Zinc Ores

ZnS - Sphalerite or zinc blende (Zn,Fe)S - Marmatite ZnCO3 - Smithsonite ZnSiO4 H2O - Hemimorphite or Calamine

Zinc Ores Zinc ores range from 2.0 to 7.5 % Zn metal. Zinc concentrates assay 47 to 60 % Zn, 1.5 to 2.5 % Pb up to 3.5 % Cu, 3 to 10% Fe about 0.2 % Cd and 29 to 33 % S as well as minor quantities of thallium, Indium, gallium, germanium, selenium and tellurium. A zinc concentrate is a powdered material with 5095% particles less than 0.07 mm on side, the grains measuring more than 0.6 m accounting for not over 0.1 to 0.3 %. Oxide concentrates usually consist of smithsonite and calmine. Metallurgy of Zn is divided into two fields: pyrometallurgy and hydrometallurgy. Former is presented by the distillation processes and the latter by the electrolytic processes. The distillation processes appeared well before the electrolyte methods.

Flow Sheet for Pyrometallurgical Extraction of Zn

A mixture of roasted Zn concentrate and anthracite screenings or coke breeze is charged in to a grog retort which is then placed in a furnace heated to1400 C. In the retort zinc is reduced according to the reaction: ZnO + CO =Znvapour + CO2 The nose of the retort opens into a condenser of fire clay. In the condenser, the retort gas cools in contact with its walls, the droplets run down the sides and fall from the top, collecting in the pool at the bottom. The liquid zinc is drawn from the pool as it accumulates there. Zinc vapour that escapes from the condenser is precipitated in the prolong, a sheet-iron extension to the condenser as dust. The other oxides present in the charge, such as those of Cd, Pb and Cu may also be reduced in the retort. Only Cd and Pb vaporize to an appreciable extent. Material left in the retort is called the retort residue.

Horizontal retort process is simple but of low capacity producing metallic zinc contaminated with Cd and Pb. These retorts are made from 300 to 370 mm in diameter, with walls 30 to 50 mm thick; thicker walls would hamper heat transfer inside the charge and slow down the rate of distillation. Length should not exceed 1700 to 1900 mm as at a temperature of 1400 C the retort will fail under the bending load. Condensers and especially retorts must be fire resistant , strong and impervous to Zn vapours. Retorts and condensers are extruded from a damp and well pugged mixture of fire clay grog and coke. Green retorts and condensers are dried and fired.

A single charge of such a retort weighs 80 to 90 kg containing up to 30 kg metallic zinc. With a distillation cycle of 24 hrs and a liquid zinc yield of 80 to 83 % of the charge weight, a single retort can produce 25 kg of zinc a day at the most. An average smeltery have several thousand retorts in operation simultaneously. Retort process involves arduous manual labour. The size of the retort furnace varies with its construction. Three row furnaces for 240 retorts measure about 20 m in length, 5.3 to 5.5 m in width and .8 m in height. The bottom of the furnace is 2.75 m above the floor of the shop.

Horizontal retorts arrangement

Arrangement of retorts in furnace

As the art of zinc smelting stands at present, the production of 100 tons of zinc a day requires over 3000 retorts. The retorts are stacked in vertical rows. Their closed ends rest on shelves inside the furnace , while their open ends or noises stick out of the furnace through openings. The retorts are inclined towards their noses. High temperature required for operation has to be distributed uniformly throughout the furnace space. Gaseous fuel is used for heating up the furnace. The basic reaction of zinc distillation is the reduction of solid zinc oxide with gaseous carbon monoxide.

For the reduction and distillation to proceed at a sufficiently high rate, the grains of the concentrate should be small, as this increases the surface area of the ZnO exposed to the reducing agent. Too fine a concentrate, would form a very dense bed in the retort, obstructing the escape of zinc vapours. Local accumulations of zinc vapours may eject the charge out of its retort. The formation of zinc ferrites is no limiting factor, since the zinc from them can be driven off as easily as from ordinary zinc oxides. After the retorts are hand charged, the condensers are setup and luted in place with a wet mixture called loam and prolongs are put some time after.

Higher iron oxides begin to be reduced to FeO at 640C. Impurities copper, cadmium and lead are easily reduced at the beginning of the cycle due to the weak affinity of for oxygen. Liquid zinc separates out of the retort gas as a slowly coagulating metallic fog at 830 to 870 C. The equilibrium of vapour pressures above the droplets is attained at a lower temperature than over the flat surface of the molten pool. The retort gas remains in the condenser for 13 to 15seconds and the zinc vapour that escapes from the condenser into the prolong is precipitated there as powder due to rapid cooling.

Incomplete condensation of zinc vapours in the condenser is also due to the changes in the composition of the retort gas with cooling. The ratio of CO to CO2, which is at equilibrium at the temperature of the retort is shifted towards a greater partial pressure of CO2 due to dissociation of CO: 2CO = CO2 + C The carbon dioxide partly oxidises the zinc vapours in the condenser: CO2 + Zn = CO + ZnO

 When droplets of molten metal have experienced superficial oxidation they fail to coalesce and blue powder is formed in the condenser. The zn vapours, condenser blue powder, Zn oxide and soot that escape from the condenser precipitate in the prolong to form prolong blue powder which contains 60 to 70% metallic zinc and 13 to 15% zn as oxide and carbonate. Cd is reduced in the retort before Zn and is more volatile and very little Cd vapour reaches the prolong. Retort residue carries 10 to 13% of all zinc, gold, silver and copper as well as excess reduction coal and is usually retreated for the recovery of its values.

 Distilled zn contains 98-99 % Zn, up to 1.8 % Pb, 0.05 -0.1 % Fe, 0.004-0.02% Cu and 0.2-0.4% Cd. Prolong dust consists of finely divided particles measuring a few microns in diameter. It carries from 0.7 to 2.3 % Cd and is treated for Cd recovery. Condenser dust is produced in limited quantities and carries about 0.1 % of all Zn and the impurities mechanically carried off with the gases and returned to the retort.

Broken retorts are inevitable for the service life of the retort is 15-25 days at the most. Approximate % of distillation products: Distilled Zn 82.8; Prolong dust- 4.8; Retort residue-6.3; Broken condensers: 1.1; Broken retorts:0.7; loam-3.2; Losses with gases-1.1;

Vertical Retort Furnace The basic disadvantages of the horizontal retort process are its intermittent nature, cumbersome furnaces an difficulty of mechanisation. Vertical retort furnace operates continuously and use s carborundum retorts. Powdered carborundum is mixed with 6-12% of fireclay.

The batch obtained is wettened, pressed in moulds, dried and fired at 1400 to 1600 C. The refractories retain mechanical strength up to 2000C are chemically neutral and are 3-4 times as heat conductive as grog. A vertical retort is a shaft rectangular in cross section, made of SiC blocks or bricks.

Vertical Retort Process 1-Retort 2- gas combustion chamber 3charging device 4-discharging device 5- condenser

 Retort is fired with producer gas which is burned in chambers on either side of the retort. The heated portion is about 7.5 m high while the internal dimensions may be 0.3 m by 2.2 m. The charge is introduced in the form of briquettes from above through a firebrick chamber called the charge column which also serves to provide an escape for zinc vapour.

The bottom portion of the retorts terminates in a residue extraction mechanism which is an iron box fitted with a water seal. The spent residue is discharged continuously and retains the original shape of briquettes. The briquettes are prepared from a mixture of roasted zinc concentrate, anthracite, coking coal and suitable binders such as coal tar. After mixing, the batch is passed through a briquetting press and heated to 750-900C.

The coal and tar are coked and the briquettes attain a strong and porous structure.

Chemistry of the process does not differ from that of the horizontal retort process.

The rate of heat transfer through the SiC walls of the vertical retort and the briquetted charge is higher than in ordinary distillation.
Zn recovery is more complete and its content in the retort residue is usually under 3 to 5 %.

The normal life of vertical retort is 3 to 5 years and its productive capacity is 4 to 5 tons of zinc per calendar day or upto 90 kg per square metre of heated area (as against 15 kg per square metre of heated area in the horizontal retort). Zinc vapour leaving the retort is condensed to liquid zinc in condensers which are made of fire brick and have inside partitions to extend the path covered by the zinc vapours.

85% of zinc is condensed to liquid metal. The remaining uncondensed zinc vapour and entrained blue powder passing out of the condenser with the zinc is recovered as a fine dust. The scrubbed carbon monoxide gas is pumped back into the retort setting which saves about 20% fuel.

Vertical Retort Zinc Condenser

Comparative Performance and Economics of he Horizontal and Vertical Retort Processes (per ton of zinc)

Variable Heating and reduction fuel (coal), tons Labour, manhours Zinc recovery, %

Horizontal retort 2.2-2.39

Vertical retort 1.54-1.71

29-43 86.4-87.8

7.7-12.5 90-94

Electrothermic Furnace Though more efficient than the HR process, the VR process is disadvantageous in that heat has to be transmitted through the retort walls. The heating of the charge with in would raise distillation temperature and consequently zinc recovery while the walls would remain relatively cold.

It is also a continuous process with a zinc production of close to 100 tons per day at an efficiency of 92% recovery. Heat is generated internally by resistance to current flow by the charge in the furnace between sets of graphite electrodes inserted through the top and bottom furnace walls. The furnace is circular 45 feet high and 7.5 feet in diameter and constructed of a series of sections of high and superduty firebrick. Steel water jackets enclose the lower half of the main smelting zone of the furnace below the vapour ring.

This annular vapour ring is about in the middle of the furnace and through it the distilled zinc vapor and furnace gases pass to the condenser.
The vapor ring and condenser are both lined with SiC bricks. Charge is primarily ZnO sinter and coke but other Zn bearing materials such as granules, dross, screenings etc. are also used. Furnace is kept full of charge and the time required for the charge to pass down through and out of the furnace is about 22 hrs.

Electrothermic Smelting Furnace

 Heating is accomplished by the resistance of the

charge to the current flow between eight equispaced pairs of graphite electrodes, one of the sets of pairs is situated near the top of the shaft and other set of pairs is close to the bottom.

Total power to the furnace will be 10,000 kW at 200230 volts and resistance heating gives a temperature in the center of the furnace 1200-1400C and temperature of 1300C at the lower electrode elevation. The gases escape from the furnace at 850C : 45% Zn vapour and 45% CO and the remainder N2, H2 and CO2. The condenser is situated below the vapour ring is Ushaped with a vertical inlet and outlet.

The bottom part of the U- is the liquid zinc pool and furnace gases are drawn in to this to increase the pool volume operating under a vacuum of 25-30 cm Hg. This zinc is tapped periodically and cast into slabs or goes to the refinery. The gases pass through the condenser and in to a high velocity water scrubber for the removal of entrained solids and blue powder.

 This slurry is treated to recover the solids which are briquetted and returned to the furnace. The clean gas (80% CO) is piped as a fuel. The spent residue from the bottom of the furnace consists of coke, sinter residue and liquid slag. A rotating table is provided at the bottom of the furnace for the removal of spent residue.

Zinc Blast Furnace

Introduced in 1950. Largest production unit 300 tons HR 0.06 tons VR 10.0 tons elec.-thermic furnace 100 tons

Charge

hot lump sinter, preheated coke & small addition of lime

Sinter analyses 42% Zn & 20% Pb

Coke 5 & 7.5 cm

coke preheater

800C.

Accurate proportioning (coke, sinter and hard burned lime) important.

Imperial Smelting Furnace

 rectangular in shape rounded ends Pb blast furnace. Upper part of the furnace fire brick-lined steel shaft, lower part hollow water cooled steel jackets. Two stoves are used air to 950C operates on a 40 min on blast cycle & 30 min firing cycle. Dome shaped roof supports two double bell & hopper charging units

Cold air is introduced between the two bell valves to prevent gas leakage. 4-equispaced top air inlets located in the furnace sides above charge level. Preheated air is bled from tuyere bustle pipe through these inlets.

This air burns CO & raises temperature of whole gaseous mixture at this location 100C. Resultant temperature 1050C is too high to reoxidise Zn metal vapour It passes out through two off takes located opposite each other just under domed roof in to condensers

Mixed sinter of PbO & zinc oxide is used in the BF in the proportion of about two zinc to one lead. The reduction of ZnO to metal is endothermic but the reduction of PbO is slightly exothermic:
PbO = CO =Pb + CO2

CO gas diluted with CO2 gas from lead reduction, but still high enough in CO to preheat coke and tuyere air blast.

Furnace gases :20% CO and 12% CO2.

Liquid along with precious metals, Cu, other reduced trace metals & slag flows to bottom of furnace Tapped every one and half hours through a water cooled copper tapping block into a fore hearth. Slag runs over top into a granulation system & from these goes to the dump. Metal values in slag : 5% Zn and 0.5% Pb.

Two lead splash condensers connected to gas off takes on either side Curtain of Pb droplets by rotor blades absorbs heat from vapour & reduces 550C. Zn vapor is quickly condensed to liquid metal & absorbed in liquid lead. Common type of condenser three stages, with four in first stage, two rotors in second stage & two in third stage. Rotors are rotating vertical shafts with blades dip into pool of Pb bottom of condenser & throw up the condensing & collecting spray of metal droplets.

Droplets small size maximum liquid to vapour contact Droplet size shape of the rotor blades immersion depth of blades speed of rotation. Hot Pb with Zn in solution is run at 550C from condenser through an under flow baffle forming a gas seal in to a cooling launder.

Hot Pb as it leaves condenser contains 2.5% Zn and is unsaturated; cooled down to 440C in the launder, Pb has less solubility for Zn and is saturated at 2.25% Zn. Excess Zn containing 1.2% Pb rises as liquid layer above Pb in a mild steel quiescent separation bath, overflows continuously from here & into a heated Zn holding bath.

 Pb from separation bath runs by gravity under a weir, holds back separated Zn layer & returns to metal pool in condenser Cooling duty in condenser is heavy & this cooled Pb is quickly reheated by great amount of heat it absorbs from entering hot furnace gases. For heat extraction requirements 400 tons of Pb must be circulated through closed system- condenser, cooling launder & separation bath/ for a furnace output rate of 300 tons of Zn per day, 120,000 tons of Pb must be circulated.

Furnaces gases leaving condenser at 450C & low in temperature as to carry minimum amounts of uncondensed Zn.
Gases pass through two stages of cooling: washing in spray towers mechanical scrubbers, producing a clean gas below 40 C. Solids removed are returned to the sinter plant Gas containing 20% CO used as fuel in the coke preheater and BF stoves.

Zinc Vertical Fractional Distillation

To remove Pb & Cd impurities 98%-99.995%+ Priciple: Divergent boiling points Pb (1620C), Zn (907C) & Cd (778C) Zn & Cd vaporised in 1st column at 1220C Pb remains liquid in two-column vertical unit In second column at 850C, Zn remains as liquid Cd vaporises. Liquid Zn runs from vertical retort /electrothermic furnace condenser through a launder to a holding furnace & from there to 1st distillation column.

Vertical Fractional Distillation

Section Through Fractional Distillation Column

 25 tons Zn is fed into circuit & 15 tons recycled Zn from 1st column total of 40 tons per day being treated. Recycled 15 tons: Pb, Fe & other high boiling point impurities that flow out in to a two compartment holding pot is separated by liquation. First compartment is cooled to settle out a high density Pb layer & Zn-Fe dross with liquated Znnc now reasonably free of Pb and Fe overflowing into the second compartment and back to the initial holding furnace for feeding into the distillation column. Each of the two distillation columns is made of 50 rectangular silicon carbide trays, 2 feet by 4 feet and 6 inches deep.

These trays are super imposed to fit tightly together and prevent vapour leakage. These are adopted to hold a pool of metal, the depth of which is set by an overflow dam around a 3 inch diameter opening near the end of the tray. The trays are stacked with the openings on successive trays alternatively from side to side so that the metal overflow from one tray is caught on the tray below and the descending flow of metal follows a zigzag path downward from tray to tray. The design facilitates heat transfer and provides an extremely large surface from which the vapour can escape as the whole tray is covered with molten metal, but only to a shallow depth as each tray is an independent unit.

The ascending metal vapours follow the same path upward as the liquid takes downward, so that here is good liquid-vapour contact and liquid scrubbing of the vapour as it passed up through the column. Liquid zinc from the holding furnace runs into the first so called lead column in a steady stream at a height of two or three trays above the top of the heating furnace, and this flow is regulated to ensure that all the trays are full of metal and over flowing steadily into the trays below, in order that no tray may run dry or become overheated.

The design of the trays differs somewhat inside the furnace in that these distilling trays have a trough extending around the outer periphery and a raised center, to present the maximum amount of heated tray wall to the liquid zinc and at the same time to have a greater holding capacity for the liquid feed. The refluxing trays, positioned above the furnace are flat with no peripheral trough and hold a much smaller quantity of liquid metal. Controlled cooling (refluxing) takes place in these upper trays with some condensed liquid metal from the rising vapour phase produced in the furnace zone collecting and overflowing to run down from tray to tray.

The vapour phase passes off at the top of the lead column consists of two thirds of the zinc fed in and all of the Cd and this travels into a second so called Cd column. Two Pb columns can operate in series with one Cd column, as the greater amount of impurities are removed in the first processing stage and a much smaller amount of material is treated in the second stage. The design and operation of the Cd column is essentially the same as that of the Pb column except for the lower furnace temperature and the fact that all the trays are flat type similar to those used in the upper refluxing section of the Pb column.

To ensure adequate refluxing, a condenser is set on top of the column of trays and the vapour passing through this condenser goes into a second , smaller condenser to give a Zn-Cd alloy containing 15% Cd. The Zn metal running out of the bottom of the Cd column is special high-grade Zn, 99.995% pure and is used for applications such as die casting alloys which requires this type of purity.

Liquation
Used to separate Pb and Fe from retort Zn but has no effect on Cd. o The principle of this refining operation is to reheat or melt the zinc in a reverberatory furnace and then allow the temperature to drop to near the freezing point. o Pb in excess of that soluble in the Zn at the lower temperature will now settle out as a liquid layer on the bottom of the and can be withdrawn. o Zn purity can be increased from 98% to 99% with Pb in the Zn being decreased from 2% to 1% and iron decreased from 0.1% to 0.025%. o A two compartmented reverberatory furnace is used fired with coal and kept short of air to have a reducing atmosphere above the liquid metal bath to prevent Zn
o

Slab zinc is added to the large compartment of he furnace and melted at temperature above 800C at which temperature the Pb and Zn are completely miscible. The furnace is then cooled to slightly above 418C at which point the eutectic temperature is reached and Zn will dissolve only 0.85% Pb. The excess Pb over this eutectic quantity comes out of solution and settles as a bottom layer in the furnace. The Pb is still quite fluid at this temperature because of its low melting point 327C and is easily tapped from the furnace.

Flow Sheet for Hydrometallurgical Extraction of Zn

Leaching of Zinc Concentrates

The primary purpose of leaching a zinc concentrate is

to dissolve zinc oxide: ZnO + H2SO4 = ZnSO4 + H2O Process is complicated due to the dissolution of unwanted elements and compounds which have an adverse effect on the electrolysis and recovery of zinc. A two prong approach is adopted for leaching operation: Firstly to minimise the amount of impurities passing into solution; Secondly to purify the solution. Many of the impurities can be reduced in amount or eliminated by neutralising the zinc sulphate solution with ZnO, with the formation and precipitation of ferric hydroxide.

 Iron purification is usually carried out simultaneously with leaching. Any ferrous iron present is first oxidised to the ferric state with manganese dioxide and by hydrolysing the ferric sulphate:
2FeSO4 + MnO2 + 2H2 SO4 = Fe2 (SO4)3 + MnSO4 + 2H2 O Fe2 (SO4)3 + 2H2O = 2Fe(OH)SO4 + H2 SO4 First reaction is possible in an acid medium; therefore the iron has to be oxidised at the beginning of the leaching operation. The second reaction is feasible only at the end of the leaching when the acid has been depleted and the solution is almost neutral. As and Sb are removed from the solution simultaneously with iron.

Good elimination of the two impurities is obtained if the amount of iron present is 10 to 20 times that of As and 20 of 40 times that of Sb. Complete recovery of Zn is requires an excess of sulphuric acid. On the other hand the solution should be neutral towards the end of the leaching operation if the iron is to be withdrawn successfully. To meet these conflicting requirements, the leaching operation is carried out in two stages (double leaching). First roasted concentrate is treated with acid solution of ZnSO4 containing about 100 to 130 gm of Zn per litre of and 1 to 5 gm of free sulphuric acid per litre, and it is used for neutral leaching.

Rate of leaching depends on the concentration of acid. Other factors affecting leaching are temperature, the grain size of the roasted concentrate, agitation etc.
Equipment for leaching may be either air-operated or mechanical. Air operated Pachuka tank is a tall cylinder with a conical bottom made of wood or steel plate.

The tank measures 3 or 4 m in diameter and 6 to 8 m in height and has a capacity of up to 100 cu m.

A wooden pipe opened at both ends is placed centrally. Compressed air under a pressure of about 2 atm is supplied to its bottom end. Pulp is fed into the tank from above and overflows continuously as it fills the tank at a level somewhat below the top end of the central pipe.

Bubbling through the pulp, the air raises the level of the pulp causing it to flow out of the pipe and in to the tank.
Bubbling through the pulp, the air raises the level of the pulp causing it to flow out of the pipe and in to the tank. Pulp is continuously drawn in to the pipe from below. As a result pulp is made to circulate in the tank.

Pachuka Tank

Leaching methods may be divided in to batch and continuous systems. In batch leaching a mixture of roasted concentrate and solvent is charged into a tank, agitated for a prescribed period of time, worked up with additions of calcine and discharged. Its advantage is that elimination of impurities is more complete. It suffers from some waste of time on filling and discharging the tanks. In continuous leaching the pulp passes through several leaching tanks in succession. Batch system uses mechanically agitated tanks and the continuous system air agitated tanks.

Purification of Neutral Zinc Sulphate Solution

Impurities such as Cu, Co, Fe, As and Sb may appreciably reduce current efficiency in subsequent electrolysis. In the presence of some ions such as As, Sb and Co the cathode deposit will be rough and of low density. Neutral solution be purified of its copper and cadmium prior to elctrolysis. The principal reaction of Cu and Cd elimination is that of electrolytic reduction.

Electrolytic Precipitation
Zinc sulphate leach solution after purification is pumped to storage house and flows from there to the electrolytic cells for precipitation: ZnSO4 + H2O + e = Zn + H2SO4 +0.5 O2 As electrolysis proceeds and the acid strength rises to 150 to 200 gpl some of this high acid solution is withdrawn from the cells and sent to the acid storage tanks from where it will be recycled to the leach circuit for reuse. This withdrawn solution is replaced in the cells by fresh neutral leach solution, which reduces the cell acid strength to about 115 gpl, the normal range for electrolysis.

The fresh leach solution in addition to being low in H2SO4 carries from 100 to 160 gpl zinc as zinc sulphate.
Electrolysis removes from 50 to 70% of this by deposition of Zn metal on the cathodes, depleting the solution to about 50 gpl and the remaining Zn sulphate content is withdrawn in the high acids solution recycled to the leaching circuit and forms a consistent circulating load. The cells are constructed of Pb- lined concrete and have typical dimensions of 15 feet long by 2.8 feet wide by 5.5 ft deep. These cells can be arranged in cascades of 6 to 12 cells each so situated that solution will flow by gravity from the highest head cell of each cascade to the second from the second to the third and so on down the series with the last cell discharging in to a launder.

A cell room has 300-400 cells divided in to 2 or 4 units, with each unit having its own electrical circuit for flexibility. Cell temperature is important and is held at 35 to 45C by circulating water through lead coils placed in each cell . High temperatures intensifies the bad effect of impurities in the cell; and as heat is generated during electrolysis, the cooling coils are needed to keep this heat with in reasonable limits. Anodes are fabricated form 99 % Pb -1% Ag sheet (1.25 cm thick) are inert to the electrolyte solution. A cell typically has 46 anodes and 45 cathodes and smaller sized cell has 28 anodes and 27 cathodes. Most plants operate with a current density in the range of 20-40 asf of cathode area, with variations at different plants ranging from 20 to over 100 amps.

 The voltage required for the electrolysis of a zinc sulphate solution is theoretically 2.35 volts, but in actual practice 3.25 to 3.5 volts is required due to current loss and leakage throughout the electrical circuitry. The decomposition voltage of zinc sulphate is above that of hydrogen, and normally it would be expected that hydrogen would evolve instead of Zn. However, hydrogen over voltage w.r.t. Zn in an acid solution is high enough to let zinc plate out of the zinc sulphate solution without the evolution of a great amount of hydrogen at the cathode. Ampere efficiency : 87- 94%; Cathodes are pulled from the cells every 24 48 hours to strip off the layer of deposited zinc and 99.995 % pure.