Ullmann’s _ Encyclopedia of Industrial... Chemistry Fifth, Completely Revised Edition Volume A 28 Water to ZinNumerical data, descriptions of methods or equipment and other information presented this book ‘have been carefully checked for accuracy. Nevertheless, authors and publishers do not assume any liability for misprint, faulty statements, or other kinds of errors. Persons intending to handle ‘chemicals or to work decording to information derived from this book are advised fo consult the | original sources as well as relevant regulations in order 10 avoid possible hazards, Editorial Director: Christina Dyllick-Brenzinger Editorial Assistants: Ilse Bedrich, Reinhilde Gutsche, Ingeborg Harders, Monika Pikart Miller, Ulrike Winter Library of Congress Card No. 84-25-829 A\ catalogue record for this book is available from the British Library, Die Deutsche Bibliothek ~ CIP-Finheitsaufnalime Ullmann’s encyclopedia of industrial chemistry /ed.: Barbara Elvers; Stephen Hawkins. [Ed. advisory board: Hans-Firgen Arpe ...]. — Weinheim ; Basel (Switzerland) ; Cambridge; New York, NY Tokyo : VCH. ‘eilw. executive ed.: Wolfgang Gerhartz Bis 4. Aufl. ud:T- Ulimanns Eneyklopadie der technischen Chemie ISBN 3-527-20100-9 NE: Gerhertz, Wolfgang [tsp]; Elvers, Barbara [Hrsg]; Encyclopedia of industrial chemistry Vol. A. Alphabetically arranged articles 28, Water to zirconium and zirconium compounds. ~ 5., completely rev. ed. — 1996 ISBN 3-527-20128.9 1996, © VCH Verlagsgesellschaft mbH, D-69451 Weinheim (Federal Republic of Germany Printed on acid-free and low-cblorine paper Distribution YCH Verlapsycselchlt, P.O, Box 101161. D-60481 Weinheim (Fedsrl Republic of Germany) Switarland: VCH Verlag AG, P.O, Bos, CH-4020 Be (Switzetland) ‘Great Briain and Ireland: VCH Publishers (UK) Lud, 8 Welington Court, Welington Stree, Cambvidge (CBr Az (Gres Bai) ‘USA and Canada: VCH Publishes, 353 Seventh Avenue, Filth Floor, New York, NY 10001 (USA) Japan: VCH, Eikow Building, 10-9 Hongo tchome, Bunkyo-ku, Tokyo 113, Japan All rights reserved (including those of translation into other languages), No part of this book may be reproduced in any form — by photoprint, microfilm, or any other means — transmitted or translated into a machine language without written permission from the publishers Authorization to photocopy items for internal oF personal use, oF the internal or personal use of specific clients, is granted for libraries and other users registered with the Copyright Clearance Center (CCC) Transactional Reporting Service, provided that the base fee of $5.00 per copy, plus $0.50 per page is paid directly to CCC, 27 Congress Street, Salem, MA 01970. 0740-9451/85 $ 5.00 + 0.30. Registered names, trademarks, etc, used in this book and not specifically marked as such ate not to be considered unprotected. Production Managers: Claudia Baumann, Peter 1. Biel Cover design: Wolfgang Schmidt ‘Composition, printing, and bookbinding: Graphischer Betrieb Konrad Triltsch, D-97070 Wiirzburg Printed in the Federal Republic of GermanyVol. A28 tain FeO and MnO as Man)O - (Fe, Mn,)0, has rsition 21% Zn0, 59% 8% Mn,0,, and can con- 1 MgO as impurities. ts ky magnetic, and it forms shs hardness 6.0-6.5, and ls of minor metallurgical xe bloom or hydrozincite, fed zine ore or zincite, bainite, (2n,Mn),SiO, ineral reserves worldwide L3x1O°C zine. Potent 8.1 x 10°. The undoubt- nese deposits are not in- {a9 no concrete informa be. otential reserves are listed vith 37.7% 10° t 20.3%), ‘of any country, over 90 ‘ed vuicanogente-sedimen- ad South America account known deposits. Western f world zinc reserves, of slant are in Ireland, Sun. (Kosovo). Australia. ac fof world reserves, the Vin Mt fea (Quaensland) v South Wales) 14 deposits in the GUS, ac- the total, are in the central Usbek. and Kirghiz. The Jpper Silesia) are also im- \w Materials [16), (1 y wine raw materials i ss containing 20-3 ne thigh sade) Tal zine production containing Vol. A28 Table 1. The ane reserve f the wold [2 12} 131 Conese ry United States 3 ral Mexico 3600 08 Peru n1s0 Rest of Latin 2360 fica sso 9s at Gemany 150 1313 Fialand 2000 ro 08 Ireland ss 300s Spain 5060 1001.0 Tsay 208 100 a Yogosiia 3900192000 (Kosov0) Rest of sas 25019 ian a7 20 ta 15 India 265016350030 Japan Yiu 50 ow 3 Res of Ava 116006 = 310026 GUS and 000 16210000 &S Europe Teal work! 185260 1000118050. 1000 ‘Thermal enrichment of such products in the Waelz kiln process gives a Waelz oxide contain ing 50-58% zinc and $—12% lead. The lead content can be reduced by calcination. Other sources of secondary raw materials include zine dross, which is produced 1n galvanizing plants and has relatively high zine eontent (50-85%) Zine-containing sludges (10-65% zine) spen catalysts (30-00% zine), and dusts from the brass industry (60 75% zine) The increasing problems in disposing of zine containing materials are resulting in the continu al extension of the range of zine-containing see ondary raw materials Zinc 513 4, Pretreatment af Raw Materials for the Production of Zine Metal 11) 14) 10), (18) (23) Pyrometallurgical and electrolytic zine pro- duction require an oxidic raw material. Sulfidie concentrates must be prepared for metal extrac tion by roasting, which removes the sulfur as 0, and converts ZnS to ZnO, but docs not remove gangue material Low-zinc oxic ores that are not suitable for ‘mechanical beneficiation (e.., by flotation), slag fue dusts, and other secondary raw materials are subjected’ to a thermal concentration stage, which usually consists of either slag fuming or roasting in a Waelz kiln 4.1, Roasting Both electrolytic and pyrometalturgical zine production require oxidic raw materials. Sulidie aw materials must therefore be converted to the oxidie form (known as calcine) before leaching Whereas early accounts of zine metallurgy listed a large number of roasting processes, Nu idized-bed and sinter roasting have now almost completely replaced older processes such as mul fiple-heurits aud Mush roasting, An essential 16 uirement of any roasting process i that it must be possible to recover and use the SO, from the waste ga. The various zane production processes re: quire feed materials with fundamentally diter- cet phiysical properties. A fine-grained calcine is necessary lor leaching with dilute sultunic acd Flotation concentrates meet this requirement if oxidized by roasting in a fluidized bed. On the hand, thermal processes requite a porous feed material in lump form, as provided by sinter roasting [18} Fluidized-Bed Roasting. Given a processed concentrate of suitable chemical constitution ‘and particle size, the fluidized-bed reactor allows a calcine suitable for the leaching process to be produced, The parameters to be optimized are bed height, gas velocity, residence time, and tem- perature, In the fuidized-bed reactor, the reac tion conditions are easily controlled and stabi tized. The theoretical relationships, as shown in the phase diagram Zn—Fe-S-O (Fig. 1), have514 Zine 15 0 os 2980,+Fe {SOs ins Fes 9001200 1600 “oo 500 600800 Temperature, °C Figure 1 Phase diagram ofthe spite 2a-Fe-S-0 [23} ‘The condition tha exis in most Mudinal-bd oases are sna ty the hatch area been thoroughly investigated (19), (22), (23). Flu idized-bed roasters generally operate at condi tions in which ZnO and Fe,O, are stable. Devel opments in clectrolytic processing technology have enabled the presence of sulfates and ferrites in the calcine to be tolerated Fluidized-bed furnaces are often operated in two stages, in the first of which the roasted product contains 6 8% S, This overflows while hot into a second fluidized bed and is roasted with an excess of air to a residual sulfur content of <1.5% [3, p. 662] Simter Roasting. The frst industrial applica- tion of sinter roasting was in the roasting of lead orein sintering pans. The erucial development in processing technology came from the sintering of iron ores the results from which are transferable tothe sinter roasting of sulfidic concentrates [21] Tris important that the temperacure of the mis- ‘ure should reach the sintering point. This is de- termined by the fuel content ofthe mixture (ie., fi single-stage sinter sousting, by the racy of concentrate to roasted recycled material), the particle size distribution of the mixture, and the flow resistance (controllable by means of the Vol. A28 Table 2. Charctersic values fr sater and flv be roasting compared with multiple heath roasting, p Maitiple Sintering Fidized-bed hearth bel aster easing spasiy, 00807 ~~ Throughout, d@ 6 «5008 Grins mm 15 5 3 Dustconten % 11S 2-33 80, inexhawst 4 no particle size), whieh ia (urn determines the air pressure difference both in the induced-draft and pressure sintering processes. The moisture con- teu of de uisture ipa important fassor here. Tt is important that all parameters affecting the process should be Kept as constant as possible. ‘Autumuatic utilis wut yet widely used. In contrast to fhidized-hed roasting, where ‘maximum reaction temperatures are in the range 990-930°C and no volatilization oevurs, mni- ‘mum temperatures in the sintering zone reach 1450°C, so that the cadmium and lead are ‘olatilzed to a considerable extent, For tis rea son, it is necessary to limit the maximum temper- ature in the sintering zone. In principle, the temperatures in the reaction zone during sinter roasting are sufficient to en sure homogeneous sintering not only of concen: trates but also of udded five dusts, dross, sludge, and other zine-containing materials. An impor- tant advantage of sinter roasting is thus that it enables theie materials to be prepared for shaft furnace treatment (Section 5.2) continuously land by the shortest route. The important charac teristic parameters for sinter roasting, Muidized- bed roasting, and roasting in a multiple hearth furnace are compared in Table 2 (3, p. 662}. 4.2, Pyrometallurgical Concentration Processes ‘The aim of pyrometallurgical concentration processes usually he venuval of zine from flue dusts, slags, and low-grade, zine-containing raw materials oF raw materials of complex compostVol. A28 les for sate ant idind bod ile hearth roasting, p. 663} ple Sintering Fh bed 07 so 00 0 0 10 wa tau determines the air thie the induced-draft and cesses. The moisture con- snimportant factor here. Tt parameters affecting. the 2L as constant as possible aot yet widely used. dized-hed roasting, where aperatures are in the range olatlization occurs, maxi the sintering zone reach cadmium and lead are rable extent. Pus dhs tea ‘mit the maximum temper- saperaturcs in te seautiou sting are sufficient to en- tering not only of concen: 4 flue dusts, dross, sludge, sing materials. An impor- er roasting 1s thus that it > to be prepared for shaft section 5.2). continuously te. The Important charac sinter roasting, Muidized- sting in a multiple hearth in Table 2 [3, p. 662} ical Concentration stallurgical concentration removal of inc from flue fade, zine-containing raw ials of complex composi- Vol. A28 ‘The Wael kiln process was originally used for the treatment of low-grade oxidic ores to obtain ‘oxide suitable for smelting (24). It is now mainly used as an enrichment process to Leal secon raw materials from zine metallurgy, e-., slags flue dusts, and sludges, Tn the Welz kil prowess, de zine and lead from the raw materials appear in the oxide product, together with much ofthe sulfur, chlo- Tine, sd Muoriae, both from the raw material and from the carbonaceous reductant. The zin: ‘metal is usually obtained from the oxide product by a thermal process. For ths, the oxide can be compacted by sintering or forming it into bri aquettes. If oxide with a low lead content is re ‘Quired, it must be calcined, i., reheated to 1100-1350°C without addition of ‘reducing agents, to volatilize the Pb as PbO. The Ws killa process is carried out in a slighty inclined, slowly rotating, lined Wael of rotary kiln through which ai is passed at a controlled rate so that the mixture of raw material and coke breeze does not fuse together. The residues are \scharged in a sintered but not molten state. Air from the furnace atmosphere diffuses ta limited extent into the reaction mixture which is carried up the walls of the rotating furnace, and strongly reducing CO/CO; atmosphere formed. This causes reduction not only of ZnO Dut also ot zinc ferrites and silicates, and reox dation to ZnO occurs after discharge. The fob Jowing reactions take place in the rotating turnace: Reaction inthe sod charge: 2a0 1 C »Zig) CO Reseton inthe ms paces TZnig) + 00+ 0, = 780 + CO, The heat liberated is due only to the overall reaction, ie, the combustion of C to form CO>, as the reduction of 2x0 to Zn is immediately reversed in the gas space above the charge The zine oxide leaving the furnace space is collected in bag fillers, As Uae sulfur saad halogens in the waste gnses are hound to the zine oxide, there are ‘no environmental problems. The iron com pouads in the charge are seduced to wuestite ani fo some extent ta iron metal. In practical opers- tion, the composition of the reaction mixture must be correctly formulated and an excess of fake breeze mnst he present to prevent the itor ‘containing components from fusing and forming incrustations in the furnace. The temperature Zinc 518 ‘Tale 3. Composition in wt) of reaction products from lag fuming plant in Por Pre, Aue Za_P GO FO 80, F_ GS Sag boos 183-26 147 256 210 O17 Za removal Oride 660 o2s 02 regime ofthe process can be controlled by means of the fling height, residence Gime, and ait Now ratein the upper part ofthe furnace. Overheating can cause inerustations to form and must be pre vented [24]-[27). Slag Fuming. In contrast to the Waelz kiln method, with which a range of raw materials ccan be treated, the slag fuming process is only used to remove zinc from molten slags from lead ‘and copper smelting (28) The zine oxide so ob- tained can be used for zinc production. The ‘molten slagis blown with reducing gases, so pro- ‘ducing zine vapor, which is burnt in the gas space above the molten slag by secondary air. The re sulting high-grade oxide is cooled ina waste heat boiler in an EGR and collected (3, p. 65]. The composition of the reaction products from slag fuming in Port Pirie (Australia) is given in Table 3 Oxide Caleination. The oxides obtained from ‘waelz kilns oF slag timing plants can be com- pacted in preparation for further processing by sintering or briquetting, without pretreatment. However, for electrolytic processing for pigment use, o for production of other zine compounds, removal of harmful elements such as Pb, Cl, and F isrequired. Thisis carried out by calcination in rotary kilns at 1100-1150 °C, Not only are the harmful impurities removed, but the material is, also densified (29), [30] 5. Production of Zine Metal (1)-(5} ‘There ate Give industial processes for the production of zine: one electrolytic and four pyrometallurgical. Their relative importance sdusing recent decades isillustrated in Figure 2, . 664), Although the horizontal retort was the ‘most important zine production process at the516 Zine wor 4) Percentage annual output —= dl ‘950 80 Figure 2 Annus outpts of the various ne produstion PEs eapesed as a pecentageof otal enna outpe ated curves) [8.65 tur of the century and stil accounted for ca. 50% of total production capacity in 1950, the process is no longer of practical importance. The {Question of whether the energy-intensive elec frolytie vine production process can retain or ever extend its lead depends on the development Of the energy supply situation 5.1. Pyrometallurgical Zine Production by the Retort Process Zine oxide, produced by roasting, is reduced by carbon according to the equation 200+ 0 +00 s ‘The reaction is 50 strongly endothermic that 5.4 MJ of heat is required to produce 1 kg of ‘anc. The reaction starts at ea. 110°C: and is Complete at 1300 °C, and the zine (bp 920°C) is therefore produced as a vapor. Zine production by the retort process hence involves not only r= duction ofthe oxide but also condensation ofthe zine from the vapor to the liquid state. Care must be taken to prevent reoxidation, and the zinc Vol. A28 ‘vapor must not come into contact with the com. bustion gases. The reduction must therefore be carried out either in vestels with exterior heating {fetorts) or by the electrothermal method. Hori= ontal, batch-operated retorts with circular or ‘dliptical cross section can be used, or furnaces Containing vertical, continuously operated re tors wth a rectangular cross section. The quai ty of the furnace vessels is of great importance for the process, especially their stability at high temperature, resistance to large temperature fluctuations, good thermal conductivity, imper meability 10 reaction gases, and resistance to- ‘wards chemical attack by the charge materials. Reduction in Horizontal Retorts. Zinc has been produced ia horizontal retorts since ca. 1800 in Belgium and Upper Silesia from smith- somite and later from roasted zine blende. Re- torts vary in their shape and arrangement in the furnace and in the fitting of receivers, in which the zine vapor produced in the retort condenses is a guid, Detachable devices made of shset metal (So-called allongen) are fitted to the con= onsers to collect zine escaping in the form of dust “The retort furnaces ate equipped with regen- erators or recuperators which utilize the hot sraste gases 10 preheat the combustion air and Nometimes the fuel gas. The retorts used to be charged by hand, an extremely labor-intensive ‘operation: one worker smelted ca. 0.5 t ore per Shift Moreover, the yield was poor, only 60% of the zine being obtained as molten castable meta 10% remaining uneeacted in the ash produced, tnd the rest reporting to the dross and dust in equal amounts. Although efforts were made to mochanize the process, especially the charging land discharging of the retorts, the main problem, i the poor efficiency (ca. 20%), could not be solved. The horizontal retort is no longer an i {ustrially important vine production proces, Reduction in Vertical Retorts. The poor eff ciency, batch operation, and above all labor in~ tensity of zine production in horizontal retorts provided the incentive to develop an improved process. The fact that the horizontal retort Was Inconsistent with the natural downward move tent ofthe charge and upward movement of the “ine vapor suggested that a vertical arrangement ‘would be better. Zine reduction furnaces were therefore constructed with vertical retorts, but fonly after overcoming major difficulties. TheVol. A28 {0 contact with the com- tection must therefore be sels with exterior heating ‘thermal method. Hori retorts with circular or an be used, or furnaces tinuously operated re- cross section. The quali- $ is of great importance ly their stability at high Sto large temperature ‘nal conductivity, imper rases, and resistance to- by the charge materials, ntal Retorts. Zine has zontal retorts since ea, pper Silesia from smith- ‘sted zinc blende. Re- and arrangement in the ag of receivers, in which ‘in the retort condenses 2 devices made of sheet ‘) are fitted to the con: ‘escaping in the form of are equipped with regen- 5 which utilize the hot the combustion air and ‘The retorts used to be xtremely labor-intensive smelted en, 0.5 ore per 4 was poor, only 60% of as molten castable metal, ted in the ash produced, 10 the dross and dust in th efforts were made to especially the charging sorts, the main problem, (a, 20%), could not be tort is no longer an ine fe production proces. TRetorts. The poor efli- ‘and above all labor i ‘on in horizontal retorts to develop an improved hhe horizontal retort was tural downward move- apwvard movement of the aa vertical arrangement reduction furnaces were sith vertical retorts, but major difficulties. The Vol. A28 Figure 3. Schematic diagram of vert stor [3,9 665) New Jersey retort ith plate condenser fore facovery ‘The ef aad und ight hao tions ae oated with respect to etch other, o) Charging bucket; b) Cone; c) Lead collector; d) In ‘lined channel, ) Condenser; f) Tap bole: g) Retort 1) Fa sift) Air nets) Ext sus exit open ings 1) Ask removal equipneat i) Ash bocket Re system is known as the New Jersey process. The furnace, illustrated in Figure 3, consists of a re- tort 13.5% high, 1.83m long, and 0.3m wide, constructed of silicon carbide. The retort isexter nally heated over a vertical length of 8 m (stat ing at 1.5 m from the lower end) to a temperature ‘of 1250~1300°C. Producer gas is fed from above into the heating chambers, and the exhaust gas phases out of the furnace at the bottom. The reaction airs fed through the sides ofthe furnace along its whole length. Above the heated part of the furnace is an unheated part 4m in length Which acts as a reflux condenser for the lead formed and is known as the lead collector. In the original design, the gas mixture passing out of the retort at 850°C was cooled to 500°C by a plate cooler, which also condensed and collected the zine. This was tapped off from time to time. ‘The zine dust formed was collected by means of ‘a water spray. The process was much improved by replacing the plate cooler by a spray con- denser. A graphite dsc, partially immersed inthe pool of molten metal and spinning at ca, 400 rpm, atomizes the metal so that the waste ‘gases From the retort passes through a metal fog. Zinc 517 The metal is collected at S00°C in an exterior ‘cooler. This prevents formation of dross, and the amount of zinc dust formed is reduced to 3% of the zine product. ‘The charge material, containing 60-70 caleine and 30-40% coal, is formed into bri quettes, which are then coked in a coke oven. The coked briquettes are charged into the top of the retort, After extraction of the zine from the briquettes, they are discharged from the bottom of the retort through a water lute. The zine-con taining gases discharged from the top of the re- tort are cooled to ca, 500°C in a condenser, in ‘hich the molten zinc collects at the bottom. The tail gases produced, which contain ca. 85% car bon monoxide, are scrubbed and reeycled to the producer gas stream, Furnaces with vertical torts are much more thermally efficient than those with horizontal retorts, and they have the further advantages of providing higher capacity, higher zine purity, and longer working life ofthe retorts, and, above all, do not involve heavy ‘manual labor or batch operation 5.2. Zine Production in the Shaft Furnace [31] Prolonged and extensive development work in the 1950s, aimed at utilizing the improved thermal efficiency and higher reaction tem peratures of the coke shaft furnace, led to the Jead~zine shaft furnace ofthe Imperial Smelting Corp. Thus, a process became available that could be used with raw materials of complex composition, such as mixed ores and secondary raw materials containing impurities that would cause severe problems in electrolytic zine pro- duction. Im the shaft furnace, the heat for the reduc- tion is provided by the oxidation of C to CO, ‘and CO. Under the eaetion conditions normally used in a shaft furnace, the zine vapor formed would be reoxidized to ZnO by the CO, in the furnace gas, Intensive research on the equilibria «enabled conditions to be found under which this reoxidation does not occur, In normal shaft furnace operation, the best possible heat utilization is achieved by using countercurrent flow to heat the charge materia ‘The furnaces are relatively tall, and furnace gas exit temperatures of ca. 200°C are aimed for. In faocordance with the Boudouard equilibrium, this results in higher CO, contents inthe Furnace518 Zine ‘eas. The zine shaft Furnace requires gas tempera fures of 1000°C. In order not to lower the fi nave gas exit temperature by the addition of the fold charge material, the coke is heated to = 800°C and the caleine is added as hot sinter “The shaft furnace obtains its heat of reaction from the combustion of coke in the reaction zone. This leads to large amounts of nitrogen in the furnace gas, lowering the partial pressure of the zine. Therefore, the heat required is generat fed to. large extent outside the furnace. Thus, the Combustion ar is preheated to 700--980°C, en- STbling the amount of furnace gas to be much reduced. The CO-rich furnace gas is cooled as it passes from the furnace tothe condenser. To pre- ent reoxidation of zine to ZaO, a small amount ff atmospheric oxygen can be auded to avoid a emperature drop. This process step must be carefully controlled. The zinc collects in a spray condenser. In contzast 10 the vertical retort process, lead is tised as the condensing Fiquid instead of zinc Dissolving zine in lead greatly reduces its active ty. As the solubility of zinc in lead is strongly temperature dependent, the zine can be precipi- {ated by cooling. In practice, a temperature of ca 550°C is maintained in the spray condenser, The Vol. A28 metal flowing out of the condenser is cooled to £440°C, causing the zin to separate from the lead ‘and float on the surface. It then flows over a weit and is collected. AAs the process does not take place under equilibrium conditions, the recovery Df f Line does not require the theoretically cal- ulated amount of lead (60 0), but ea. 400 t. The ine is either cast as commercial grade ingots (08.5% Zn) ot refined to higher grades. The first full-scale industrial furnace went in- to operation in Swansea in 1960. The eross-sec- tional area of the shaft was 17.2m', and this remains the standard size even today. ‘On licensing its ISO process, Imperial Smelting required that licensees should compare theit ex petiences of the process, and this has led to stan- Gardization of the major zine-producing plants fand to improvements in the plant performance: For example, the annual output of a furnace with a cross section of 17.2m? has been increased from 35000 t zine and 17000 ¢ lead in 1963 to $0000 t zine and 40000 Tead in 1990. At the same time the zine yield was increased from 91.7 to 95.5%, and the lead yield from 94 to 95% The P:Zn ratio in the charge material was in- creased from 0.49 to 06, further enhancing the main advantage of the process ic, is ability to J Novertiow Coarse f0 Dore sine thickener fst Figure 4 Zine shaft furnace |_+ Fee Zine ad etchant; ) Wat esd) Gas subbing tower) Wate al or ie th en Blowers 2) Surcrss ) Air protester: 1) Jess) Fvding vs Tor hot cohen aking; K) Cone; 1) Fence 5) Mower: a) Sie AS, ump sump: p) Water jacket «) Conder) Water-coled tough: 3) Led eye trough: sting val 9) Zine PathVol. A28 ve condenser is cooled to to separate from the lead Tt then flows overa weir « process does not take ‘conditions, the recovery ue the theoretically cal- (60 0, but ca. 400. The commercial grade ingots to higher grades. ‘dustrial furnace weat in- ‘in 1960, The eross-sec was 172%, and this ze even today. process, Imperial Smelting should compare their ex and ths has led to stan. Dr zine-producing plants 1 the plant performance, output ofa furnace with bm? has been increased 17000 ¢ lead in 1963 to 0 lead in 1990. At the ‘was increased from 91.7 1 yield from 94 to 954%, charge material was in 6, further enhancing the process, Le, is ability to Togas scrubber Zine overflow seal for nine dust semovl 2eie: K) Cone: 1) Furnace: ‘led troughs) Lead reyele Vol. A28 treat ores of complex composition. In addition to Zn and Pb, many ores also contain Cu. Most of this is reduced to the metal and dissolved by the lead. Copper contents below 4% give few prob- Tems, as the copper separates as dross on cooling the lead and can be removed in the form of a solid crust. Higher concentrations can give prob- lems due to the limited solubility of copper in lead. Special techniques are then required. A schematic diagram ofa lead zine shaft furnace is given in Figure 4 5.3, Refining of Crude Zine Zine produced hydrometallurgically (ee S tion 54) does not need to be refined. However, crude zine produced by pyrometalluray contains Fe, up 00.3% Cd, and is of As, depending on the production method and the composition of the ore. The zine used (© produce pressure casting alloys should have @ purity of 99.99 199.995%, and galvanizing processes require a purity of 98.5-99.95%, depending on the pro- cess used. Commercial grades of zine cannot be produced simply by remelting and liquation or by treatment with fluxes. Simply cooling zine melts until they approach the eutectcs in the systems Zn—Pb or Zn—Fe does not produce the theoretical compositions 0.8% Pb and 0.02 Fe, respectively. The concentrations obtained in practice are 1.2% Pb and 0.03% Fe. Hence, these processes are only suitable for producing zinc for the next stage of purification by distillation or for producing zine dust. The refining of commercial zine produced by a pyro: ‘metallurgical process (today usually the Imperial Smelting Shaft Furnace process) is carried out by distillation in high-temperature distillation columns constructed of ceramic-bonded SiC ele- meats, The process was developed by the New Jersey Zine Co., Palmerton United States), and the first plant went into operation in 1932. The distillation process makes use of the comparatively low boiling point of zinc (906°C) However, as not only impurities with a high boil ing point such as lead, copper tin, and iron must be removed, but also cadmitim, which boils at (, the refining process must be carried out in two stages. A plant based on the New Jersey process is illustrated in Figure S. Molten crude Zine is fed into the top third of a distillation column, the lower part being heated to a Fare 5. Zine refining pant using the New Jersey process [B.Vol Ia, p 116 Fig. 34) 1) Mekingfroace;) Lead column; ©) Condenser purty in furnace; g) Washed ie furnace 110°C. The upper part acts as a reflux cooler forthe less volatile constituents, so that only Za and Ca pass into the condenser. Because of the relatively small difference in boiling point be tween zine and cadmium and the low cadmium content, a further very careful fractional distila- tion must be carried out. The column for this is heated t ca, 950°C, and the Cd which distil off| is collected as a dust with a high zine content. Depending on the composition ofthe initial ma terials and the quality of the process control, the zine produced can have a purity of 9.996% and the concentration of the undesired elements Po, (Cd, and Fe can be <0.001 "The “washing” zine produced in the lead column contains Pb, Fe, Cu, and sometimes also In and Tl. The washing zine is liquated, giving hard zine and very impure lead. The hard zine is recycled to the process, but the lead eam be treat- ced separately. In practice, this very impure lead is ‘often added to crude lead from a smelter before itis refined, The working life ofthe distillation columns is 2-3 years, and the energy consumption for {tof purified zine is 6.5~7.3 GI520 Zine Production 5.4, Hydrometallurgical Zi (1)-15), (10), (13) Zine can be deposited electrolytically both from aqueos solutions and molten salts. How: ever, only aqueous electrolytes (i. solutions of zine sulfate in dilute sulfuric acid) have so tar heen nse in industry. Other proposed processes such as the electrolytic production of zinc dust, amalgam electrolysis, and sulfate-chlonde elec- trobysis have not alisinod industeial importance. Although a full-scale version of the electrolytic refining process, in which the impure zin Forms the anode, has ben developed, it is not used, the reasons being mainly economic. The electrolytic production (electrowinning) of zine from solu tious of zine sulfate in sulfuric acid has under ‘gone unparalleled growth in recent decades, Ap- proximately 80% of total world production {oines from this process today, although a num. ber of probiems still need to be solved, principal- ly in the preparation of pure electrolyte solu- Like the thermal processes of zinc produc: tion, the industrial electrolysis of zinc uses oxidic starting materials. The most important natural raw material, zine blende, therefore sill needs to be roasted to be converted to oxide. To ensure rapid dissolution ofthe calcne, the roasting pro: cesses used should therefore conserve the fine {grained structure ofthe concentrate obtained by flotation. Commercial zinc oxide can usually be used directly and need only be treated if it con tains impurities that have a harmful effet on the cleotrolytic process. Roasted oxide must be ground to improve its solubility. Using typical Sarting materials the electrolyte process uf cm, production consists of the following stages (ig. 6) 1) Roasting 2) Leaching 3) Liquor purification 4) Electrolysis 5) Melting und casting, The main problem in leaching and liquor pu- ‘ification is 2ine- tron separation. In earlier pro ‘cesses, leaching was carried out such that a large excess of acid was avoided. Thus, the ealcine and fcid (exhausted electrolyte) were added simulta- neously to the leaching tanks, the amount of acid being exactly that required to dissolve the zine onde. High yields of ine conic only he orained. Vol. A28 Sulfide ine concentrate ‘ir_JOrcdative]_waste gas____ fis, ircasing Tofdtction ee Residue SO, ro eosin Heatet opus aa ever Liquor }—=Cu, Ca residues [purification Cu, resi Parties To treatment meatal er | cay Hettotyte | sce (Hestragai ae Tine dust Cathode zine | | | (esse =] | Commertial ine {Zine dust] etant Figure 6, Flow diagram of the slstlyi zine production proces (2p. with concentrates containing <3% Fe. Iron in higher concentrations was dissolved lu some ex tent. The solid residues contained ca. 20% Zn and 30% Fe, However, as a result ofthe roasting Process, part ofthe zine in the ealeine is in the form of zine ferrite (ZnFe,0,), which can only be dissolved at higher acid concentrations (30— 130 g H,S0,/L). Maxinum yields of zine and also of other valuable impurities such as copper ind cadmium require the use of fugher acid Cconcentrativus in the leaching process. Hence, almost complete dissolution of the iron content of the zine blende cannot be avoided. AS the iron Iterferes with the clevtwlytic process even atVol. A28 containing egos we 80, To residue treatment Cu, Cd residues Ta treatment Tine cust z= + he letotc sine production aining <3% Fe, tron in ‘vas dissolved to some ex s contained ca, 20% Zn ‘asa result ofthe roasting ve in the caleine ie in the 2Fe,0.), which can only acid concentrations (50— mum yields of zinc and purities such as copper the use of higher acid leaching process. Henoe, tion of the jron content aubeavoided. As dhe ion strolytic process even at Vol. A28 ow conveuttations it must be precipitated from the zinc sulfate solution obtained Precipitation of Iron Hydroxide, Previpitir tion of irom as its hydroxide has now been largely superseded owing to the poor ne yteld obtained (65-88%). The process is usually carried out in two stages. The readily dissolved zinc oxide fraction is brought into solution by “neutral leaching” in a ‘mixture of cell acid (150-200 g H,S0,/L) and the acidic solution (ca. $0 g H,S0,/L) produced during iron precipitation. At this stage of the process it should be ensured that impurities suck 4$ iron, arsenic, antimony, and germanium are retained in the solid residues, A solid liquid sep- aration is carried out, giving an impure neutral liquor which is fed to the purification stage and a aineric esidue which is fol Ww the sewn, ‘acid leaching stage, for which hot (ca. 95°C) cel ‘acid is used, A furtier suld—Tiguid separation prodiices a solid residue containing up to 5% zinc and any lead and silver present (which can be processed ia lead smelter) aad a zine sok tion containing ca. 80 g/T-zine together with the iron and other impurities, such as arsenic, anb- sermanium, nickel, and cobalt After oxidation of Fe(II) to Fe(II) in the solution obtained by “neutral leaching,” the ron is puaipitated as its ydronie by adding further calcine. The precipitation starts at pH 2.6 and ‘continues up to pH 5.0, This gives solutions wath Isilual ison contents of 1020 mg/L. Because precipitation of iron causes arsenic, germanium, and zinc to be adsorptively coprecipitated, and the caleine used for neutralization cannot be sub- Jected to hot acid leaching. this process gives ur salislactory zinc yields. Higher zine yields are ‘only possible ifthe leaching residues can be more cdily filtered. Three methods of achieving this are available, Le., precipitation of the iron as jarorite, goothite, oF hematite Iron Removal by the Jarasite Process. In the jarosite process, an Fe(III) compound of the type X[Fe(SO,)(OH),], where X represents HO", Nat, K*, or NH, is precipitated by adding alkali metal or ammonium ions. Thee compounds correspond to the mineral jaosit The process was independently developed be tween 1960 and 1965 in various zine smelt plants arount the world. It makes use ofthe fact hat jarosite prosipicates have the following ad vantages over iron hydroxide: Zinc 521 2) They are almost insoluble in slr ac 2} They faves ugh wou soaten a0 that the amount of reitate formed i fos 3 They have s00d filtering properties However, jarosite precipitates do not adsorb Ue harmtul hiuputues as effectively, so that the purification effect ofthe process is inferior The additional cations needed for the precip- itation are added to the liquor in the form of sulfates. In practice, ammonium sulfate, which forms an ammonium jarosite, is usually used. ‘A Tlow diagram of the process is given in Figure 7, Precipitation ofjarosite begins at pH_ <1 and is complete at pH 1.5. Jarosite formation and precipitation being a temperatuce-dependent process, two alternative industrial processes ex Ist, the first operating at temperatures up to 180°C wud with solatvoly high acid concentra tions (60-90 g H,SO,/L) giving a high reaction rate, and the second at ca. 95°C and consider- ably lower acid concentrations (510 g/L). The lower temperature method is more widely used, mainly because of the lower equipment costs. Jarosite theoretically contains 37% iron and 13% sulfur as sulfate. In practice, these values are not reached, asthe caleine added for pH con trol is not completely dissolved and hence adds impurities to the solid residue, For this reason, additional leaching processes are carried out, ivingzine contents of4_ 63% in the residue, Zine Yields of 96-98% can beachiewed by the jarosite process, As the jarosite contains sulfate, it helps regulate the sulfate balance of the plant Worldwide, the jarosite process hus super seded the precipitation of iron hydroxide. Hows ever, probloms are caused by the fact that the Jarosite contains sana aumouns of soluble ziue land so must be deposited in special waste dis- posal sites. New processes aimed at further in creasing the rin yield have therefore been devel- oped. Iron Removal by the Goethite Process. As the flow diagram (Fig. 8) shows, the first stages of the goethite procs are the same as in the jurosite process, The solution frou te First hot leach is then treated with zine concentrate, The zinc dissolves, reducing the iron to the divalent State, and elemental sulfus is precipitated, so that compounds other than goethite (e.g. jarosite) ‘are not precipitated in the final precipitation pro- ‘ess. The excess zinc concentrate and the elemen= tal sulfur are recycled to the roasting proces.522 Zine Caleine H;S0, content up £9 ca, Ba/L : estat] unpre i [each] peaia tus FI fo ane H fama ~ ara oom —Calcine L_ sarosite ai 16% 2m) Figure, Flow diagram of the jaosite proces with prenestaition (p78) Jaroste pre Oxygen is added in controlled manner, pre- sipitating yoethite, FeO(OH), at pH ?~3.3 and 70-90°C. ‘The advantage of the gocthite process is that the amount of residue that must be disposed of is considerably less than in the jarosite process Whereas the zinc yield is comparable to the larosite process. the vield of canper is lnwer (80% instead of 90%) and that of silvers higher (96% instead of 90%). As the gosthite pro- duced, which contains 40-45% icon, always contains small amounts of basic sulfates, it can- not be used in blast furnaces, Vol. A28 cell aca ro Aral leaching th Pong residue = ans. (ewratay Sulfur resiove \[ ek LL Sy Coline L__Seetite >= [precipitation =~ To neutral leaching Sold aug S07 Goetite residue ™ (6-894 Zo Fleue& Flow diagram of enethite pres [p67 Iron Kemoval by the Hematite Process, The hematite process (Fig. 9) was developed to en- able iron-containing residues from zine produc tion (o be disposed of at moderate cost and with ‘out ecological problems, It differs from the other Processes in that the residues are subjected to reductive leaching in which the reducing agent is an excess of aine concontrate, The inn is re- duced with formation of elemental sufur. The insoluble solids and the liquor are heated in au- toclaves, causing the sulfur to melt ane wet the excess of zine blend, forming small pellets, These are cooled, classified, and fed to the roastingVol. A28 ese from neutral Yur residue 1945. 10-20% Za) Caleine Calc ~ hie Goethite residue (6.6% Zn) the gout proces, . 69] fe Hematite Process, The 9) was developed 10 en- sidues from zine produc- {moderate cost and with 3. Itdffers from the other ‘ssidues are subjected to vhich the reducing agent reentrate. The iron is re- of elemental sulfur. The Tiquor are heated in au alfur to melt and wet the ‘ming small pelts. These and fed to the roasting Vol. A28 Reside from Gell add neal aching, did Reductive leaching removal eoarse particles) ie soci fo roasting solar separation SO bag residue 220760 | Preneutralzaio} aaa | [eopve | [cenentaton Solid tguig separation partion ae. [Seiad] S22 21997 Gypsum residues | T ta processing en Oxygen preci tion To neutral leaching Sonia Igepararan| Henatite SWhIn, 64% @ eure, Fw agra ore nematic proses, 8 Zinc 523 plant, A lead~silver residue which separates from the solution is sent to lead smelting plant. ‘The liquor is preneutralized with caleine, and the resulting precipitate is reeycled to the hot redi tive leaching stage. The copper is precipitated from the zinc~iron solution by addition of zine (cementation), and the solution 1s then neutral- ied with calcium carbonate. This is followed by ‘the most important stage ofthe process, pressure ‘treatment in an autoclave at 200°C at an oxygen pressure of 10-15 bar. Under these conditions, iron is precipitated as Fe,O, (hematite), which ‘can be used in iron metallurgy. The zinc solution is recycled to the neutral leaching stage. The gyp- ‘sum produced is dewatered and can then be used in the building materials industry. The yields of zine and other valuable metals are comparable to ‘those in the jarosite and goethite processes. AS the iron can be produced in the form of a useful product, no landfill space is required. However, the costly and complex technology is restricting more widespread use of the proces. 5.5. Treatment of Leaching Residues Residues from caleine leaching ate primarily subjected to pyrometalturgical treatment. In some plants of older design, the residues from the neutral leaching stage are treated in a Weelz kiln, This removes the lead, and the resulting sinter oxide is ground and recycled to the leach ing process. In a development of the classical ‘Waelz kiln process, vaporization is carried out in ‘a Waelz kiln fitted with an external burner. A rotary flame-fired furnace of the Dérschel type ean also be used in 2 batcn process. A combination of flotation with pyrometal- lurgical and hydrometallurgical processes (sul fating roasting followed by leaching) enables the valuable metals to be recovered from lhe leach ing residues. 5.6. Liquor Purification Impurities still present in the unpurified neu- tral liquors from the iron precipitation stage can lead to 1), Lower current efficiency 2) The presence of impacto in the ciiane 3) ‘Ravers effets onthe anode andthe cathode hodically depos524 Zine Ifthe critical impurity concentrations ave ex- ceeded and several impurities are present simul- taneously, the electrolytic process may no longer bbe possible. The concentration limits of the harmful impurities cannot be precisely specified but the following guidelines can be used (mg/L): As 001-1 Sb 0.03-0.1 Ge 0.002005 Ni 005-30 Co 01-10 Fe 20-30 In the formerly used iron hydroxide precip tation process, the adsorptive effect of the by- Groxide precipitate caused most of the arsenic, autiuouy, and germanium to be removed along with the iron, so reducing their concentrations below the acceptable limits However, when ta residues from the neutral leaching. are subjected to hot acid leaching (mainly in the interest of higher zine yields), the ducutialliquyis conan aul igh Revels oF ite fries. As these are not removed either in the iron precipitation or the leaching stage, careful purification uC ue lquor is nevessary. 18 prin ple, there are the following possibilities: 1) Chemical precipitation 2) Electrochemical deposition 3) on exchange (solvent extraction) 4) Cementation with zine For high quality requirements, a combina- tion of methods ean be used. Chemical precipita tion is mainly used for nickel and abl. For ‘example, nickel can be precipitated by dimethy!- alyoxlme and cobalt by a-nitroso-p-naphthol. However, as these reagents aro expensive, their use can only be considered in exceptional cases for liquors with very low levels of impurities, Processes involving the ute of fluidized bed electrolysis to remove impurities more noble au zine and the use of solid and liquid ion ‘exchangers are still at the development stage. In most zinc electrolysis plants, the liquor is purified by cementation of larnful elements on zine dnst inn continuous, multistage process. Aa inert coating can form on the zine particles or they may be chemically dissolved, Therefore, nol all the vine diet added can take part in the ce ‘mentation process and a large excess of zinc dust (5-10 fold) is necessary to ensure effective pu lication, Vol. A28 inpure neutral liquor [festng Fark] Ass Soid-rqud eeraratinn ers Residve to C Co eneichnent Eoctan eH sexe 1 (even rae igor far electraiysis Figure 10, Hot cold liquor purfcsion (2, p67) A typical process used in many plants is the hhot-cold liquor purification process (Fig, 10), Which has twa successive precipitation stages In the list stage, copper, nickel, atd cobalt are precipitated by adding zinc dust in the pres ‘ence of an added activator, usually As,0,. Tn the second stage, copper sullate isthe activator, and ‘cadmium is removed. In many eases, a hitd fine purification stage is included. The conventional hot=cold liquor purifica- tion process has a number of disedvantages: ‘present in tbe starting materials 2 The post of rousing Mihi tose anne 3) Thepreseace ofthe impurities arsenic and stimony in the presptated copper 8) The posit hat tbe prsipiated metalsmay re These disadvantages have led to dhe develop- meat of the alternative reversed liquor purifies 7Vol. A28 (4 enrichment Co envichment wrifeation Pp 07] ed in many plants is the sation process (Fig. 10), t precipitation stages ‘oper, nickel, and cobalt 1g zine dustin the pres- or, usually As,O,. In the fate is the activator, and {many cases, a third fine luded. t-cold liquor puritica- ber of disadvantages: oppor i too litle copper ‘steals ig high toxe arsine ines remind sntimony in recited metas may rei have led to dhe develop reversed liquor puritica- Vol. A28 PUFF que | Fe a Cu sludge | eo | & au a siulge fo electralysis gee 11. Keversed hguor purieation 2p. 68] tion process (Fig. 11). Here, itis not necessary to add copper to remove cobalt and other impuri- ties, The low concentrations of arsenic are sulf- cient to act as activator, the costly copper addi tions are avoided, and relatively pure cementates are obtained in both precipitation stages. This Zinc 525 process can alte be operated continuously. ‘hereby the addition of zinc dustis controlled by measuring the electrode potential, which is a function of the copper and cadmium concentra- tions in the liquor. 5.7. Electrolytic Production of Zine 11)-15), (101, 1131 Principles of Zine Electrolysis. As the stan. dard electrode potential of Zn** is —0.763 V, a solution of zine sulfate should not deposit zinc ‘on electrolysis: hydrogen should be liberated in stead. Zine deposition is only possible because of| the hydrogen overvoltage at the zine electrode, which causes a voltae shift of magnitude ap- proximately equivaleat to the standard electrode potential of zine. The avervoltage is influenced by a number of factors. For example, the effect of current density is expressed by the Tafel equa- n=e + blog! 1 decreases with increasing temperature, but, as the conductivity decreases with decreasing tem: perature, the energy consumption increases. With these effects in mind, two typical methods of performing zinc clectrolysis were used in in dustry for a long time. Either the electrolytes were slihtly acidic and current densities were ca, 325 Aim? or they were strongly acidic and cur rent densities were ca. 830 A/m?, The process parameters widely used today give good current yields in zine electrolysis using current densities in the range 400-600 Am? and a process tem- perature not exceeding 40°C However, the hydrogen overvoltage is also influenced by the condition of the surface of the electrodes. Smooth surfaces lead to high over- voltages. For this reason, the cathode plate must be stripped every other day in practical opera- tion, Zine electrolysis is extremely sensitive to impurities in the electrolyte. These fall into sever- al groups: 1). lmpuites that are move elcronegtie than ine fins potas, sodium calcium, magnesium, a tminum, end mangunese. These impurities do not di Fooly interfere with he leroy proces, I concer {tats ae too high the mscosy of the electro increas and the difosion process inthe Boundary layers ae disturbed A ont of 60 iL. is used a8 tuieline ure, 2), Tnputtes whose clstrode potential ies betwove those © of a and Hn the case of ead, cad, thal