Russian Journal of Applied Chemistry, Vol. 76, No. 2, 2003, pp. 191!194.

Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 2, 2003, pp. 201!204. Original Russian Text Copyright + 2003 by Zarubitskii.

INORGANIC SYNTHESIS AND INDUSTRIAL INORGANIC CHEMISTRY

Refining of Lead To Give Bismuth-Enriched Drosses

O. G. Zarubitskii
Vernadskii Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received June 3, 2002

Abstract The results obtained in testing an improved technique for reagent refining of crude lead, which yields bismuth-enriched drosses in the form of a powder, are presented. The advantages of the method put into industrial practice are described.

The pyrometallurgical method proposed by Kroll and Betterton [1, 2] is mainly used at lead works to remove bismuth admixtures from refined crude lead (lead bullion). This, the most complicated procedure is carried out after silver removal. It involves dissolution of blocks of circulating bismuth drosses at 400oC and subsequent introduction of magnesium and calcium into melted crude lead at 360 3370oC. These metals react with bismuth to form intermetallic compounds: Ca3Bi2, Mg3Bi2, Mg2CaBi2, which are poorly soluble in lead and are deposited on the bath surface. They are extracted as the so-called [enriched] bismuth drosses with bismuth content of 335%. Then the bath is cooled to 340 3350oC and [lean] circulating drosses containing 0.5 32% Bi are extracted. Repeated circulation of drosses can increase the bismuth content up to 5 311%, to give a lead3bismuth alloy containing 8 315% Bi [1]. The increase in the bismuth content from 5 311 to 8 315% results from removal of magnesium and calcium from the drosses with molten NaOH. A 5 3 6% fraction of Bi passes into the resulting alkaline melts. The existing technology for Pb 3Bi alloy production does not ensure isolation of bismuth-enriched (to more than 8 315%) products and is characterized by repeated dross circulation, which leads to loss of the target metal and involves additional consumption of reagents (magnesium, calcium, and sodium hydroxide). Various methods for dross enrichment with bismuth have been proposed. For example, centrifugal refining can enrich drosses to Bi content of 18 321% at its initial concentration of 5.7% [3]. Air bubbling through liquid metal (cupellation) at 900 3 950oC can raise the bismuth content of a Pb 3Bi alloy being treated from 14 to 40 3 60%, with simultaneous re-

moval of antimony, tin, arsenic, and tellurium [4]. This method has been implemented in industry. Of special interest are the publications [5 37] describing the possibility of using organic compounds in pyrometallurgical processing of lead3bismuth alloys. For example, in purifying bismuth to remove lead and copper by adding sulfur to a metallic melt, friable yields can be obtained if carbon or masut is introduced into the metal being refined [5]. It is recommended [6] that coal-tar pitch should be added to a melt to enrich dross with bismuth, which yields an alloy containing 40% Bi and 60% Pb. Dry drosses are obtained by adding sawdust to crude lead (modified Kroll and Betterton method [6, 7]). However, the authors of [5, 7] did not consider the mechanism by which the above-mentioned organic compounds affect the metallurgical processes under consideration. EXPERIMENTAL Our experiments and pilot tests made it possible to develop and put into industrial practice an improved method for lead refining, which provides lead alloys with high bismuth content. The technological process consists in the following. First, magnesium and calcium are introduced into crude lead at 3753 400oC (rather than the commonly used circulating dross), and then the temperature of the refining bath is raised to 475 3 490oC and circulating drosses are loaded. After settling for 25 335 min, dead oil (0.133 0.18 kg per 1 ton of lead to be refined) is introduced in portions with continuos agitation at 400 3 470oC. After liquation, solid powdered drosses (30 3 40% Bi, 50 3 60 Pb, 5310 Zn, 0.0153 0.02 Ag) are extracted, cooled to room temperature, and classified by sieving with 0.10 3 0.15 mm mesh. Drosses remaining on the sieve

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are loaded in the lead bath for recirculation, whereas sifted drosses (3 0.10 3 0.15-mm class) are remelted to obtain a lead3bismuth alloy. After the removal of dry drosses, the temperature is lowered to 330oC, and circulating bismuth drosses are taken off. The refining process is finished according to the standard scheme. Powder drosses of the +0.10 3 0.15-mm class, containing (%) 12317 Bi, 50 355 Pb, 25 3 40 Zn, and 0.06 3 0.07 Ag, are purified to remove silver, which diminishes the expenditure of metallic zinc by approximately 50%, and loss of silver and bismuth, by approximately 30%. Thus, in contrast to the common technologies, this method does not involve a laborconsuming procedure of lead bullion purification to remove zinc introduced into lead to recover silver. Powder drosses of the 3 0.10 3 0.15-mm class are remelted under a layer of slam (spent PbCl23ZnCl23 KCl3NaCl electrolyte used at the plant in electrochemical reactors for separating lead3bismuth alloys in ionic melts [8]). In this case, the following reactions occur
Mg3Bi2 + 3PbCl2 = 3MgCl2 + 3Pb + 2Bi, Ca3Bi2 + 3PbCl2 = 3CaCl2 + 3Pb + 2Bi.

at elevated temperature, and, simultaneously, lead is deoxidated and cooled. Thus, complete use of the reagents is achieved, and drosses very rich in bismuth are obtained in small amounts. This is also important for the subsequent introduction of a solid product of heavy oil residuals, e.g., dead oil, to be carried out successfully. Under these conditions, fine particles of bismuth intermetallics do not aggregate, which makes it possible to obtain bismuth-rich drosses. In carrying out this operation, dry powder drosses with high bismuth content (33 337%) are formed as a phase on the lead surface. The results of X-ray diffraction, mass-spectrometric, microscopic, and chemical analyses suggest that the forming particles of intermetallic compounds, and especially bismuth intermetallide Mg3Bi2, are wetted with bituminous hydrocarbons (asphaltenes etc.). This phenomenon eliminates wetting of intermetallic particles by liquid lead, because the adsorption energy of hydrocarbons on the surface of solid intermetallic particles is higher than the energy of lead adsorption. Consequently, bismuth drosses are formed as powders containing no coarse conglomerates with adsorbed or adhering lead. This results in that the bismuth drosses are obtained in powdered (dry) form and contain much lesser amounts of lead and greater amounts of bismuth. According to a mass-spectrometric analysis of the gas content of samples, the fine powder contains 2.5 and 3 times greater amount of, respectively, hydrogen and carbon dioxide than the coarse fraction does. This may indicate that bitumen is mostly adsorbed on fine-fraction particles of bismuth drosses. Our physicochemical study has shown that powder drosses with particle size less than 0.10 3 0.15 mm are largely composed of bismuth intermetallides (mainly Mg3Bi2 in amount of 30 335%, according to X-ray analysis). Drosses with particles larger than 0.10 3 0.15 mm additionally contain intermetallic compounds of zinc and lead. It was established that the fine fraction of dry powder drosses with particle size less than 0.15 mm contains (%) 43 350 Bi, 35 3 45 Pb, 0.13 0.5 Zn, 0.0023 0.003 Ag, and Ca and Mg the rest. Drosses of the +0.10 3 0.15-mm class are complex intermetallic compounds of zinc, bismuth, lead, silver, calcium, and magnesium. The expenditure for production of bismuth from an alloy containing 55 3 65% Bi is considerably less than that for production of the same amount of Bi from an alloy with bismuth content of 15% (this is the maximum Bi content ensured by the currently existing procedures). In this case, the expenditure of electric power and electrolyte, number of electrolyzers, floor
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Such a procedure is expedient because lead, which was previously dumped as a salt in a chloride mixture, is returned into the production cycle. The resulting lead3bismuth alloy contains 55 3 65% Bi and the balance lead. In pilot tests, we used dead oils of BN-IV and BN-V brands, which have softening points of 70 and 90oC, respectively. Special bitumens of A and G brands, and also pitches and other products of straight-run masut distillation, can be used for this purpose. The tests have shown that the initial introduction of calcium and magnesium into crude lead at 375 3 400oC and subsequent addition of circulating drosses at higher temperature (475 3 490oC) diminish the loss of active metals (magnesium and calcium) and thus make lower the process costs. According to this technique, the purification to remove bismuth is carried out at bath saturation with bismuth higher than 2%. The introduction of calcium and magnesium at 375 3 400oC ensures high dissolution rate at minimum loss of the active metals, which can be oxidized by atmospheric oxygen or moisture. At 475 3 490oC the dissolution of circulating drosses proceeds faster, the solubility of all the components added is higher

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area, and maintenance staff are diminished. This is confirmed by the following simple calculation of, e.g., the electric power expenditure. Let us assume that a plant accomplishes electrochemical separation of a lead3bismuth alloy containing, on average, 12% Bi and 88% Pb by the formerly used technology, i.e., it is necessary to transfer electrochemically 88 tons of Pb from anode to cathode in order to produce 12 tons of Bi. If, however, a lead3 bismuth alloy enriched with bismuth to 60% by the new technology is subjected to electrolysis, it is necessary to dissolve at the anode and precipitate at the cathode only 8 tons of Pb in order to obtain the same amount of Bi (12 tons). Consequently, the amount of lead to be electrolyzed in the second variant is 11 times less than that in the case of the standard technology. The expenditure of electric power, number of electrolyzers, etc. will be equally diminished. The results obtained in industrial tests of the lead refining technique under consideration, which yields a bismuth-enriched Pb 3Bi alloy, are presented below. The experiments were carried out in cauldrons with capacity of 125 3130 tons of crude lead (lead bullion). The sequence of operations was described above. The size classification of powder drosses yielded 5.3 3 6.0 tons of a fine fraction containing 43.7350.6% Bi and 2.8 33.8 tons of grit with Bi content of 12.6 317.2%. After remelting of the fine fraction under a fluxing agent (PbCl23ZnCl23KCl3NaCl), 4.23 4.5 tons of alloy with Bi content of 55.1359.9% were obtained. The process was implemented industrially and ensured a significant technological and economic effect. The environmental safety was improved, because we used a lesser number of electrochemical reactors producing lead by high-temperature electrolysis of a lead chloride melt. A somewhat different technique for lead3bismuth alloy enrichment was also developed and applied in industry. At one of lead-manufacturing plants, a Bi3Pb alloy is separated by electrolysis in hexafluorosilicon electrolyte, following the Betts procedure [1, 9]. A semi-finished product with Bi content of 8 315% is used as the starting alloy. It is desirable to raise the content of this metal, but to no more than 30%. If the bismuth content in Pb 3Bi anode plates is greater, the anodic process is significantly complicated. As lead is dissolved, the solid alloy lattice is disrupted and narrow channels are formed, in which lead hexafluorosilicate is crystallized. At the same time, a large amount of bismuth is dissolved and deposited at the cathode. Small pieces of the anode are crumbled and
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entrained by slam. The surface layer of the pieces consists of virtually pure bismuth, and the inner layer, of electrochemically unreacted lead. Industrial tests have shown that the Betts method for processing of Pb 3Bi alloys containing more than 30% Bi is inexpedient. Taking into account the aforesaid, we proposed, developed, and implemented industrially a somewhat different method for enrichment of bismuth drosses. The method, which is simpler and less expensive, consists in the following. To refine lead containing 0.5 + 0.1% Bi, a mixture of bitumen (45 375 wt %) and sawdust (25 355 wt %) is added, and the process is performed at lower temperature (370 3390oC). As a result, powder drosses containing 23 327% Bi are obtained and delivered to hydroelectrolytic processing by the Betts method. This procedure involves separation of drosses and thus eliminates the additional stage of bath heating to a temperature of 400 3 470oC, at which drosses are separated in the method described above. The addition of sawdust (which is less expensive than bitumen) prevents the possible inflammation of bitumen particles floating-up to the surface of a lead bath. Sawdust contains moisture, which evaporates to cool the upper layers of molten lead. It should be noted that sawdust is introduced into the liquid metal being refined not simultaneously with dead oil, but later, when obtaining [dry] powder drosses. In addition, sawdust plays the same part in the separation of intermetallic compounds of bismuth as dead oil. This method makes lower the cost of bismuth removal from lead because of the use, in addition to bitumen, of such a less expensive material as sawdust. Labor conditions are improved owing to the elimination of the possibility of bitumen inflammation. The energy expenditure, labor intensity, and reagent consumption are much lowered owing to a significant decrease in the amount of lead3bismuth alloy to be processed by an electrolyzer in a hexafluorosilicon acid solution. CONCLUSIONS (1) A modified Kroll and Betterton method for lead purification to remove bismuth has been proposed and subjected to pilot tests. The improvement consists in that dead oil or its mixture with sawdust is introduced into metal melt in a certain stage of refining to yield rich bismuth drosses in the form of a powder. The separation of the product is also a specific feature of the process.
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ZARUBITSKII 2. Betterton, J.O. and Lebedeff, Y., Trans. Metallurg. Soc. Am. Inst. Met. Eng., 1936, vol. 121, pp. 205 209. 3. Khodov, N.V., Suturin, S.N., Meshkov, E.I., et al., Byull. Tsvet. Metallurgiya, 1982, no. 6. pp. 22 24. 4. USSR Inventor Certificate, no. 653 916. 5. Polyvyannyi, I.R., Ablanov, A.D., Batyrbekova, S.A., and Sysoev, L.N., Metallurgiya vismuta (Metallurgy of Bismuth), Alma-Ata: Nauka, 1973. 6. Zelenova, E.I., Byull. Tsvet. Metallurgiya, 1971, no. 15, pp. 33 37. 7. German Patent 1 132 731. 8. Zarubitskii, O.G., Tsvetn. Met., 1990, no. 6, pp. 41 42. 9. Shivrin, G.N., Metallurgiya svintsa i tsinka (Metallurgy of Lead and Zinc), Moscow: Metallurgiya, 1982.

(2) The method for lead and bismuth separation, which was developed and implemented industrially, makes it possible to produce a bismuth3lead alloy containing up to 55 3 65% Bi. ACKNOWLEDGMENTS The author is grateful to I.P. Brovin and V.A. Shleenkov (DVGMK, Far-Eastern Mining and Swelting Combine) for help in the study. REFERENCES
1. Smirnov, M.P., Rafinirovanie svintsa i pererabotka poluproduktov (Lead Refining and Semiproduct Processing), Moscow: Metallurgiya, 1977.

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