CN102534660B - Method for electrolytically refining crude lead - Google Patents
Method for electrolytically refining crude lead Download PDFInfo
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- CN102534660B CN102534660B CN201210010362.XA CN201210010362A CN102534660B CN 102534660 B CN102534660 B CN 102534660B CN 201210010362 A CN201210010362 A CN 201210010362A CN 102534660 B CN102534660 B CN 102534660B
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- lead
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- sodium hydroxide
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- electrolysis
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000007670 refining Methods 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 7
- 239000011975 tartaric acid Substances 0.000 claims abstract description 7
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract 5
- 150000002500 ions Chemical class 0.000 claims abstract 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002161 passivation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 abstract description 19
- 239000002253 acid Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002893 slag Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000003595 mist Substances 0.000 abstract description 2
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000428 dust Substances 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 239000010802 sludge Substances 0.000 description 21
- 235000011121 sodium hydroxide Nutrition 0.000 description 17
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 13
- 229940095064 tartrate Drugs 0.000 description 12
- 229910052787 antimony Inorganic materials 0.000 description 10
- 229910052797 bismuth Inorganic materials 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 229910017518 Cu Zn Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052785 arsenic Inorganic materials 0.000 description 6
- -1 plumbum ion Chemical class 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000003500 flue dust Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
一种电解精炼粗铅的方法，将氢氧化钠、酒石酸依次加入水中，在常温下搅拌溶解制得混合溶液，在混合溶液中加入氧化铅粉末，溶解过滤后所得滤液为电解液，将制得的电解液加入电解槽中，采用不锈钢板或纯铅板作为阴极，采用待精炼的粗铅制成阳极，通入直流电进行电解。本发明避免了火法精炼产生的各种烟尘、中间渣，提高了精炼过程铅的直收率和各种有价金属的综合回收率，且不会产生挥发烟尘或酸雾，克服了硅氟酸体系电解液污染环境的缺点；同时，电解液中加入氢氧化钠和酒石酸可以与氧化铅形成配合物，大大增加了电解液中铅离子的浓度，提高了电解效率。A method for electrolytically refining crude lead, comprising adding sodium hydroxide and tartaric acid into water in sequence, stirring and dissolving at room temperature to obtain a mixed solution, adding lead oxide powder to the mixed solution, dissolving and filtering the filtrate obtained as an electrolyte solution, and preparing The electrolyte solution is added to the electrolytic cell, the stainless steel plate or pure lead plate is used as the cathode, the crude lead to be refined is used to make the anode, and direct current is passed through for electrolysis. The invention avoids all kinds of dust and intermediate slag produced by fire refining, improves the direct recovery rate of lead and the comprehensive recovery rate of various valuable metals in the refining process, and does not generate volatile smoke or acid mist, and overcomes the silicon-fluorine The acid system electrolyte has the disadvantage of polluting the environment; at the same time, adding sodium hydroxide and tartaric acid to the electrolyte can form a complex with lead oxide, which greatly increases the concentration of lead ions in the electrolyte and improves the electrolysis efficiency.
Description
Technical field
The present invention relates to plumbous purification refining field, a kind of method of performing electrolytic refining on lead bullion specifically.
Background technology
In order to remove detrimental impurity in lead bullion and to reclaim precious metal, must carry out refining to it, the method for the refining of lead bullion is divided two kinds of pyrogenic process and electrolytic process.The master operation of fire refining process is: 1. copper removal: first liquate or condensation copper removal, then add sulphur deep copper removal; 2. add caustic soda except tellurium; 3. with oxidation style or alkali-chloride improving arsenic removal, antimony, tin; 4. zincification reclaims gold and silver; 5. dezincify; 6. add calcium magnesium except bismuth; 7. final refining ingot casting obtains lead bullion.The slag of each operation output processes respectively to reclaim wherein valuable element.Pyrorefining lead bullion produces quite a large amount of leaded (and other metal) flue dust, various middle slag and sulfur dioxide gas, and contaminate environment is serious, and plumbous direct yield and comprehensive recovery is lower simultaneously.
Compared with pyrogenic process, the waste gas that electrolytic process produces is few, and energy consumption is low, and therefore superior product quality is widely used in the refining of lead bullion.The method that current industrial lead bullion electrorefining extensively adopts is Bai Zifa, and lead bullion is cast positive plate, is processed into starting sheet with negative electrode lead, is containing PbSiF
6with free H
2siF
6in solution, carry out electrolysis.Bai Zifa is widely used in the plumbous smeltery of the states such as China, Canada, Italy, Japan, Peru, Russia at present.But there are some shortcomings in Bai Zifa, as H
2siF
6volatile, job site can produce a large amount of acid mists, and the smell is awful, PbSiF
6preparation process in can emit HF and SiF
4gas, to human body and environmental hazard very large volumes such as (, heavy non-ferrous metal smelting design manual: plumbous zinc bismuth volume, Beijing: metallurgical industry press, 1995, P88-106, P119-146) Beijing Nonferrous Metallurgy Design Research Institute.Other acid system of once studying has muriate, nitrate, borate salt system etc., but only limits to plumbous electrodeposition, there is not yet the report that is applied to the refining of lead bullion, and acid electrolyte is volatile, pollutes generally larger.
Summary of the invention
The present invention be solve prior art in the time of lead bullion electrorefining to environment and the very large problem of harm, a kind of method of performing electrolytic refining on lead bullion is provided, the method, by containing the electrorefining that carries out lead bullion in tartaric basic solution, can alleviate the environmental pollution of electrolytic process and the harm to human body.
The present invention solves the problems of the technologies described above the technical scheme of employing to be: a kind of method of performing electrolytic refining on lead bullion, sodium hydroxide, tartrate are added to the water successively, stirring and dissolving makes mixing solutions at normal temperatures, and the add-on of tartrate and sodium hydroxide is in every liter of mixing solutions, to add 100 ~ 160g tartrate, 80 ~ 160g sodium hydroxide; Then in mixing solutions, adding lead oxide powder, is stirring and dissolving under 40 ~ 98 ℃, the condition of stirring velocity 200 ~ 400r/min in temperature, and time 1 ~ 6h, then filters, and gained filtrate is electrolytic solution; The granularity of described lead oxide powder is less than 200 orders, and in the electrolytic solution preparing, plumbum ion concentration is 80 ~ 130g/L;
The electrolytic solution making is added in electrolyzer, adopt stainless steel plate or pure stereotype as negative electrode, employing treats that the lead bullion of refining makes anode, pass into direct current and carry out electrolysis, concrete electrolytic process parameter is: 40 ~ 60 ℃ of electrolyte temperatures, the circulation of elecrolyte cycle is 45 ~ 120min, and circulation of elecrolyte mode is bottom in and top out, cathode current density 100 ~ 160A/m
2, bath voltage 0.25 ~ 1.0V, anodic current density 100 ~ 160A/m
2, with interpole gap 80 ~ 130mm;
In electrolytic process, rise to 1.0V when bath voltage, while there is anode passivation, take out positive plate and scrub or double teeming positive plate, scrub or double teeming after positive plate return to participation electrolysis;
According to the steam output of electrolytic solution, timing is to make up water in electrolytic solution, to maintain plumbum ion concentration 80 ~ 130g/L in electrolytic solution, sodium hydroxide 80 ~ 160 g/L and tartaric acid concentration 100 ~ 160 g/L;
The dirt settling of collecting on negative electrode is the lead obtaining after refining.
In the present invention, described tartrate, sodium hydroxide and plumbous oxide are analytical pure or technical grade reagent.
The present invention can carry out in the time of the dirt settling of collecting on negative electrode in the time scrubbing anode.
In the present invention, in the time of preparation electrolytic solution, add sodium hydroxide and tartaric reason to be: sodium hydroxide and tartrate can form a kind of structure that is similar to title complex with plumbous oxide, can greatly increase the concentration of lead ion in electrolytic solution, the electrolytic solution of alkalescence is also more stable in the time of electrolysis simultaneously, can not produce environment and the harmful gas of human body.
In the present invention, in electrolytic process, the anode of being poured into a mould by lead bullion, under the effect of electric current, lead constantly enters into electrolytic solution and forms title complex, and then title complex obtains electron reduction for plumbous at negative electrode; Anode constantly dissolves, and final anode is remaining is the anode sludge of anode scrap and precious metal composition.
The present invention is applicable to the lead bullion of plumbous smelting process output, and its main component scope is: Pb 96% ~ 99%, Sb 0.5% ~ 3%, Cu 0.05% ~ 3%, As 0.005% ~ 1.5%, Sn 0.02% ~ 1%, Bi 0.1% ~ 1%, Ag 0.1% ~ 3%; Also be suitable for processing lead antimony alloy, lead bismuth alloy etc.
Beneficial effect: the present invention and traditional plumbous refinery practice comparison, have following advantage: 1, the present invention has avoided various flue dust, the middle slag that pyrorefining produces, and has improved the direct yield of refining process lead and the comprehensive recovery of various valuable metals;
2, alkaline organic electrolysis system is environmentally friendly, can not produce volatilization flue dust or acid mist, has overcome the shortcoming of silicofluoric acid system electrolyte contamination environment;
3, in electrolytic solution, add sodium hydroxide and tartrate to form title complex with plumbous oxide, greatly increased the concentration of lead ion in electrolytic solution, improved electrolytic efficiency.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
Lead content in lead bullion is 98.30%, and major impurity composition is tin 0.0008%, antimony 0.8281%, bismuth 0.1363%, arsenic 0.5127%, copper 0.0795%, zinc 0.0006%, silver 0.1406%, iron 0.0013%.Tartrate, sodium hydroxide and plumbous oxide are analytical pure.
Take lead bullion 500 g, in retort furnace, 600 ℃ of fusing 15 min that heat take out, and are cast into positive plate in graphite jig, are of a size of 10cm × 10cm.
Take 200 g plumbous oxide, 180 g sodium hydroxide, 180 g tartrate add in 1.5 L water, and 70 ℃ of magnetic agitation 4 h filter, and obtain electrolytic solution, and wherein plumbum ion concentration is 110g/L.Control 55 ℃ of electrolysis temperatures, current density 140 A/m
2, pole span 4 cm, polar plate area 9.7 cm × 9.9 cm, circulation of elecrolyte speed 30 mL/min, when bath voltage is increased to 1.0V, take out positive plate, scrub to put into electrolyzer after the anode sludge and continue electrolysis, and electrolysis time amounts to 24h.Average cell voltage 0.32V, current efficiency 98.93%, negative electrode energy consumption 83.69 kWh/t Pb.The constituent content of negative electrode lead and the anode sludge is respectively in table 1 and table 2.
The foreign matter content (× 10 of table 1 negative electrode lead
-6%)
| Element | Sn | Sb | Bi | As | Cu | Zn | Fe | Ag | Ni | Cd | Summation |
| Negative electrode lead | ＜8.9 | ＜8.9 | 2880 | 15.8 | 573 | ＜8.9 | 310 | ＜8.9 | ＜8.9 | ＜8.9 | ＜3832.2 |
| GB (≤) | 500 | 800 | 4000 | 500 | 1000 | 400 | 500 | 800 | - | - | 6000 |
The constituent content (%) of table 2 anode sludge
| Element | Sn | Sb | Bi | As | Cu | Zn | Fe | Ag | Ni | Cd |
| The anode sludge | - | 12.28 | 10.84 | 33.83 | 7.188 | - | 0.464 | 10.66 | 0.109 | - |
As can be seen from Table 1, the foreign matter content in negative electrode lead is very low, and the purity of negative electrode lead is higher, higher than 99.99617%, has reached the standard of Pb99.994 lead pig in GB/T 469-2005.As can be seen from Table 2, the enrichment of element such as silver, bismuth, antimony is in the anode sludge.
Embodiment 2
Plumbous content in lead bullion is 98.10%, and major impurity composition is tin 0.0008%, antimony 0.9106%, bismuth 0.1959%, arsenic 0.5451%, copper 0.0933%, zinc 0.0006%, silver 0.1521%, iron 0.0015%.Tartrate, sodium hydroxide and plumbous oxide are analytical pure.
Take lead bullion 500g, in retort furnace, heat to 650 ℃ of fusing 15min, take out, in graphite jig, be cast into positive plate, be of a size of 10cm × 10cm.
Get 180 g plumbous oxide, 210 g sodium hydroxide, 210 g tartrate add in 1.5 L distilled water, and 80 ℃ of magnetic agitation 4 h, obtain electrolytic solution after filtration, and wherein plumbum ion concentration is 100g/L.Control 45 ℃ of electrolysis temperatures, current density 160 A/m2, pole span 4 cm, polar plate area 9.7 cm × 9.9 cm, electrolytic solution volume 1.5 L, circulation of elecrolyte speed 30 mL/min.When bath voltage is increased to 1.0V, take out positive plate, scrub and put into electrolyzer after the anode sludge and continue electrolysis, electrolysis time amounts to 25h.Average cell voltage 0.39V, current efficiency 98.77%, negative electrode energy consumption 102.16 kWh/t Pb.The constituent content of negative electrode lead and the anode sludge is respectively in table 3 and table 4.
The foreign matter content (× 10 of table 3 negative electrode lead
-6%)
| Element | Sn | Sb | Bi | As | Cu | Zn | Fe | Ag | Ni | Cd | Summation |
| Negative electrode lead | ＜9.5 | ＜9.5 | 3100 | 19.8 | 540 | ＜9.5 | 335 | ＜9.5 | ＜9.5 | ＜9.5 | ＜4042.3 |
| GB (≤) | 500 | 800 | 4000 | 500 | 1000 | 400 | 500 | 800 | - | - | 6000 |
The constituent content (%) of table 4 anode sludge
| Element | Sn | Sb | Bi | As | Cu | Zn | Fe | Ag | Ni | Cd |
| The anode sludge | - | 14.58 | 9.431 | 31.53 | 6.673 | - | 0.312 | 9.85 | 0.0845 | - |
As can be seen from Table 3, the purity of negative electrode lead is 99.99596%, has reached the standard of Pb99.994 lead pig in GB/T 469-2005.Can find out by 4, the enrichment of element such as silver, bismuth, antimony are in the anode sludge.
Embodiment 3
Lead content in lead bullion is 98.30%, and major impurity composition is tin 0.0008%, antimony 0.8281%, bismuth 0.1363%, arsenic 0.5127%, copper 0.0795%, zinc 0.0006%, silver 0.1406%, iron 0.0013%.Tartrate, sodium hydroxide and plumbous oxide are analytical pure.
Take lead bullion 500 g, in retort furnace, 600 ℃ of fusing 15 min that heat take out, and are cast into positive plate in graphite jig, are of a size of 10cm × 10cm.
Take 100 g plumbous oxide, 120g sodium hydroxide, 150 g tartrate add in 1.5 L water, and 70 ℃ of magnetic agitation 4 h filter, and obtain electrolytic solution, and wherein plumbum ion concentration is 80g/L.Control 40 ℃ of electrolysis temperatures, current density 100 A/m
2, pole span 4 cm, polar plate area 9.7 cm × 9.9 cm, circulation of elecrolyte speed 8.5 mL/min, when bath voltage is increased to 1.0V, take out positive plate, scrub to put into electrolyzer after the anode sludge and continue electrolysis, and electrolysis time amounts to 24h.Average cell voltage 0.27V, current efficiency 99.15%, negative electrode energy consumption 70.45 kWh/t Pb.The constituent content of negative electrode lead and the anode sludge is respectively in table 5 and table 6.
The foreign matter content (× 10 of table 5 negative electrode lead
-6%)
| Element | Sn | Sb | Bi | As | Cu | Zn | Fe | Ag | Ni | Cd | Summation |
| Negative electrode lead | ＜8.9 | ＜8.9 | 1850 | 12.6 | 435 | ＜8.9 | 230 | ＜8.9 | ＜8.9 | ＜8.9 | ＜2581 |
| GB (≤) | 500 | 800 | 4000 | 500 | 1000 | 400 | 500 | 800 | - | - | 6000 |
The constituent content (%) of table 6 anode sludge
| Element | Sn | Sb | Bi | As | Cu | Zn | Fe | Ag | Ni | Cd |
| The anode sludge | - | 13.44 | 10.97 | 35.27 | 8.322 | - | 0.489 | 10.83 | 0.112 | - |
As can be seen from Table 5, the foreign matter content in negative electrode lead is very low, and the purity of negative electrode lead is higher, higher than 99.99741%, has reached the standard of Pb99.994 lead pig in GB/T 469-2005.As can be seen from Table 6, the enrichment of element such as silver, bismuth, antimony is in the anode sludge.
Embodiment 4
Lead content in lead bullion is 98.30%, and major impurity composition is tin 0.0008%, antimony 0.8281%, bismuth 0.1363%, arsenic 0.5127%, copper 0.0795%, zinc 0.0006%, silver 0.1406%, iron 0.0013%.Tartrate, sodium hydroxide and plumbous oxide are analytical pure.
Take lead bullion 500 g, in retort furnace, 600 ℃ of fusing 15 min that heat take out, and are cast into positive plate in graphite jig, are of a size of 10cm × 10cm.
Take 250 g plumbous oxide, 240 g sodium hydroxide, 240 g tartrate add in 1.5 L water, and 70 ℃ of magnetic agitation 4 h filter, and obtain electrolytic solution, and wherein plumbum ion concentration is 130g/L.Control 55 ℃ of electrolysis temperatures, current density 160 A/m
2, pole span 4 cm, polar plate area 9.7 cm × 9.9 cm, circulation of elecrolyte speed 30 mL/min, when bath voltage is increased to 1.0V, take out positive plate, scrub to put into electrolyzer after the anode sludge and continue electrolysis, and electrolysis time amounts to 24h.Average cell voltage 0.38V, current efficiency 98.27%, negative electrode energy consumption 100.05 kWh/t Pb.The constituent content of negative electrode lead and the anode sludge is respectively in table 7 and table 8.
The foreign matter content (× 10 of table 7 negative electrode lead
-6%)
| Element | Sn | Sb | Bi | As | Cu | Zn | Fe | Ag | Ni | Cd | Summation |
| Negative electrode lead | ＜8.9 | ＜8.9 | 3250 | 17.4 | 698 | ＜8.9 | 421 | ＜8.9 | ＜8.9 | ＜8.9 | ＜4749.8 |
| GB (≤) | 500 | 800 | 4000 | 500 | 1000 | 400 | 500 | 800 | - | - | 6000 |
The constituent content (%) of table 8 anode sludge
| Element | Sn | Sb | Bi | As | Cu | Zn | Fe | Ag | Ni | Cd |
| The anode sludge | - | 11.13 | 10.62 | 31.53 | 6.205 | - | 0.375 | 10.35 | 0.115 | - |
As can be seen from Table 7, the foreign matter content in negative electrode lead is very low, and the purity of negative electrode lead is higher, higher than 99.99525%, has reached the standard of Pb99.994 lead pig in GB/T 469-2005.As can be seen from Table 8, the enrichment of element such as silver, bismuth, antimony is in the anode sludge.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210010362.XA CN102534660B (en) | 2012-01-13 | 2012-01-13 | Method for electrolytically refining crude lead |
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| CN109055982A (en) * | 2018-09-20 | 2018-12-21 | 湖南省桂阳银星有色冶炼有限公司 | A kind of lead bullion electrolytic smelting method |
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| 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 |
| CN104131317B (en) * | 2014-08-01 | 2016-08-24 | 昆明理工大学 | The method of thin lead powder is prepared in a kind of electro-deposition |
| CN105714329B (en) * | 2014-12-05 | 2017-10-20 | 上海奇谋能源技术开发有限公司 | A kind of method of Direct Electrolysis scrap |
| CN106011931A (en) * | 2016-08-08 | 2016-10-12 | 昆明冶金研究院 | Large-pole plate long-time cycle lead anode two-step electrolytic refining method |
| CN107059064A (en) * | 2016-12-08 | 2017-08-18 | 汤恭年 | The electricity growth powder method processed of lead-acid accumulator special-purpose nanometer lead powder |
| CN109778230B (en) * | 2019-01-22 | 2021-03-12 | 河套学院 | A kind of method for electrolytic separation of lead and copper with high lead matte |
| CN113215619A (en) * | 2021-04-26 | 2021-08-06 | 太和县大华能源科技有限公司 | Electrolytic refining system of lead bullion |
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| CN109055982A (en) * | 2018-09-20 | 2018-12-21 | 湖南省桂阳银星有色冶炼有限公司 | A kind of lead bullion electrolytic smelting method |
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