N.

Sevryukov
MeTajijiyprHH
I],BeTHbIX
MeTajijioB

NONFERROUS METALLURGY
Translated from the Russian by I. SAVIN

EONIKO METSOBIO nOAVTEXNElO BISAIOeHKH rXOAHZ WIHXANlKnN METAAAEinN-METAAAOYPrnN

METALLURGY OF LEAD

Mir Publishers
H S ^ A T E J I b C T B O METAJIJiyprHfl MOCKBA

Moscow

CHAPTER 4

METALLURGY OF LEAD 28. Chemical Properties of Lead Lead is an element of group I V of the periodic tabl Similarly to carbon, silicon, germanium and t i n , i t is capa le of giving off four electrons. However, as i t possesses largest atomic number of the group, lead is more metall ill properties, while its oxides are amphoteric. Lead is known from ancient times, as its use in fifth the seventh millennia B. C. is now a well established fa An early acquaintance of man with lead was favoured the ease of reduction of the metal from ores, its low melti point and ductility which facilitated its working. Natural lead of atomic mass of 207.21 is composed four stable isotopes Pb^^*, Pb^o^, Pb=*o' and W\g to a relatively low boiling point, lead tends to vaporize in metallurgical processes as its vapour pressure even at 1000G is about 133 N/m^ (1 mm H g ) * ; at 1170C, 1330 N/m^ (10 mm Hg); at 1500C, 26 660 N/m (200 mm Hg). Volatility is not only undesirahle because of losses of metal with gases, but also hazardous due to the toxicity of vapours which bring about acute or chronic poisoning. Lead salts are toxic as well. I t is assumed that a low mean life-span of ancient Romans, not higher than 32 was caused by chronic poisoning from extensive use of lead for the manufacture of kitchen ware and water pipes. Lead is usually divalent. Compounds of this valency are for the major part salt-like. They dissociate with the formation of Pb^"*" cation, however, plumbites, salts of metals in which the anion is VhOl~, are not infrequent. Tetravalen lead derivatives plumbates with anions PbO|~, PbOJ" a
I I I accordance with the SI system of units, 1 mm Hg correspo to 433 N/m.

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other c o m p l e x anions, are but r a r e l y found i n the field of m e t a l l u r g y . C a t i o n Pb*"^, w h i c h enters the composition of P b C l i , P b ( S 0 4 ) 2 , ai^d other salts is also k n o w n . Because of a l o w negatfve v a l u e of the p o t e n t i a l (high h y d r o g e n overvoltage) lead is poorly soluble i n h y d r o c h l o r i c , s u l p h u r i c and h y d r o f l u o r i c a c i d s . I t s resistance to the a c t i o n of these a c i d s is further enhanced b y surface f i l m s of P b S O i , P h C l s or P b F whose s o l u b i l i t y i n w a t e r is l o w . S u l p h u r i c a c i d i n concentrations above 8 0 % oxidizes l e a d , g i v i n g rise to a r e l a t i v e l y r e a d i l y soluble a c i d s a l t Pb(HS04)2Corrosion resistance of lead to the action of a c i d s , a l k a l i s and m a n y other compounds h a s promoted its w i d e use i n the m a n u f a c t u r e of or for t h e protection of c h e m i c a l apparatus at the t i m e w h e n s t a i n l e s s steels and p l a s t i c s were s t i l l unknown. I n the n i t r i c a c i d l e a d dissolves v i g o r o u s l y according to reaction

Lead sulphide PbS, whose m e l t i n g point is 1114C, read i l y oxidizes i n the air at temperatures i n excess of 500C to give sulphate, basic sulphate PbS04-nPbO and oxide PbO. Lead silicates are manufactured by m e l t i n g together l i t h a r ge and silica. Of these compounds, the most easy m e l t i n g are PbgSioO^ (705C), P b o S i 0 4 (lAO^C) and their m i x t u r e s . Lead oxides and silicates can readily be reduced to metal by carbon monoxide at 600-700C. 29. Source Materials for Manufacture of Lead. Dressing of Lead Ores Lead is derived from ores and reclaimed lead. I n ores i t occurs i n the form of various minerals, the major of w h i c h is lead glance, or galena PbS. Ores of oxide lead minerals, cerussite PbCOs and anglesite P b S O i are treated as w e l l . However, the b u l k of lead is obtained from sulphide ores. Ores are generally of a complex v a r i e t y , chief lead associates being zinc, copper and silver. Content of zinc often exceeds t h a t of lead. Lead-zinc ores are chief raw materials for the manufacture of lead and zinc. Zinc occurs i n sulphide ores as sphalerite and w u r t z i t e which are polymorphs of ZnS, also termed zinc blende, and as marmatite w h i c h is contaminated w i t h i r o n . I r o n occurs as pyrite FeSg, less frequently as Fe^Sg, w h i l e silver is represented m a i n l y by argentite AggS. I n oxide ores, zinc is found as smithsonite ZnCOg, w h i l e silver, as m e t a l or A g C l , cerargyrite. Copper is often present i n lead-zinc ores i n i n d u s t r i a l l y valuable concentrations. I n sulphide ores, as sulphides, and i n oxide ores, as malachite and azurite. P o l y m e t a l l i c ores often carry gold, silver, b i s m u t h , a n t i mony, arsenic, cadmium, t i n , g a l l i u m , t h a l l i u m , i n d i u m , germanium, selenium and t e l l u r i u m . Gangue of sulphide lead-zinc ores is composed of quartz, barite, calcite and small amounts of a l u m i n i u m , i r o n , magnesium and calcium silicates. Ores occur i n solid masses or as disseminated ores, contained most frequently i n quartzites and siliceous shales.

3 P b + 8HN03

3Pb(N03)2 + 2NO-i-4H20

and w h a t m a y be of interest, at a lesser rate i n concentrated acid as c o m p a r e d to a s l i g h t l y d i l u t e d one, because of a poor s o l u b i l i t y of P b ( N 0 3 ) 2 i n a strong a c i d . O x i d a t i o n of m e t a l i n the air at u s u a l temperatures is prevented b y a t h i n surface f i l m of oxides. Mo ten lead at temperatures i n excess of 500C v i g o r o u s l y oxidizes to P b O , t e r m e d l i t h a r g e . I n m o l t e n a l k a l i s , l i t h a r g e dissolves to give p l u m b i t e PbO + 2NaOH NazPbOa + H2O

W h e n separated from m e t a l l e a d , l i t h a r g e is oxidized b y air oxygen to Pb304 ( m i n i u m ) w h i c h is used for the m a n u facture of l e a d storage b a t t e r i e s , p a i n t s and p u t t i e s ; at temperatures higher t h a n 550C, m i n i u m decomposes

2Pb304--v6PbO + 02
L e a d d i o x i d e PbOa is obtained t h r o u g h o x i d a t i o n of m i n i u m b y n i t r i c a c i d and other oxidizers and b y e l e c t r o l y s i s of acid lead n i t r a t e s o l u t i o n s . L e a d d i o x i d e is used i n the m a n u f a c t u r e of storage batteries and as a strong o x i d i z e r i n c h e m i c a l syntheses.

234

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235

Approximate below, % :

compositions
Pb Zn Cu Fe S . . . . , . . . . . .

of
1.2 1.35 0.6 5.0 5.0

lead-zinc ores are g i v e n 2.3 2.5 1.0 1.8 6.2 1.6 4.0 0.5 8.5 16.0

noble metals generally pass to the copper-lead concentrate, their amounts i n the zinc concentrate being r e l a t i v e l y low. Another distinguishing feature is the predominant passage of b i s m u t h to lead concentrates and t h a t of cadmium to zinc concentrates, this being of a major importance for their subsequent recovery together w i t h lead and zinc.
Table T y p i c a l Performance of a P o l y m e t a l l i c Ore F l o t a t i o n
Yield, Ore c o n s t i t u e n t s mass of ore Cu Pb Zn Au Ag

Necessity for a complex u t i l i z a t i o n of lead ores and a c o m p l e x i t y of their composition have conditioned a wide use of f l o t a t i o n for t h e i r processing. Lead is no longer smelted d i r e c t l y f r o m ores, as f l o t a t i o n allows enriching even the lowest ores, ones t h a t contain a mere 0.3-0.5% Pb. F l o t a t i o n enrichment of lead-zinc or copper-lead-zinc ores involves the f o l l o w i n g steps. First separated is a b u l k lead-copper concentrate, then a zinc concentrate and a p y r i t e concentrate follows i n succession. Lead-copper concentrate is next d i v i d e d b y re-flotation into copper and lead concentrates. P y r i t e concentrate is separated from these ores for the production of sulphuric acid or for the recovery of gold and silver, associated w i t h p y r i t e . Sometimes direct select i v e f l o t a t i o n is more advantageous, when p u l p is treated w i t h various reagents t o y i e l d i n succession a lead, a copper, a zinc and a p y r i t e concentrates. Sulphide minerals of copper and lead are more amenable t o f l o t a t i o n t h a n sphalerite and p y r i t e . The former are floated i n the f r o t h b y the action of small amounts of xanthate (a collector). I n r e - f l o t a t i o n , copper minerals are depressed b y sodium cyanide, w h i l e galenite is floated t o f r o t h . NaCN adsorbed b y the surface layers of copper minerals t o coat t h e m w i t h f i l m s t h a t accept no collectors, whereas galenite behaves d i f f e r e n t l y and retains i t s f l o t a b i l i t y . Sphalerite and p y r i t e are separated by carrying out the f l o t a t i o n i n an a l k a l i m e d i u m , i n the presence of l i m e . F l o t a b i l i t y of p y r i t e is then depressed, w h i l e sphalerite is activated b y additions of copper sulphate. Table 20 presents a t e n t a t i v e performance of a p o l y m e t a l l i c ore f l o t a t i o n . I t can r e a d i l y be seen t h a t the b u l k of noble metals is d i s t r i b u t e d between copper and lead concentrates. A part of gold and silver is associated w i t h p y r i t e , a fact w h i c h makes i t i m p e r a t i v e t o separate the p y r i t e concent r a t e . I f the copper concentrate is not separated i n f l o t a t i o n ,

20

% of

%
2.3 47.2 0.8 0.18 0.1 1.08 4.86 14.5 48.1 1.0 0.98 6.96 3.67 6.6 0.84 0.79 0.01 0.72

g/t

C o p p e r concentrate Lead concentrate Z i n c concentrate P y r i t e concentrate Tailings S t a r t i n g ore

9.44 27.8 1.41 3.7 11.45 2.47 0.84 15.0 62.7 0.1 3.14 100.0

163.0 73.4 32.3 27.7 0.005 37.0

D i s t r i b u t i o n of cadmium and disseminated elements among products of selective f l o t a t i o n of lead-zinc ores is shown i n Table 2 1 .
Table D i s t r i b u t i o n of C a d m i u m a n d D i s s e m i n a t e d E l e m e n t s A m o n g Products of S e l e c t i v e F l o t a t i o n of L e a d - Z i n c Ores*, %
Concentrates Elements lead copper zinc p y r i te Tailings

21

Cadmium Indium Thallium Gallium Germanium Selenium Tellurium

* According N o . 6, p . 3 9 . to

2-12 2-6 7.1-100 1.4-2 U p to 20 24 32

19 10

39.9-74.1 2.3-66.0 U p to 5 3.6-5.2

Vinogradova,

5-56 4-93 U p t o 12 U p t o 90 91-98 74-98 30-87 20 13 30-87

data

by M . A ,

Tsvetnye

MetaUy, 1959,

2S6

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Cadmium, i n d i u m , t h a l l i u m and germanium are mostly isomorphic w i t h zinc blende, i n d i u m a d d i t i o n a l l y w i t h galenite, w h i l e selenium and t e l l u r i u m predominantly w i t h i r o n and copper sulphides. A l l these disseminated elements f o r m no minerals of their own or are found i n rarely occurri n g minerals, t h i s fact u n d e r l y i n g their generalizing name. Lead concentrates from lead-zinc ores may be exemplified b y a f o l l o w i n g composition, % : 39-78 Pb; 2-15 Z n ; 0.3-4 Cu; 2-7 Fe; 14-20 S; 1-4 SiO.; 0.3-2.3 CaO; 0.1-0.6 A l ^ O , . Secondary raw materials are various lead and lead alloy scrap; up to 3 0 % of a l l lead are now smelted from secondary raw materials. 30. Techniques for Smelting Lead from Concentrates Reducing Smelting

Coke

Fluxes

concentrate

Raastina Sinter

and

r
I

siniering_^ dust-laden carrvna Remavai af gases SO2 dust

Blast ^

furnace

smslting ' lead \flrnacr ^hlast: bullion

y,

Gazes contain I no SC

Dust

To damp ar addltiRefining anal treat meni fur Cu. recoverj/ of lead * and zinc -1 \i Commercial

To sulpfiuric manufacture

add f^^SO^

to remove fis.Sb.SnMf^t^.^.BiMf^a J 1 Wizste

A smelting technique t h a t has found t h e most extensive use i n lead manufacture is a reducing blast furnace smelting w h i c h is preceded by an o x i d a t i o n sintering intended to t u r n sulphides i n t o oxides and obtain the charge materials i n the f o r m of sinter. Galenite is oxidized according to reaction (12). Sinter is smelted together w i t h coke to reduce lead PbO + C O - > P b + COa (131)

To separate ireaimeni for recovery of lead and impurities

F i g . 52. Load

reducing s m e l t i n g

Ore-Hearth

Smelting

This technique known from ancient times is now used for the processing of very r i c h concentrates containing 7578% Pb. . . 1 . A i r is injected into the charge composed ot almost completely pure lead glance and l i m e . Lead sulphide oxidizes to PbO (12) and to PbSO* 2PbO-t-2S02 + 0 2 - > 2PbS0; (132) The o x i d a t i o n is slow. The remaining sulphide interacts w i t h oxide t o y i e l d lead 2PbO + Pi)S - ^ 2 P b + S02 (133)

Smelting conditions are adjusted by c o n t r o l l i n g the cons u m p t i o n of fuel and coke i n a manner t o reduce i r o n to FeO only and t o transfer the latter to slag. I m p u r i t i e s of a great a f f i n i t y for oxygen are collected i n the slag, w h i l e others are reduced to metals and become dissolved i n lead. Resultant lead b u l l i o n , contaminated b y i m p u r i t i e s , is separated w h i l e molten^from the lighter slag and transferred t o refining units. Reducing s m e l t i n g is carried out i n blast'furnaces w h i c h require a l u m p feed, the way t o solve t h e " p r o b l e m being sintering combined w i t h roasting. Fluxes required i n smelti n g are introduced into the sintering feed. A flowsheet for a lead reducing s m e l t i n g is shown i n F i g . 52.

The reactions are endothermic, Mi > 0, and t o make up for the heat losses a small amount of fine coal or coke is added to the concentrate.

Ore-hearth smelting reactions are possible at temperatures as low as 700-800"G, which are insufficient for the melting of the charge which remains solid. Droplets of reduced lead evolve from the loose charge incompletely, and besides, the reactions among sulphides and oxides are broken off because of the separation of the

238

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239

Fig. 53. Ore-hearth for smelting lead Jbasin; 2water jacket; 3apron plate; 4frame; 5rabbUng mechanism

interacting substances by various impurities. Lead's extraction is but partial, and the process waste, grey slag, contains up to 30% Pb and requires additional treatment.
A hearth for lead smelting is shown in Fig. 53. The basin is an elongated cast iron box about 2.4 m long, 0.5 m wide and 0.25 m deep with walls 50 mm thick. The hearth is placed on a brickwork or a steel frame. The furnace working space is enclosed on three sides by water jackets, and on the front, by a curtain of sheet steel that stops short of the basin and leaves a 500-mm opening above the basin which extends throughout the length of the front edge.

A cast iron apron plate with a runner along its outside edge adjoins the basin. The rear water jacket carries tuyeres arranged in-line somewhat above the edge of the basin. The hearth is started-up by heating the basin and filling it with molten lead. The charge, composed of lead concentrate, lime and fine coke or coal, is fed upon the surface of molten lead. The quantity of lime is 2-3% of the mass of the concentrate, and consumption of coal is 3-8% of the mass of the charge. Lead is pro-mixed with the concentrate. The materials are charged in a manner to slope from the back wall to the front open edge of the bath. The tuyeres are underneath a layer of charge materials. During smelting the charge is stirred by means of a rabble-arm actuated by a mechanism that slides along suspended tracks throughout the length of the front open edge of the basin. The end of the bar, that dips into the charge materials, moves in a vertical plane and simultaneously travels throughout the length of the hearth. The melter who operates the hearth withdraws at regular intervals a portion of the charge materials onto the sloping cast iron plate and grades them by appearance. Poorly smelted charge is pushed back into the hearth, while gray slag is removed. Lead droplets that have separated in the process trickle into the runner on the outside edge of the plate. Gases from the furnace working space are exhausted via a flue to dust catchers. An amount of dust carried away by the gases runs up to 25-30%, and, therefore, an adequate dust collection is essential to the ore-hearth smelting. Coarse dust settles in flues and settling chamber, while the finer sizes are collected in sleeve filters or electrostatic precipitators. When 70 to 75% lead concentrates are processed, direct extraction to crude lead is 70%, while overall recovery, inclusive of the metal extracted in treatment of gray slag, is 95-97%. The distribution of lead among ore-hearth smelting products may be described in the following terms: lead bullion, 65-70%; gray slag, 15%; dust, 15-20%. These data are conclusive evidence that as present-day standards go ore-hearth smelting is but an auxiliary treatment technique that allows a partial recovery of lead from rich concentrates in a single operation against small consumption of fuel and fluxes. Hearth capacity is 6-10 t of concentrates in 24 hours per metre length of basin. Basins are not built in lengths greater than 2.5 m because of difficult servicing.

A smelting technique, similar in chemistry to the orehearth method, is sometimes carried out in electric furnaces. The starting lead concentrate, with 65-70% Pb, is pelletized together with ground recycled sinter and dust. The pellets

Reaction

Smelting

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are sintered i n sintering machines at 800C. Sinter which carries 5-6% S is smelted i n electric furnaces at 1350G. U p t o 9 8 % Pb are extracted t o lead b u l l i o n and sublimates and 1.5% only is lost w i t h slags. Because of a s m a l l consumpt i o n of fluxes t h e y i e l d of slags is rather s m a l l , sublimates being recycled i n sintering. Electric power consumption is about 600 k W h per t o n of charge. The major advantages of this technique core considered t o be i t s h i g h smelting rate and improved w o r k i n g conditions as compared t o t h e blast furnace or ore-hearth smelting. 3 1 . Roasting and Sintering of Lead Concentrates I n order t o obtain calcine as l u m p sinter t h a t is suitable for a reducing blast furnace smelting, lead concentrates are roasted fused together w i t h fluxes i n sintering machines whose design is k n o w n f r om Para. 25. Sulphides inflame on t h e surface of t h e charge from the action of i g n i t e r gases.Then, as t h e pallet cars move above the w i n d boxes, t h e u n d e r l y i n g layers of t h e charge burn as w e l l . Oxidizing roasting i n the sintering machines differs from t h a t i n m u l t i - h e a r t h furnaces b y a greater speed of gas flow w i t h respect t o a r e l a t i v e l y motionless charge and r e l a t i v e l y h i g h temperatures inside the body of materials. The chief sources of heat are ox i da ti on of PbS (12), AH = = - 840 k j ( - 2 0 0 kcal), and of p y r i t e (69), AH = = - 3310 k j ( - 7 9 2 ) kcal). Zinc blende, of w h i c h there is l i t t l e i n the charge, oxidizes according t o t h e reaction 2ZnS + 302-^2ZnO + 2S02; AH = - 8 8 0 k j ( - 2 1 0 kcal) (134)

by their bonding w i t h lead oxide i n t o stable arsenates, a n t i monates and sulphates. Oxides of lead, cadmium, sulphides of lead^ a n t i m o n y , t i n and metallic lead possess appreciable vapour pressures (see Table 22) at sintering temperatures. They evaporate p a r t l y and are carried away by gases.
Table 22

A p p r o x i m a t e D a t a on V o l a t i l i t y of Some Metals a n d T h e i r Compounds Vapour pressure, N / m 2 (mm H g ) , at temperatures, C

750-850 1000-1100

Metals and compounds

Lead Lead oxide

3.5
(2.6-10-2)

Lead sulphide Antimonous sulphide

Arsenic trioxide

13.3 (0.1) 266.6 (2.0) 1200 (9.0) 10131 (760)

6G6.5-799.8 (5-6) 533.2-1999,5 (4-15) 2266.1 (17.0) 17 329 (130)

O x i d a t i o n of such i m p u r i t i e s as arsenopyrite (72) and other arsenic sulphides, as w e l l as of a n t i m o n i t e Sb^Sg results chiefly i n readily v o l a t i l e trioxides, as,

2Sb2S3 -f IIO2

2 S b A 4 6SO2

(135)

Formation of higher oxides of these elements and of sulphur t r i o x i d e according t o reaction (18) is enhanced

The charge sinters because of t h e formation of r e a d i l y melting compounds and alloys. Lead silicates and their alloys melt i n the range from 670 to 883C. Eutectics i n the system S i O j FeO CaO soften at 1030-1050C, and sulphides and their mixtures, do so w i t h i n the temperature i n t e r v a l between 800 and 1100G. A n early sintering is objectionable as the easy-melting constituents may coat the s t i l l unoxidized sulphide p a r t i cles, preventing a l l access of air t o their surface, w i t h the effect that unoxidized sulphur w i l l remain i n the sinter. However, adequate decomposition of sulphates and agglomeration sintering should be completed at 1000-1100C. Premature sintering of charge materials can be prevented by m i x i n g the concentrate w i t h ground fluxes (in amounts required for the subsequent melting) and returns (fine sinter unsuitable for smelting) which separate the easy-fusing concentrate particles. Besides, the limestone t h a t is i n t r o -

16-0S15

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Chapter 4. Metallurgy of Lead

243

duced into the charge dissociates in sintering to CaO and CO2 with an absorption of heat, thus preventing a sharp increase in temperature. A similar temperature control at ignition is exerted by water which is sprayed on the charge materials before they are fed to the sintering machine. Moistening to 8-10% promotes sticking of concentrate particles into small balls which form a less compact bed

F i g . 54. P a n pelletizer opeHetizing diagram; bgeneral view of pan pelletizer

than a powder and prevent dust formation when charge materials are fed to the machine. The charge is blended with 2 or 3 parts of the previously formed fine sinter, unsuitable for smelting because of its fineness, or i t is roasted twice (double sintering). The choice of the technique is governed by the composition of raw materials and local conditions. The amount of sulphur, burned per 1 of sinte-

ring pen conveyor in 24^hours is practically unaffected, lying between 0.7 and 1.2 t. Pelletizing (agglomeration) gained a wide recognition industrially in processing of powder materials. A humidified powder material is mixed by tumbling in a slowly rotating drum (barrel) or on the bottom of an inclined rotating pan. In the process, the material balls up or pelletizes to spheroid pellets (balls) up to 20 mm in diameter. I n many instances, it is more advantageous to roast pellets than powder in sintering machines. A pan pelletizer is shown in Fig. 54. A 4.2-m dia pan has a capacity of 20 to 50 t/h. Lead concentrates particles are for the most part finer than 0.1 mm, A similar fine grinding of fluxes and recycled sinter would have promoted greater homogeneity of the charge, but this would have lowered its gas permeability and increased processing costs. Therefore, fluxes are ground down to 6 mm, and recycled sinter down to 8 mm. Fluxes are crushed in jaw and cone crushers, and sinter, in roll breakers. The charge is fed to the sintering machine by an apron feeder via a humidifier from which the materials are discharged to a pendulum feeder that oscillates in a plane at right angle to the machine longitudinal axis (Fig. 55). The pendulum feeder spreads the charge over the width of the pallet car, and as the latter moves the charge is levelled by a fixed blade. Bed thickness is governed by gas permeability of the charge and lies between 200 and 300 mm. The degree of oxidation of sulphides depends on the lime the car resides above the suction boxes, its travel speed being 0.6-1.5 m/min. Sulphide oxidation rate and the temperature inside the bed of materials are affected by the quantity of air being sucked and can be adjusted by varying the vacuum inside the suction boxes. Sintering gases contain SOg, vapours of volatile compounds and dust. Dust is collected in dust catchers, and clean gases may be used for the manufacture of sulphuric acid, but only when their SO2 content is above 4%. A most concentrated gas is obtained at the beginning of sintering, in the first few suction boxes. As sulphur oxidizes, SOg percentage falls off. To minimize the effect of dilution, the
16*

Chapter

4. Metallurgy

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Lead

245

suction box is compartmented. A frequent practice is recyc l i n g of lean gases and their repeated suction through the charge bed. I n recent t i m e , much a t t e n t i o n is being given to up-draft sintering. I n this technique, suction boxes become blastd i s t r i b u t i o n boxes, a pressure, not a vacuum being provided inside t h e m . The blast permeates the bed of charge from below upwards. This technique prevents r a p i d disintegrat i o n of pallet car grating and facilitates recycling of sinter i n g gases (Fig. 56). I n the metallurgy of lead dust is often collected, i n bag filters which are sleeves 160-220 m m i n diameter and 2.8 to 3.5 m long, of cotton, wool, synthetic fabric or glassfibre. Bag filters operate on the principle of f i l t r a t i o n of dustladen gas through the fabric. A schematic diagram i l l u s t r a t i n g bag filter design is given i n F i g . 57. Dust-laden gas arrives along a pipe underneath a horizontal p a r t i t i o n provided w i t h branch pipes for gas-tight fastening of the open ends of sleeves. Closed ends of bags are suspended to a frame connected t o v i b r a t i n g mechanism. Gas is sucked through the fabric by a f a n , the dust remaining on the inside surface of the sleeves. The frame t h a t supports upper ends of sleeves is v i b r a t e d at regular intervals b y mechanisms 5. I n the process, gate 6 closes a u t o m a t i c a l l y , and the gas m o t i o n ceases. Dust t h a t has settled inside the bags falls from them i n t o u n d e r l y i n g bins and is discharged by screw conveyor 7. Bag filter dust collection efficiency may be as high as 90%, r u n n i n g costs being l o w . A shortcoming of this type of filters is a low capacity, w h i c h is mere 1-2.5 m^ per square metre per m i n u t e . Bag filters for cleaning large quantities of gases would have been quite b u l k y , and, therefore, they find chief a p p l i cation i n small-scale manufactures. I n p a r t i c u l a r , they are w i d e l y used i n the m e t a l l u r g y of lead where the amounts of treated gases are r e l a t i v e l y s m a l l . The temperature of gases entering the dust collectors should not exceed 100C otherwise the bags are l i k e l y to be damaged. A t the'same t i m e , gases should be heated above the water vapour dew p o i n t , as condensation of water on the surface of bag:s blocks fibre pares. Bags of n i t r o n , glass-

Chapter

4. Metallurgy

of

Lead

247

fibre and lavsan are more heat-resistant (respectively 130, 150 and 250C), but they are more expensive. Bags may be cleaned of dust not only by mechanical v i b r a t i o n , but by air blown i n the reverse direction to norm a l gas flow. To this end, a number of sections are disconnected from the common gas h a n d l i n g system and cleaned w i t h air flow i n a reverse direction to remove dust that has i n f i l t r a t e d inside the pores. I n modern practice, bag filters are preferably replaced by electrostatic precipitators w h i c h are of a greater efficiency although their collection a b i l i t y w i t h respect to lead and zinc oxide particles is lower. 32. Lead Bullion Smelting
Smelting Procedure

Sinter is smelted i n blast furnaces s i m i l a r to those for smelting copper or oxide nickel ores. Furnaces are provided w i t h an internal hearth from refractory b r i c k on a concrete foundation i n the form of a trough about 600 m m deep. Hearth fireclay walls are faced i n t e r n a l l y w i t h magnesite brick, the b r i c k w o r k being reinforced by a steel casing and a framework of steel beams (Fig. 58). Lead is tapped continuously through a siphon, a canal 250 X 250 m m i n cross-section. One end of the canal enters the hearth at the furnace b o t t o m , while the other end opens into a flat dish w i t h a discharge spout. After the hearth is f i l l e d , excess q u a n t i t y of lead flows from the siphon t o the dish and then to a ladle. Should the siphon be plugged, m e t a l can be tapped through holes located at the b o t t o m . The siphon adjoins the middle of one of the longer sides of the hearth. Modern large-capacity furnaces are provided w i t h two siphons spaced 2 m apart. Water jackets are s i m i l a r to those of copper smelting blast furnaces, but they are of a lesser height and arranged i n ^ t w o rows, one above the other. B o t t o m water jackets t h a t rest on the hearth are sloped 5-7 degrees to the inside. End-face water jackets are v e r t i c a l and have openings for accommodating the tapping water jackets which are iron plates w i t h cast-in coiled pipes and slag and matte tap holes.

Chapter 4. Metallurgy

of Lead

249

The tuyeres are arranged s i m i l a r l y t o the copper smelting blast furnaces and their diameter ranges usually from 100 t o 125 m m . The furnace top arrangements for charging materials and exhausting gases are of a gas-tight design t o i m p r o v e sanit a r y conditions. Lead smelting blast furnaces are up t o 8 m long. A t tuyere level they are 1.4 t o 1.6 m i n d i a , and t h e i r height from the tuyeres t o the furnace top is 5 to 6 m . The furnace is charged w i t h coke and sinter t h a t carries fluxes necessary for slagging. A n alternative practice is t o charge fluxes (gold-bearing ones preferably) d i r e c t l y i n t o the furnace, thus o b v i a t i n g the need for costly g r i n d i n g . The b u l k of the charge is less t h a n 100 m m i n size. Content of fines (lumps less than 25 mm) should not exceed 10 t o 1 5 % . Charging rate is governed by the descent of the column of materials, i t s level at the furnace top being maintained constant. Most of coke burns in the tuyere zone, the temperature there reaching 1400-1500C and even 1550G i n separate sections. Combustion products flow upwards, permeate the charge and give i t its sensible heat. Temperature inside the hearth is lower (900-1200C) than i n the tuyere zone. The temperature of waste gases at the furnace top is 150200C. Composition of gas gradually changes along the height of the furnace. Coke burns t o CO^ at the tuyere l e v e l . As the carbon dioxide ascends w i t h other gases t o higher levels of incandescent coke, i t is converted t o carbon monoxide. As the gases move further up, CO content falls off, w h i l e t h a t of COj rises, chiefly because of the reduction of m e t a l oxides. S t i l l i n sintering a part of lead is bound into silicates having a m e l t i n g point of about 700C. Soon after charging into the blast furnace, silicates begin t o melt and dissolve oxides of other metals. Therefore, oxides of lead, i r o n and other metals are reduced i n blast furnace smelting chiefly from a silicate melt t h a t trickles down countercurrently t o the stream of hot reducing gases. The a f f i n i t y of iron for oxygen is much greater t h a n t h a t of lead. I n smelting, the temperature and the CO concentra^

Heavy

Nonferrous

Metals

Chapter

4. Metallurgy

of

Lead

251

e d at such values t h a t w o u l d cause a reduction of lead and allow iron as ag. d i n part only, lead is not contaminaoluble i n m o l t e n lead. Despite this ot t o reduce i r o n , since i t causes b u i l d c h hamper furnace operation, and a ide content loses some of its essential er, b i s m u t h , a n t i m o n y , arsenic and d simultaneously w i t h lead and dissolr o n sulphides t h a t have not oxidized ther t o give mattes of m e l t i n g points G. Irrespective of what metals s u l the sinter, those metals pass t o m a t t e , affinities for sulphur and oxygen are copper, lead and iron. The f i n a l comis the effect of i t s interaction w i t h n t- [FeSl [PbS] ICusSi + (FeO) [CuaS] + {Pb}* (136) (137)

zinc and other metals are reduced t o 4 + 2C - > PbS + 2CO2 4H-2C^ZnS+2C03 (138) (139)

hates t h r o u g h i n t e r a c t i o n w i t h silica ossible - ] - CO PbSiOg + SO2 + CO2 (140) (141) + C O - ^ ZnSiOa-fSOg-f CO2

t reduction of sulphates proceeds at t h e i r decomposition, and, therefore,

closed i n r o u n d brackets are concentrations ets i n m a t t e ; and i n f a n c y brackets i n

desulphurization i n lead smelting generally lies between 20 and 4 0 % , the remaining sulphur passing to m a t t e . Lead smelting mattes have a density of 4800 to 5200 kg/m^. I n the hearth, they form a molten layer of their own, located between the lead and slag. Noble metals i n a sinter are i n elemental state (silver may be found a d d i t i o n a l l y as AggS). M o l t e n lead and matte are good solvents for gold and silver, and the noble metals concentrate i n these smelting products. Recovery of gold, silver and lead from mattes necessitates a d d i t i o n a l t r e a t ments i n v o l v i n g losses of metals and costs. Therefore, formation of mattes is undesirable and may be j u s t i f i e d i n smelting of cupriferous concentrates. I f such a concentrate were roasted t o a complete e l i m i n a t i o n of sulphur, copper would have been reduced to metal i n smelting and dissolved i n lead. I n the furnace hearth, where the temperature is lower than t h a t at the tuyeres, copper may settle out and plug the siphon and give w a l l accretions i n the hearth, grad u a l l y decreasing l a t t e r ' s capacity. This p o s s i b i l i t y is m i n i mized by leaving sulphur i n the sinter i n amounts sufficient t o form mattes. I n this case, most of the copper passes i n smelting t o matte and no accretions appear i n the hearth. I n lead smelting, zinc oxide is reduced to m e t a l whose vapours are entrained by gases and re-oxidized. Some of zinc oxide dissolves i n slag. Zinc sulphide is d i s t r i b u t e d between matte and slag. Zinc sulphide is poorly soluble i n slag and is found i n the latter as a suspension t h a t increases slag's viscosity. For this reason, i t is good practice t o roast dead ( u n t i l complete e l i m i n a t i o n of sulphur) z i n c i ferous concentrates. When both copper and zinc are present, a dead roast is also to be preferred as zinc is a greater smelting risk than copper whose crystallization can be countered b y increasing the temperature inside the hearth. The y i e l d of matte i n lead smelting is rather s m a l l . Separate t a p p i n g of matte is d i f f i c u l t because of a small t h i c k ness of layer, and, therefore, slag and matte are tapped together into the heated forehearth. As matte accumulates, i t is w i t h d r a w n from the forehearth through tapholes and treated b y a separate process. A p p r o x i m a t e matte composi-

eavy

Nonferrous

Metals

Chapter

4. Metallurgy

of Lead

2S3

%:
10.2 48.8 7.8 5.4 23.0 19.5 37.1 11.6 5.5 21.7 700 28.8 19.8 17.7 7.0 20.0 35.0 '15.0 15.0 7.0 20.0 1000

When materials high i n zinc are smelted, account should be taken of the fact t h a t slag dissolves much zinc oxide, whose s o l u b i l i t y increases w i t h higher FeO content and falls off w i t h higher S i O j and CaO contents. Given below are compositions of slags most suitable for the smelting of zinciferous charges, % :
SiOa FeO CaO ZnO 30.6 38.3 16.1 5.0 23.5 39.2 12.3 15.0 19.8 39.9 9.9 20.0 16.3 40.1 8.6 25.0

e column of charge materials carry but generally they are d i l u t e d w i t h as fuel. es settles p a r t l y inside flues, w h i l e llected i n electrostatic precipitators flues is recycled to roasting charge. ed metals, whose v o l a t i l e compound of the furnace b y gases, concentrate i c h are processed separately after rious values. ositions of dust collected from lead static precipitators and bag filters,

Slags contain from 0.9 t o 1.5% lead and from 0.2 t o 1.0% copper. Part of lead is present as unsettled droplets of m e t a l and m a t t e , and, therefore, i t is good practice t o settle slags i n heated settlers, where the slags are averaged i n the process of their accumulation before further t r e a t ment. Settlers are s i m i l a r i n design to electric furnaces and are equipped w i t h three carbon electrodes t h a t pass through the roof and d i p i n t o the slag m e l t . Electric current f l o w i n g through the layer of slag overheats i t , enhancing the s e t t l i n g of values. Volatilization of Lead and Zinc from Slags

0.40 77.8 2.51 0.045

1.57 63.83 13.20 0.34

2.30 )7.58 8.80 0.54

onstituent is c a d m i u m , its recovery ment. smelting conditions should melt on 50 and 1200C. Excessively fusible a rate i n t o the hearth so t h a t t h e i r t incompletely. I f slags are'excessionsumption of fuel is unavoidable. slag is t o b i n d and e l i m i n a t e f r o m nd silica. However, slags including o h i g h a density and their sepaoor. Besides Fe^SiOi t h a t is low, a fact w h i c h promotes reduction rocess of smelting. slag density and enhances reduci n g for i t i n silicates, since the a f f i silica is much greater t h a n t h a t of GO. -~^?h + CaSiOg + GO, (142)

Lead and zinc, dissolved and dispersed as matte and metal i n slag can be recovered by v o l a t i l i z a t i o n i n a slag-fuming furnace (Fig. 59) w h i c h is b u i l t of water-cooled jackets resting on a cast iron plate. The furnace measures 3 X 7 m i n p l a n and is up t o 10 m h i g h . The longer sides of furnaces carry 11 t o 36 tuyeres up to 100 m m i n diameter. Slag is_poured t o some level above the tuyeres, and pulverized coal, serving b o t h as fuel and reducer, is injected i n t o the furnace via tuyeres. CO from combustion of coal inside f l o a t i n g gas bubbles reduces zinc and lead oxides of the slag. Coal particles, w h i c h float up i n the slag chiefly w i t h the aid of gas bubbles formed of a m i x t u r e of CO and C O 2 that attach themselves t o the particles, also participate i n the reduction. A t a temperature of about 1300C reduced metals and lead sulphide v o l a t i l i z e . Their vapours, carried t o the slag surface, are oxidized and entrained by gases as fine dust w i t h 15 t o 25% PbO and 60 to 75% ZnO. Gases are cooled^

Chapter 4, Metallurgy

of Lead

255

^ 1

their sensible heat being recuperated i n waste-beat boilers and air heaters, and dust is f i n a l l y collected i n sleeve f i l l e r s . After the slag is blown (fumed), i t is good practice to settle i t once more i n a heated settler. This technique allows a recovery from slag of up t o 9 0 % Z n and 95 to 9 8 % Pb. Dust is processed i n zinc manufactures. Slag-fuming furnaces are batch apparatus t h a t process 40-50 t of slag at a t i m e over a period of about 2 hours. Coal consumption averages 2 0 % of the mass of the slag.
Lead Smelting Performance

Capacity (smelting power) of load smelting blast f u r n a ces varies from 40 t o 80 t / m ^ per 24 hours depending on charge composition and q u a l i t y of sinter. Homogeneous as to size and strong sinter is readily permeable to gases, this promoting uniform combustion of fuel and i m p r o v i n g its efficiency. These conditions also govern the combustion of costly fuel, coke, whose consumption varies f r o m 8 t o 17% of the mass of the charge. Coke consumption m a y be brought down by heating air i n recuperators w h i c h burn natural gas and by enriching air i n oxygen. Oxygenation of blast to about 2 6 % of oxygen reduces coke consumption b y 10-15%, increases furnace smelting power by 25% and brings down dust entrainment by 20-25%. Recovery of lead t o lead b u l l i o n is governed by charge composition, f a l l of side products and processing techniques i n v o l v e d . Concentrates contaminated w i t h small amounts of copper and zinc allow a recovery of Pb and noble metals of 9 5 % , recovery f a l l i n g off t o about 9 0 % , i f content of copper and zinc is h i g h .
Lead Reducing Smelting Charge Calculations

Calculate a charge for roasting and smelting containing 50% Pb, 12% Z n , 3 . 1 % Cu, 20% 6.5% Fe and 3% CaO. The available fluxes are materials listed i n From practical data on smelting of s i m i l a r

a concentrate S, 2% SiOg, Table 23. concentrates,

Chapter 4. Metallurgy 1. Heavy Nonferrous Metals Table 23 Composition of Fluxes

C o n t e n t of, % l

of Lead

257

SIOz

Fe

CaO

dissolving zinc oxide, i t is necessary to introduce all the three fluxes. Of the slags given in page 253, we choose the following composition: 20% ZnO, 20% SiO^, 3 1 % Fe, 10% CaO (ir rounded off figures). The yield of slag, calculated on the basis of dissolved zinc oxide, w i l l be 1 0 0 - 6 0 kg Denoting by x, y and z the quantities of iron, quartz and limestone respectively, we set up the equation of charge balance:
Amount to be slagged. kg I n iron ore, kg I n quartz, kg I n Umestone, kg I n slag, kg

artz

10.0 ] 80.0 7.0

60.0 10.0 5.0

2.0 1.0 50.0

is assumed to be as follows: 29% Cu; 0% S; 20% Fe. er^to matte is about 80%. Amount of tte from 100 kg of concentrate is 3.1.0.8 = 2.5 kg resultant matte is
2.5 29

Fe . . . . SiOa . . . CaO . . .

4.8 2.0 3.0

+ + +

O.G:r OAx 0.02J:

+ + +

OAy O.Sy OMy

+ + +

O.OSz O.OTz 0.50z

= = =

60-0.31 60-0.2 60-0.1

After multiplication by 100 and conversion, we obtain

100=8.6 kg

ur in the matte is 8.6-0.20 = 1.7 kg n in smelting is assumed equal to 20%, nt of sulphur in the sinter is
1.7'100 80

60x + iOy + 52 = 1380, 10:c + SOy + 7z = 1000, 2a: + 1/ + 502 = 300 The solution of the system of equations w i l l give us = 21.5; y = 9.4; z = 5.0
X

= 2.1 kg

To verify the calculation, we draw up a charge balance sheet, as shown in Table 11. 33. Lead Bullion Refining Lead bullion is generally of a following composition, %: 96-99 Pb; 0.05-2.4 Cu; up to 0.45 As; 0.6-0.9 Sb; up to 0.2 Sn; 0.005-0.07 B i ; up to 0.6 Ag. The USSR State Standard COST 3778-65 specifies six grades of lead bullion*, containing lead in quantities not less than, %: CO, 99.992; C I , 99.985; C2, 99.95; C3, 99.9.
I n c l u s i v e of extra-pure l e a d : COOO, 9 9 . 9 9 9 5 4 % 99.99852% P b .
17-0515

in sintering^is
20 2.1 20

.100 = 89.5%

g and smelting distributes itself between ses. Let us assume that 80% of Zn enters = 9.6 kg (12.0 kg in terms of ZnO). to be slagged (minus the amount going .5 - 0.20-8.6 = 4.8 kg f zinc that passes to slag is much greater SiOj and CaO. To form a slag capable of

P b , a n d COO.

art I . Heavy

Nonferrous'lMetats

Chapter 4. Metallurgy of Lead

259

f refining is to remove impurities and increao the specified standard level. I n the process per, noble metals, bismuth, arsenic, t i n
Lea-if buLlion Removal ^of copper I lead Copper-bearing I sHimm^ngs Removal of tin To recovery of arsenic and anfimanir Pb , Ca

The basic apparatus for operation according to the above flowsheet is a cast iron or steel kettle, heated by fuel oil, gas or electricity. Kettles are set in brickwork, as shown in Fig. 61. Combustion gases pass along a ring canal surrounding

Lead

Waste

\
Removal of stiver To recover]/ of and gold Pb, Sn. Sb, As

Lead Siliver crust Removal of zinc To recover}/ of I I ^gja,Pb,2n lead Zinc or waste val of bismuth To recovery of ' Pb.Zn Bismuth-bearing sHmmings lcium sium was^e ecovery of Fig, 61. Lead refining kettle
1brickwork; 2mantle ring; 3bottom supports; 4fircliox; platform; fistirrer; 7electric motor a n d gearbox Sworking

recover;/ of Pb, Bt

ig. CO. Refining of lead bullion

re extracted from lead as waste suitable inning of pure metals. A refining flowsheet . 60.

the kettle and are exhausted through a stack. Kettle capacity in terms of molten lead ranges from 150 to 350 tons. Kettles are filled and discharged by means of centrifugal pumps carried by an overhead crane from one kettle to another. Molten lead is agitated by portable stirrers (Fig. 61).
17*

heavy

Nonferrous

Metals

Chapter

4. Metallurgy

of Lead

261

of 100 to 160 r p m , the stirrer makes wnwards, f o r m i n g a funnel at the sure t a l . Reagents that are fed i n t o this b y the stream of lead and d i s t r i b u t e throughout the volume of the k e t t l e . ature control greatly simplifies lead own operating costs. Of a great conveelectrical heating of the kettles.
emoval of Copper

Treatment of d r y copper-bearing skimmings is a separate complicated processing stage, r e q u i r i n g the recovery of copper and lead and the noble metals they carry i n s o l u t i o n . A more advantageous technique for p r i m a r y r e f i n i n g of lead (copper removal) has been introduced of late at larger Soviet plants. Lead b u l l i o n is poured i n t o an electric furnace or a gas-fired reverberatory furnace. M o l t e n m e t a l b a t h i n the furnaces is up to 2 m deep and is heated t o 800900C at the b o t t o m , and to 450G o n l y at the t o p . A r i c h lead concentrate and soda (anhydrous) ash is fed t o molten lead, the amount of the former being about 8 % , and that of the l a t t e r , 1.5%. Copper is transformed to sulphide 2Cu + PbS - > CujS -h Pb Soda forms sodium sulphide and sodium sulphate 4Na2C03 + 4PbS SNaaS + 4Pb + 4CO2 + NasSOi (144) (143)

Combined m e l t i n g of sodium sulphide and sulphate results i n a m a t t e , w h i c h floats to the surface of the m e l t and whose m e l t i n g point is i n the neighbourhood of 650C. I t contains up t o 15% Pb and 50% Gu, w h i l e refined lead runs not more t h a n 0.4% copper. Subsequent fine r e f i n i n g b y sulphur is carried out as described above.
Removal of Tin, Arsenic and Antimony

These i m p u r i t i e s possess a greater a f f i n i t y for oxygen than lead. To remove t h e m , molten lead is treated w i t h a molten N a O H and NaCl a l l o y w h i c h contains an oxidizer, saltpeter, to oxidize the i m p u r i t i e s according t o the reactions* below 2As + 2NaN03 + 4NaOH - > 2Na3ASO4 + 2H2O + 2Sb - f 2NaN03 + 4NaOH 2Na3SbO, + 2H2O i- N2 5Sn 4- 4NaN03 - f O N a O H ^ 5Na2Sn03 + dH^O + 2N2 (145) (146) (147)

r i n lead decreases w i t h the temperat gives off crystals of copper-lead solid ty of about 9 t h a t float t o the surface. the better, the lower the temperature cooled. However, as temperature goes nds t o become more viscous, this slon g of solid particles and causing s k i m m o l t e n lead. as less lead as possible, k e t t l e is first -500G and d r y "skimmings" are remoforated bottoms, handled by overhead the purpose. A t 500C, skimmings are y r e l a t i v e l y l i t t l e lead w i t h t h e m . d i n t o a s i m i l a r k e t t l e and cooled t o mings t h e n carrying a viscous mass t e n lead. These " f a t " skimmings are r e f i n i n g stage. s are k n o w n as rough r e f i n i n g . I t redut o 0.2-0.3% o n l y . Elemental sulphur lead at 330-350G t o ensure fine r e f i phur give cuprous sulphide t h a t floats en the m e l t is allowed to settle. Fine are composed of CugS and PbS. To capture of lead, the temperature of 370''C before s k i m m i n g . A f t e r lead is , i t s copper content is not more t h a n s , containing some 9 5 % Pb and 3% ther w i t h " f a t " skimmings to the first batch of lead is treated.

A s m a l l amount of lead is concurrently oxidized t o sodium plumbite 5Pb + 2NaN03 4 SNaOH ^ 5Na,Pb02 + N2 + 4H2O
* Similar reactions of tliis type are also possible i n reduction of the saltpeter nitrogen to ammonia, but they are of a much lesser importance.

. Heavy

Nonferrous

Meatls

Chapter

4. Metallurgy

of

Lead

263

es not participate i n the process, but e the volume of the salt m e l t and t o scosity. consumption of reagents (in kg) per being removed:
NaOH . . . . . . . . 1.8 1.5 NaCl 1.0 0.6 0.5 NaNOa 1.0 0.6 0.6

usually low i n lead, and i t accumulates but r a r e l y i n the molten mixtures. None the less, a number of techniques have been developed for recovering t i n compounds.
Removal ol Silver and Gold

Silver and gold are removed i n a process k n o w n as desilverization b y i n t r o d u c i n g zinc into molten lead at a temperature of about 450G, the zinc combining w i t h silver and gold t o give chemical compounds whose m e l t i n g points are as follows, C:
AgaZng AgaZnj AuZn . . . . . . . 665 636 725 Au^Zng AuZnj . . . . . 664 475

processing stage (Fig. 62) is f i t t e d w i t h ing lead f r o m the k e t t l e to the w o r k i n g (reaction) c y l i n d r i c a l t a n k upon a layer of molten salts. The jet of lead is broken to s m a l l droplets of a greater aggregate surface area w h i c h is essential for a rapid o x i dation of i m p u r i t i e s . After passing as droplets through the layer of m o l t e n salts, the lead flows to the k e t t l e where i t is again sucked b y the pump and recirculated through the reaction t a n k u n t i l the specified p u r i f i c a t i o n is a t t a i n e d . Salts formed b y i m p u r i ties remain i n the melt as
alkali refi-

mulate i n the a l k a l i a l l o y , t e r hopper; the latter t h i c k e n S , thiS e; 5-layer ^^^^^ ^ symptom i n d i c a t i n g the necessity for alloy repis then closed, and as lead accumulates ces the a l l o y into a prepared ladle, the ng supplied w i t h a fresh p o r t i o n of the alloy is processed by a h y d r o m e t a l calcium arsenate, used in agriculture, e, u t i l i z e d in smelting of a n t i m o n y , and re-employed for lead refining. T i n is

suspensions

As

they

accu-

Besides, zinc interacts w i t h silver and gold to give numerous solid solutions whose m e l t i n g points are higher t h a n that of lead. Chemical compounds and solid solutions of zinc and noble metals are of a lesser density, and they float and form on the surface of molten lead a crust of silvery or z i n cky f r o t h . Zinc is p a r t l y soluble i n lead, its excess also floats above lead as saturated solution of lead i n zinc. Thus, the crust on the surface of lead is a complex product containing noble metals, lead and zinc. The c o n t a m i n a t i n g arsenic, a n t i m o n y and t i n increase the consumption of zinc, interfere w i t h the separation of crust, and, therefore, they should be removed first. Noble metals are removed from lead i n the same steel kettles. Zinc is introduced i n several steps b y means of a stirrer. A few crusts are skimmed i n succession. The i n i t i a l ones are r i c h and the l a t t e r , low i n noble metals. Crusts l o w in noble metals are recycled. A first addition at 500C is a lean crust from a preceding treatment. Once k e t t l e contents are completely melted, they are stirred for 20-30 m i n , then cooled to 450-480C. Then the first crust is skimmed. The procedure is repeated after subsequent additions are introduced. The second and subsequent additions of zinc are i n t r o duced i n accordance w i t h silver and gold contents in the m e t a l . Before each a d d i t i o n , lead is heated t o 450-480C.

I.

Heavy

Nonferrous

Metals

k i m m e d , cooled t o 340-350C. Three zinc lly sufficient to b r i n g down silver cone n t cycle, heating and cooling of lead 12 hours. Zinc consumption depends on ead being treated and amounts generally , whereas fuel consumption is about 3% part of lead is melted out (liquated) or press, has the f o l l o w i n g composition: nd 6 5 % Pb.
reatment of Zinc Crust

from crust b y d i s t i l l a t i o n , advantage zinc's greater v o l a t i l i t y as compared to ls. I n a now obsolete practice, d i s t i l l a t i n graphite retorts and coke furnaces over ours at a temperature between 1100 and f zinc was avoided b y charging 3-4% by coal or fine anthracite i n t o the retort ust. However, part of zinc resists d i s t i l i n the retort as semi-oxidized dust or ractice is to treat crust for zinc removal rode electric furnaces i n ratings of up ). Graphite electrodes are dipped i n t o nd calcium silicates t h a t covers molten y a mechanical feeder, coke fines being f 2 to 3 % . Some 9 0 % of zinc are driven of abont 1250C, and most of i t is coltal i n a condenser f i t t e d w i t h a stirrer, ttled out i n a dust collector. D i s t i l l a t i o n w i t h not more than 2% Z n , is discharged n zinc f r o m condenser is cast into pigs e removal of noble metals. tever i t s o r i g i n , is treated by cupellaly is o x i d a t i o n of lead to PbO i n small ces at 1200C by vigorous interaction

I.

Heavy

Nonferrous

Metals

Chapter

4.

Metallurgy

of

Lead

267

a l k a l i according to the reaction Zn + 2NaOH NazZnOs + Hg (148)

cupellation furnace, cupel, is b u i l t of losed i n a steel casing and set on a car, ed b y water jackets (Fig. 64). Molten ) t h a t floats to the surface of the alloy a w n , and the b a t h is charged w i t h fresh ead so as t o accumulate gold and silver. s been f i l l e d w i t h the alloy containing d silver, the remaining lead is completeamounts of litharge formed i n this opey the cupel walls. The gold and silver o molds and shipped to affinage plants aration t o obtain gold and silver.
Removal of Zinc

Spent alloys are leached by water to recover zinc oxide and to regenerate the a l k a l i . Vacuum refining is superior to the a l k a l i technique i n t h a t i t allows a part of the zinc to be separated as a lead

lead carries an excess of zinc i n .amounts of the mass of the m e t a l . r of techniques for removing zinc, freis vacuum s u b l i m a t i o n . A n apparatus e technique (Fig. 65) is handled by a cradard k e t t l e . A steel c y l i n d r i c a l bowl w i t h m is f i t t e d on the apparatus frame w i t h o w l communicates w i t h a vacuum pump. i n the axis of the bowl and houses the ipes w i t h impellers and steel disks at ff the pump upwards. The lead pump is a residual pressure of about 6.66 N/m^ d is continuously supplied to side pipes vacuumized space, w h i l e f a l l i n g droplets ken on the steel disks. A large aggregate plets promotes rapid v o l a t i l i z a t i o n of
Fig.

prior
of

to
VLica:/rF

appucaicjn

65.

A p p a r a t u s for

vacuum

sublimation

J k f i t t l c ; 2 f r a m e ; 5steel shell w i t h cooled bottom; 4 p u m p ; 5 p u m p motor; (jside pipes w i t h pulverizers a n d deflecting dislts

dense together w i t h some lead as large l b o t t o m . After a 5-hour operation of carries a mere 0.3-0.5% Z n . The apparak e t t l e , and the condensate w i t h 6 0 % Zn ked off the b o t t o m . This condensate is esilverization. , zinc is also removed by an a l k a l i techt i n , arsenic and a n t i m o n y which differs is required. Zinc is readily oxidized by

alloy which is suitable for the recovery of noble metals. However, vacuum refining fails to y i e l d commercial lead, and requires the removal of residual zinc by an a l k a l i method (148).

269 Removal of Bismuth

removed at a temperature of about 350C ome magnesium and calcium w h i c h comt o give chemical compounds and solid insoluble i n m e t a l l i c lead and float t o g points of some of the compounds are

addition of saltpeter or w i t h o u t i t . After this f i n a l p u r i f i cation, lead is cast i n t o moulds. The multi-stage pyrometallurgical lead refining technique described i n the present paragraph is complicated and labour-consuming. Up to 25% of lead goes to waste, direct recovery to commercial metal b u t rarely exceeding 7 5 % . Despite this fact, pyrometallurgical refining is a chief purification technique i n modern m e t a l l u r g y of lead. Electrolytic Refining

BigCa BisCaa Bi^Mga

507 928 715

n l y is used, b i s m u t h content can be broand when calcium and magnesium are n to 0.008%. Subsequent small a d d i t i o n s b i s m u t h content to 0.004-0.006% becauof i n t e r m e t a l l i c compounds of the type re insoluble i n lead. troduced i n t o lead as pigs, and calcium, lead. Lead-calcium alloy is prepared on alcium tends to oxidize i f melted d i r e c t l y refore, lead is first alloyed w i t h sodium, olten calcium chloride at a temperature y + CaCU ^ {Pb - C a } a i i y A- 2NaCl

e introduced i n 2 steps: 3/4 of the calculantroduced first, then the balance. After i c h b i s m u t h skimmings are removed and of b i s m u t h . Skimmings from the second ns are recycled. N e x t , ground a n t i m o n y he surface of lead is t h o r o u g h l y skimmed. ngs are remelted and cast i n t o anodes for b i s m u t h goes i n t o anode m u d , from melted out. of Magnesium and Calcium

f b i s m u t h lead s t i l l rims some magnesin t i m o n y , and, sometimes, zinc f r o m vacuese i m p u r i t i e s are removed simultaneousechnique through oxidation by a small

On the face of i t , electrolytic r e f i n i n g would seem t o bea more advantageous technique as i t allows manufacture of a pure metal i n one processing step only, electrolysis, w i t h a recovery of 9 6 . t o 98% Pb. However, a l l i m p u r i t i e s are collected i n a single product, slime of a rather complicated composition, whose complex processing is as yet a p r o b l e m . Extensive use of electrolysis is also prevented by the u n a v a i l a b i l i t y of a perfectly suitable electrolyte, since the solutions at hand are either too costly or toxic. Silicofluoride electrolyte, w h i c h contains 18% PbSiFg and 8% HaSiFg, allows a successful refining of lead subsequent upon a rough drossing. The process yields lead of grade CO against a current efficiency of 97-98%. Copper forms a solid insoluble crust on the surface of anodes. Regretfully, the preparation of this electrolyte necessitates a toxic and very corrosive fluoric acid. Vapours given off b y the electrolyte i n electrolysis are t o x i c as w e l l . A t some plants, silicofluoride solutions are used for the electrolysis of remelted b i s m u t h skimmings. B i s m u t h passes to slime where its content goes up to 60-70%. Slime is processed t o yield b i s m u t h . The electrolyte, w h i c h carries sulfamic acid HNHgSOg, also requires a p r e l i m i n a r y rough separation of lead. I t is non t o x i c , allows to remove a l l i m p u r i t i e s f r o m lead and obtain metal grade CO. Electrolysis is conducted i n reinforced concrete tanks protected on the inside w i t h asphaltum or v i n y l plastic. Each t a n k houses up to 20 190-kg anodes. Cathodes are manufactured from sheets of pure lead about 1 m m thick.

271 A l l elements, except for gold, are chlorinated and p a r t l y sublimated, but their b u l k goes i n t o slag. Data below on isobaric potentials of formation of chlorides at 1200C and their m e l t i n g points may serve as a rough guide on the order of chlorination of elements i n v o l v e d :
Chloride

n is, g / l i t : 130 Pb, 5 sulfamic acid, olligneol. Cathodic current density oss t a n k , 0.5 V ; current efficiency, , about 100 k W h / t . 5% Pb; 5% A g ; 10% Cu; 3 0 % Sb; anode mud to m e t a l , 8 0 % A g only ce d i s t r i b u t i n g itself between slag b i s m u t h between smelting products y. g of Gold and Silver old and Silver from Alloys

AuCls

PLCI2

PdCl2

FCCI3

AgCl

CuCl

PbCl2

ZnCl2

Melting poi n t , '^C

>o

12

45 315

60 1550

75 1366

100 950

140 732

arately manufactured f r o m alloys, t a i n , at adequately equipped res t r y plants ship their dore ingots m r e m e l t i n g of copper electrolysis crust processing to gold-refining ce, the content of noble metals i n escribed by p u r i t y standards, or of incoming raw tandard values:
Au Ag

materials are
Pt Pd

The above treatment yields gold of p u r i t y standard 995 which is stored as gold b u l l i o n or a d d i t i o n a l l y purified by electrolysis as indicated below. The latter is always necessary when content of p l a t i n u m group metals is h i g h . Chloride slag is composed chiefly of AgCl and CuCl. I t is crushed, charged i n t o bags, then placed i n a t a n k w i t h diluted sulphuric acid together w i t h sheets of i r o n . Silver is then reduced by ions Fe^"*" AgCl + Fe2^ ^ A g + Fe^^ r
''Fe3+

(149)
_.

roing

. ^^^=

0.77-0.80 0.00

60 20 0.5

900 970 700

1 " -

2 0.05 -

copper chloride oxidizes CuCl -h Fe3^

Cu^-^ + Fe2* - f C I "

(150)

ese materials are not homogeneous, an equitable settling of accounts s are averaged by m a k i n g an accepurnace and testing resultant ingots. ntaminated by zinc, lead, copper, and other elements w h i c h when e termed master alloys. f silver and the master a l l o y , melts for 1 to 3 hours at a temperature u r e of borax and quartz is charged p r i m a r y slag which is subsequentf l o a t i n g chlorides.

As ions Cu^"^ pass through bag c l o t h , they are displaced by iron (34). Ions Fe^^ are also reduced by i r o n , and, therefore, their content i n the solution is low, e q u i l i b r i u m of reaction (149) being shifted to the r i g h t . A sufficiently complete reduction of silver is attained i n two days at a temperature of the solution of 90-100C. Substituted silver deposit is pressed, melted and cast into 10-kg anodes as slabs about 10 m m t h i c k , whose gold assay should not exceed p u r i t y standard 200, and master alloy assay, p u r i t y standard 75.

Chapter

4. Metallurgy

of

Lead

273

Electrolysis

of

Silver

is a solution of AgNOg w i t h about l O O g / l i t of solution of silver at the anode and of the cathode are close to values given i n o shows t h a t copper dissolves i n advance of ulates i n the electrolyte. E q u a t i o n (26) h a t copper cannot contaminate the cathode less, contamination takes place because of a r i z a t i o n . Therefore, current density sho400-600 A / m ^ the electrolyte should be and accumulation i n i t of more t h a n ould be prevented. alloy of gold i n p u r i t y standard of more ivates the anodes w i t h the effect t h a t oxyding to reaction (24), voltage across t a n k ingly. a t i n u m and p a l l a d i u m is possible i n the the smallest amount of gold because of larization 2e ^Vd^*; E' = QMV E^i.2y (151) (152)

-2e=PPt2^

than 20 m g / l i t Te, thi explaining w h y the latter is removed to a greatest possible extent by thorough washing of cement silver, obtained from chloride. Cathodic starting sheets are made of t h i n sheets of silver or a l u m i n i u m . The deposit does not make a strong bond w i t h them. Large loosely interconnected crystals f a l l to the tank b o t t o m , from where they are removed by s k i m mers. When anodes dissolve, gold separates as mud w h i c h contains also some AggSe, p l a t i n u m , p l a t i n u m group metals and other compounds. Cathodes are coated w i t h a v i n y l chloride cloth t o prevent contamination of cathodic silver by m u d . Tanks having capacities of up t o 0.6 m^ are b u i l t of v i n y l plastics and reinforced w i t h wooden or iron frameworks. Temperature of the electrolyte is maintained at about 40C at the expense of heat given off by the passing current. The solution is air agitated. Voltage across t a n k ranges from 0.8 t o 2.6 V , depending on electrolyte composition and current density, and the power consumption is 300-600 k W h / t . Silver deposit, after i t is washed w i t h d i l u t e d n i t r i c acid and water and remelted, has a p u r i t y standard 999.9. On special order, customers may be supplied w i t h silver of a p u r i t y standard 999.99 or 999.999 w h i c h is obtained b y a second electrolysis. Spent electrolyte is stripped of silver i n separate tanks w i t h anode from low-standard alloys, w h i l e r e m a i n i n g Ag+ is then settled out as chloride. Electrolysis of Gold

, ions of the above metals may be reduced advance of silver and so contaminate i t . ccumulation i n the electrolyte should not 25 and 0.2 respectively. ent efficiency w i t h respect to silver is n when a simultaneous discharge of N O 3 ibly according t o reactions ^+ e = ; ^ N 0 2 + HaO; NO-i-2H20; = 0.80 V = 0.96 V : = 0 . 8 7 V (153) (154) (155)

i-3e~z^

+ 8 e " = f ^ N H t - f 3H2O;

s evolve (153, 154)*, probably, at an overomes down i f the electrolyte carries more
ons w i t h the formation of NO^ and NgOgQ^ are a e y are not considered here.

Treated b y electrolysis is a metal f r o m c h l o r i n a t i o n and mud from electrolysis of silver, after they have been treated by a multi-stage chemical r e f i n i n g . A l l this is melted i n induction furnaces and cast i n t o rectangular anodes of a mass of 2 or 3 k g . The latter are contaminated b y silver, p l a t i n u m group metals and r e l a t i v e l y small amounts of master alloy. The electrolyte is a solution of H A U G I 4 and H C l (up to 200 g / l i t A u and 80 g / l i t H G l ) . Gold dissolves according
18-0515

4C1- - 3e ^ AuClI; r = 0.93 (156) 2 G r - e " :^AuCl-; (157) tion (157) is possible because of a concentradue to either a high current density of fort of AgCl at the anode. disproportionate to give a metallic deposit as mud AuGla =e^ AuCl- -f Au -f 2Cr (158) of trivalent Au in the electrolyte greatly divalent Au. acidity and temperature, gold anodes pastion ceases and chlorine evolves according while oxygen fails to evolve through reacntly because of its high overvoltage on gold. onducted at a temperature of 5 - 0G and 06 f about 60 g/lit. palladium dissolve at the anode according
G r - 2 e " : ^ P t G i r ; r = 0.73V r~2e"^PdGir; 0.62V
(159)

(160)

To this end, an alternating current approximating in intensity the electrolysis direct current is caused to flow through the tank together with the direct current. It is readily apparent from Table 3 that the probability of the cathodic deposit being contaminated by impurities is quite low. However, platinum and palladium may settle together with gold, particularly at a high current intensity. To avoid this, concentration of platinum is kept below 50 g/lit, and that of palladium, below 15 g/lit. The concentration of other impurities in the solution should be maintained below, g/lit: Cu, 90; Pb, 1.5; Fe, 2; Te, 4. Spent electrolyte is stripped of gold in separate electrolysis tanks with graphite anodes, and then it is treated by various other techniques to recover the remaining gold and platinum group metals. Electrolysis of gold is carried out in porcelain, less frequently, in vinyl plastic tanks of 25-litre capacity. Anodes, 15 of them, are suspended on silver bars, three in a row, a cathode of corrugated gold foil 0.2 mm thick being placed opposite each row. The tanks are placed inside water baths, the electrolyte is agitated by bubbling air. Aggregate density of direct and alternating currents attains 1500 A/m^, and voltage across tanks is about 1 V. The purity of the cathodic deposit after mechanical cleaning by brushes and subsequent washing in nitric acid and ammonia is purity standard 999.9.
Review Questions

stituentscopper, lead, bismuth, iron, tin, ther metals form simple ions or complex ey generally have no effect upon the soluin solution as Fe^"^ reduces gold, increasing fer to mud i; + SFe^-^ Au + SFe^^ + 4Gr (161) n insoluble chloride according to reaction Cre~ ^ AgCl; E = 0.22V (162) rries less than 5% Ag, AgCl settles in the er is present in greater quantities, AgCl ith a strong crust and prevents its solution. ith up to 20% silver can be dissolved by nique which involves asymmetric current.

1. What is the usual valency of lead in metallurgical processing products? 2. 3, 4. 2. What valuable metals, in addition to lead, do polymetallic ores carry? Zn, Mo, Cu, Pt, Ag, Au, Cd, Bi, Al, Se, Te. 3. What methods are used for dressing polymetallic ores? Gravity concentration, magnetic separation, bulk flotation, selective flotation, electrostatic dressing. 4. What types of furnaces are used to smelt lead bullion? Reverberatory, blast, electric furnaces. 5. What is the succession of removal of impurities from lead in refining? Au, Ag, Zn, Bi, Cu, As, Sb. 18*