifies: installs chloride plate and lead electrode plate, first no power in electrolysis bath by normal organization of production, controls
Electrolyte circulation rate in electrolysis bath is 8L/min, within every 6 hours, detects electrolyte, electrolyte detection knot after 32 hours
Fruit is as follows: Bi 0.0026g/L, Cu 0.0020g/L, Ag 0.00065g/L, Sb 0.25g/L, and testing result meets lead electrolysis
Liquid standard, then be energized, use normal middle high current density to produce.
The electrolyte foreign metal ion cleaning of the present embodiment is the displacement of lead bismuth, i.e. positive plate and the metal of cathode plate surface
Lead is oxidized to lead ion and enters electrolyte, and electrolyte foreign metal ion is reduced to metal and precipitates.
The chemical composition of the lead pig that the present embodiment prepares is: Pb 99.99686%, impurity summation 0.00314%, Cu
0.00049%, Bi 0.001%, Ag 0.0002%, As 0.00035%, Sb 0.0004%, Sn 0.0002%, Zn 0.0002%, Fe
0.0002%, Cd 0.00005%, Ni 0.00005%.Lead pig quality meets the Pb99.994 standard-required in GB/T469-2005.
Embodiment 2
It is as follows to the Concentration Testing of electrolyte foreign metal ion that lead electrolysis reproduces the initial stage: Bi 0.012g/L, Cu
0.004g/L, Ag 0.0038g/L, Sb 0.42g/L.Wherein bismuth, copper, silver exceed standard more than 2～5 times respectively.Electrolyte impurity gold
Belong to ion cleaning: in electrolysis bath, install chloride plate and lead electrode plate, first no power by normal organization of production, control electrolysis bath
Interior electrolyte circulation rate is 10L/min, within every 12 hours, detects electrolyte, and after 24 hours, electrolyte testing result is such as
Under: Bi 0.0028g/L, Cu 0.0016g/L, Ag 0.00057g/L, Sb 0.24g/L.Testing result meets lead electrolytic solution mark
Standard, energising normally produces.
The electrolyte foreign metal ion cleaning of the present embodiment is the displacement of lead bismuth, i.e. positive plate and the metal of cathode plate surface
Lead is oxidized to lead ion and enters electrolyte, and electrolyte foreign metal ion is reduced to metal and precipitates.
The chemical composition of the lead pig that the present embodiment prepares is: Pb 99.99688%, impurity summation 0.00312%, Cu
0.00048%, Bi 0.001%, Ag 0.0002%, As 0.00034%, Sb 0.0004%, Sn 0.0002%, Zn 0.0002%, Fe
0.0002%, Cd 0.00005%, Ni 0.00005%.Lead pig quality meets the Pb99.994 standard-required in GB/T469-2005.
Embodiment 3
Earth of positive pole wash water its foreign metal ion after testing of high current density electrolysis refine output in high miscellaneous lead bullion employing
Composition is: Bi 0.48g/L, Cu 0.004g/L, Ag 0.002g/L, Sb 1.0 g/L.Wherein bismuth exceeds earth of positive pole wash water standard
Reach 16 times, it is necessary to carry out purified treatment.Earth of positive pole wash water foreign metal ion cleaning, is delivered to the earth of positive pole wash water wash water and purifies
Groove, loads stereotype in groove, the volume ratio controlling stereotype surface area and earth of positive pole wash water is 25m2/m3, after reaction is clarified 24 hours,
Groove inner anode mud wash water is sampled detection.Testing result is as follows: Bi 0.015g/L, Cu 0.002g/L, Ag
0.00045g/L, Sb 0.16g/L.Testing result meets earth of positive pole wash water standard, can allocate earth of positive pole wash water into electrolyte.
The earth of positive pole wash water foreign metal ion cleaning of the present embodiment is the displacement of lead bismuth, i.e. controls stereotype surface area and anode
The volume ratio of mud wash water is 25m2/m3, carrying out displacement reaction, metallic lead is oxidized to lead ion, and foreign metal ion is reduced to
Metal and precipitate.
The chemical composition of the lead pig that the present embodiment prepares is: Pb 99.99682%, impurity summation 0.00318%, Cu
0.00048%, Bi 0.00106%, Ag 0.0002%, As 0.00034%, Sb 0.0004%, Sn 0.0002%, Zn 0.0002%,
Fe 0.0002%, Cd 0.00005%, Ni 0.00005%.Lead pig quality meets the Pb99.994 standard in GB/T469-2005 and wants
Ask.
Embodiment 4
Earth of positive pole wash water its foreign metal ion after testing of high current density electrolysis refine output in high miscellaneous lead bullion employing
Composition is: Bi 0.026g/L, Cu 0.005g/L, Ag 0.002g/L, Sb 2.3g/L.Wherein copper, antimony exceed standard, and especially antimony exceeds standard
Nearly twice, it is necessary to carry out purified treatment.Earth of positive pole wash water foreign metal ion cleaning, is delivered to the earth of positive pole wash water wash water and purifies
Groove, loads stereotype in groove, controlling stereotype surface area with wash water volume ratio is 30m2/m3, after reaction is clarified 48 hours, to sun in groove
Pole mud wash water is sampled detection.Testing result is as follows: Bi 0.0096g/L, Cu 0.0018g/L, Ag 0.00037g/L, Sb
0.22g/L.Testing result meets earth of positive pole wash water standard, can allocate earth of positive pole wash water into electrolyte.
The earth of positive pole wash water foreign metal ion cleaning of the present embodiment is the displacement of lead bismuth, i.e. controls stereotype surface area and anode
The volume ratio of mud wash water is 30m2/m3, carrying out displacement reaction, metallic lead is oxidized to lead ion, and foreign metal ion is reduced to
Metal and precipitate.
The chemical composition of the lead pig that the present embodiment prepares is: Pb 99.99685%, impurity summation 0.00315%, Cu
0.00048%, Bi 0.001%, Ag 0.0002%, As 0.00034%, Sb 0.00043%, Sn 0.0002%, Zn 0.0002%,
Fe 0.0002%, Cd 0.00005%, Ni 0.00005%.Lead pig quality meets the Pb99.994 standard in GB/T469-2005 and wants
Ask.
Embodiment 5
Earth of positive pole wash water foreign metal ion cleaning, is earth of positive pole wash water to be delivered to wash water purification tank carry out lead bismuth displacement
Reaction, wherein the width of wash water purification tank is consistent with normal electrolysis bath with the degree of depth, 1～3 times of a length of normal electrolysis bath, internal
Using lining to mould anticorrosion, material is polrvinyl chloride.
The present invention is including but not limited to above-described embodiment, as long as using the displacement of lead bismuth to carry out electrolyte and earth of positive pole wash water
The method purified, i.e. belongs to protection scope of the present invention.
Claims (5)
1. lead electrolytic solution and the purification method of earth of positive pole wash water foreign metal ion, it is characterised in that comprise the following steps: lead electricity
Solving liquid foreign metal ion cleaning: install chloride plate and lead electrode plate in electrolysis bath, the electrolyte controlled in electrolysis bath follows
Ring speed is 8～10L/min, and sampling in every 6 ~ 12 hours detects once, until after electrolyte foreign metal ion is up to standard, then be energized
Normally producing, described electrolyte foreign metal ion concentration up to standard is Bi≤0.004g/L, Cu≤0.002g/L, Ag≤
0.0008g/L, Sb≤0.5g/L；Earth of positive pole wash water foreign metal ion cleaning: earth of positive pole wash water is transported to wash water purification tank,
Loading stereotype in groove, control the ratio of stereotype surface area and the volume of earth of positive pole wash water, reaction clarification 24 ~ 48 hours, the earth of positive pole is washed
Allocate electrolyte after water impurity metal ion is up to standard into, described earth of positive pole wash water foreign metal ion concentration up to standard be Bi≤
0.03g/L, Cu≤0.004g/L, Ag≤0.002g/L, Sb≤1.2 g/L.
Lead electrolytic solution and the purification method of earth of positive pole wash water foreign metal ion the most according to claim 1, it is characterised in that
Described foreign metal ion includes bismuth, copper, silver and antimony four metal ion species.
Lead electrolytic solution the most according to claim 1 or claim 2 and the purification method of earth of positive pole wash water foreign metal ion, its feature exists
In, described electrolyte foreign metal ion cleaning is the displacement of lead bismuth, and i.e. the metallic lead on chloride plate and lead electrode plate surface is by oxygen
Turning to lead ion and enter electrolyte, electrolyte foreign metal ion is reduced to metal and precipitates.
Lead electrolytic solution the most according to claim 1 or claim 2 and the purification method of earth of positive pole wash water foreign metal ion, its feature exists
In, described earth of positive pole wash water foreign metal ion cleaning is the displacement of lead bismuth, i.e. controls the body of stereotype surface area and earth of positive pole wash water
Long-pending ratio, carries out displacement reaction, and metallic lead is oxidized to lead ion, and foreign metal ion is reduced to metal and precipitates.
5. want lead electrolytic solution described in 4 and the purification method of earth of positive pole wash water foreign metal ion according to right, it is characterised in that institute
The ratio stating the stereotype surface area volume with earth of positive pole wash water is 25～30m2/m3。
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| CN201410115639.4A CN103938228B (en) | 2014-03-26 | 2014-03-26 | Lead electrolytic solution and the purification method of earth of positive pole wash water foreign metal ion |
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| CN104952622A (en) * | 2015-05-28 | 2015-09-30 | 南通华裕电子有限公司 | Method of purifying electrolyte of aluminum electrolytic capacitor |
| CN111519214A (en) * | 2020-06-09 | 2020-08-11 | 内蒙古兴安银铅冶炼有限公司 | Lead electrolyte purification process |
| CN112661324B (en) * | 2020-12-29 | 2023-04-18 | 江苏聚成金刚石科技有限公司 | Diamond wire electroplating liquid purification system and purification method thereof |
| CN113061941A (en) * | 2021-03-22 | 2021-07-02 | 刘罗平 | Bismuth removing method in high bismuth crude lead electrolysis process |
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| CN101713028B (en) * | 2009-11-24 | 2012-06-20 | 江西稀有金属钨业控股集团有限公司 | Method for washing anode slime of electrolytic lead bismuth alloy |
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| CN1772957A (en) * | 2005-11-01 | 2006-05-17 | 株洲冶炼集团有限责任公司 | Electrolytic method for high Bi crude aluminum |
| CN101886174A (en) * | 2010-06-23 | 2010-11-17 | 郴州雄风稀贵金属材料股份有限公司 | Process for refining high-purity bismuth from bismuth-containing material generated from anode mud recovery |
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Effective date of registration: 20190326 Address after: 421513 No. 19 Dukou Road, Shuikoushan Town, Changning City, Hengyang City, Hunan Province Patentee after: Shuikoushan Nonferrous Metal Co., Ltd. Address before: 421513 Songbai Town, Changning City, Hengyang City, Hunan Province Patentee before: Hunan Shuikoushan Nonferrous Metals Group Co., Ltd. |
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