Chapter Two Materials Engineering Assist. Lect.

Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

3 Zinc
3.1 Introduction
Zinc (Zn) has been known from ancient times as an alloy with copper. It was used in India and China in
the 5th century. The first real knowledge of smelting comes from India and China, the latter producing
zinc on a moderate scale in the early 1700s, a sample of Chinese zinc dated 1745 having been found to
contain 98.9% zinc. Production of zinc started in Great Britain in 1740 by the process of distillation. In
Belgium the horizontal-retort process was developed in 1806. By-products include cadmium, sulphuric
acid and fertilizers. The original Belgian thermal process still remains the basis for modern zinc
distillation. In this method the roasted or sintered concentrate (or both) is reduced by strongly heating with
coal in vertical retorts. Metallic zinc distills and is collected as liquid metal in condensers. Produced zinc
contains 1–2% lead and was formerly known as spelter. By fractionating spelter, 99.99% zinc can be
obtained.

3.2 Sources
The important ores of zinc are sphalerite (ZnS) and marmatite [(ZnFe)S]. Less common ores are zincite
(ZnO), smithsonite (ZnO.CO2), and franklinite. The oxidized zinc ore calamine (Zn2O.SiO3) was at one
time the main source of zinc. Zinc ore is widely distributed, the most important sources being USA,
Canada, Australia, Mexico, Germany, Poland and India. However, with the successful separation of
sulphide minerals by flotation, its importance has considerably decreased. Sphalerite (ZnS) and marmatite
[(ZnFe)S] are the main economic ores, which are always found with the lead mineral galena; they are
separated by flotation.
Zinc ores/minerals:
1. Zinc blende or sphalerite (ZnS).
2. Smithstone (ZnCO3).
3. Calamine (Zn2SiO4.H2O).
Zinc ores are often a low grade ores which contain 2–7.5% Zn. By mineral beneficiation process (i.e.
flotation), separation of sulphides of Pb, Cu take places and concentration of zinc (ZnS) is produced. Zinc
Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

concentration contains 47 to 60% Zn, 1.5 to 2.5% Pb, 3.5% Cu, 3 to 10% Fe, 0.2% Cd and 29 to 33% S;
apart from those minor quantities of Tl, In, Ga, Ge, Se and Te are also present.

3.3 Extraction of Zinc

There are two routes of extraction of zinc: pyrometallurgical process, and hydrometallurgical process
followed by electrometallurgical process.

3.3.1 Pyrometallurgical Process

The techniques of smelting and converting are applied for Cu2S in copper metallurgy. But for ZnS, they
are not possible due to high melting point of ZnS even at 1500 °C. Hence, a different method is applied
in zinc extraction.
Flow sheet for pyrometallurgical process is shown in Fig. 3.1. After grinding of ore, separation of
sulphides of lead and copper is done; and concentration of zinc (50–60% Zn) is produced.

3.3.1.1 Roasting
Oxidation of zinc concentrate (ZnS) is necessary for the subsequent reduction and recovery of zinc metal.
Oxidation is carried out by roasting, either a partial roast followed by sintering or in one operation as a
dead roast. Complete elimination of sulphur is desirable as any remaining after roasting ties up twice its
weight of zinc, which is lost in subsequent operation. The zinc sulphide concentrate always contains some
lead sulphide which is eliminated during initial stages of roasting, i.e. by volatilization; hence, the multiple
hearth roaster is used. The roaster has eight hearths and a top drier hearth. The remaining lead sulphide is
removed during sintering at high temperature. Heating is unnecessary when a partial roast is done, for the
blende contains sufficient sulphur to support combustion down to 7–8% sulphur; but for dead roasting,
external heating is necessary to drive off the last few per cent of sulphur; this is provided by a firebox on
the bottom hearth, either oil or gas is used as fuel.
Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

1.3 Flow diagram for extraction of zinc by pyrometallurgical process

Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

Partial roasting of zinc concentration (ZnS) is done at 700–800 °C to zinc calcine (ZnO, which contain 1–
4% S). For a dead roasting a higher temperature (1000 °C) is required.

Presently, roasting is carried out in a suspension roaster or fluidized bed roaster instead of earlier in a
conventional hearth roaster, because the former has certain advantages: (a) it is autogenous; (b) good
control over the temperature; and (c) high roasting rate.
Then sintering of zinc calcine (ZnO) is done at 1200–1400 °C in a Dwight-Lloyd sintering machine to
provide lump feed for retort distillation and to eliminate residual sulphur, cadmium and lead.
3.3.1.2 Retort Distillation
A) Horizontal retort
In horizontal retort process, 2 m long retorts, each having a diameter of 25 cm and a thickness of
5–6 cm, are lined up in a gas fired furnace in batches of several numbers at a time. Retorts cannot
make of metals because most of metals produce alloy with zinc when heated at high temperature.
The retorts are generally made of fireclay. The retorts are first charged with mixture of fine size
ZnO and an excess of coal (30–40% by weight), then heated to a maximum temperature to
volatilize zinc which is subsequently condensed. Theoretically, one part of carbon will reduce
seven parts of zinc oxide, but in practice it has been found necessary to use four to five times this
amount, principally to keep the carbon dioxide concentration as low as possible (C + CO2 = 2CO),
and also to protect the retorts by holding up the molten slag. This large excess of carbon, over that
the theoretically required, is necessary to insure complete reduction and to maintain a reducing
atmosphere in the retort by reducing any carbon dioxide that may be formed.
The furnace is gradually heated up to 1400 °C, distillation start around 1100 °C. The first gas
to come off is coal gas, burning with a luminous flame; as the reduction proceeds, and carbon
monoxide is given off, the luminosity diminishes and the flame becomes purple. The beginning of
zinc distillation is marked by the flame of bluish-white colour and generally at this stage the
prolongs are fitted to the condensers. Finally, when all the distillable zinc has been expelled, the
flame loses its bluish tinge and becomes purple again, indicating that the cycle has been completed.
Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

Temperature of condenser is important: if it becomes too low (below 400 °C) excessive blue
powder forms, and if too high, zinc vapour will pass off uncondensed. A temperature of 1400 °C
is generally maintained in the furnace, and retorts temperature being 100–200 °C lower.
Reduction of zinc oxide by carbon is a strongly endothermic reaction, which requires
temperature in the range of 1200–1400 °C.

( 1.2)
The liberated zinc vapour is extremely sensitive to oxidation and it is necessary to carry out the
distillation in a closed system. The carbon monoxide forms in reaction (1.2), then further reduces
to zinc oxide:

(1.3)

At high temperature the carbon dioxide is unstable, so it reacts with more carbon present in the
system to form carbon monoxide:

(1.4)
Zinc boils at 907 °C, and carbon does not reduce zinc oxide until 1120 °C, so zinc is liberated in
the vapour form. In this state it is not only susceptible to oxidation by the ordinary oxidizing agents
such as air and water vapour, but it is capable of oxidizing by carbon dioxide. Reactions (9.3 and
9.4) are reversible reactions, but the concentration must be very high before the backward reactions
take place. With zinc vapour [reaction (9.3)], however, the backward reaction occurs with small
concentrations of carbon dioxide. In general, condition of reduction is (pco /pco2)gas phase > (pco
/pco2)equilibrium, so pco should be maintained at a high level in order to prevent the oxidation of
zinc vapour to zinc oxide due to presence of CO2 gas. If the zinc vapour is much diluted with other
gases, it condenses not to liquid zinc but to a mixture of solid zinc encrusted with zinc oxide, which
is known as blue powder.
Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

B) Vertical Retorts
Vertical retorts are made of carborundum, as refractory by mixing with 6–12% of clay.
Carborundum is nothing but silicon carbide (SiC), which has a melting point above 2700 °C. The
conductivity of silicon carbide is about five times higher than that of fireclay. Vertical retort is a
shaft of rectangular cross-section. The height of the heating zone is about 7.5 m, and inside
dimensions of retort cross-section average 300 * 1500 mm.
Generally, gas is used to heat the retort by burning of gases in chambers. Modern vertical retort is
heated by electrical energy. The graphite electrodes are introduced through the silicon carbide
walls near the bottom of the retort. The electrical energy provides the heat to the system. The
charge is introduced as briquettes from the top and slag is discharged continuously from the
bottom. Modern vertical retorts are provided with automatic charging and discharging systems
which help the handling of raw materials as well as products.
The roasted zinc concentrate, coking coal and coal tar (as binder), after a through mixing, the
charge is passed through a briquetting machine. The briquettes are heated to 750–900 °C to
strengthen briquettes and make them adequately porous. Distillation in vertical retorts is no
different in chemistry than the standard horizontal retort technique. Since the conductivity of
silicon carbide is higher and therefore zinc is removed more completely, zinc content in slag is
generally less than 5%.
A condenser is lined with refractory brick and provided with internal partitions that lengthen the
path of gases. The zinc vapour is condensed very fast in order to avoid the formation of blue
powder (ZnO + Zn). 3–4% zinc, all iron, gangue, copper, and precious metals are contained in the
residues of the retort processes. Zinc recovery is about 95%. The comparisons between horizontal
and vertical retorts are shown in Table 1.1.
Zinc vapours are condensed to metal and some are oxidized. Besides zinc, retort slag always carries
lead, copper and noble metals; therefore they require additional treatment. A top layer of zinc
containing some lead (about 0.8%) and an inter- mediate layer of zinc and iron (15–20%) is called
hard metal, which is recycled to the retorts. Bottom lead layer is further smelted to recover the
lead. The zinc layer is refined by fractional distillation due to wide difference in the boiling points
of zinc (907 °C), cadmium (780 °C) and lead (1620 °C); therefore, easy separation of one metal
from the other.
Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

Table (1.1) Comparisons between horizontal and vertical retorts

3.3.2 Hydrometallurgical Process

Hydrometallurgical processes are used for the extraction of zinc from the low grade ores. These processes
produce high purity zinc and also lead to a higher rate of recovery of valuable by-products. Figure 1.2
shows the flow sheet of hydrometallurgical process.
Before leaching, the zinc sulphide concentrate is first roasted. Roasting for leaching must be very
carefully controlled to produce the right proportions of zinc oxide and zinc sulphate. The zinc sulphate
must be present in sufficient amount to make up for the sulphuric acid lost in dissolving the oxide and
processing the residues. The roasted zinc concentrate is dissolved in sulphuric acid and the valuable by-
products are precipitated out.

(1.7)
Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

Fig. (1.2) Flow diagram for extraction of zinc by hydrometallurgical process

1.
Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

Zinc dust is added to the leach zinc sulphate solution to precipitate cadmium (i.e. cementation process)
for recovery of Cd; Co and Cu are also precipitated out. Precipitation of cobalt from leach solution is done
by adding a-nitroso-b-napthol. Then electrolysis of the purified leach solution (ZnSO4 + H2SO4) of 5.3
pH is done by using a cell with an anode of cast Pb-Ag (1%) alloy and rolled high-purity aluminium sheet
as cathode. Metallic zinc is deposited at cathode and oxygen gas is released at anode. Cu and Fe present
in solution reduce the current efficiency of the electrolyte bath.

3.4 Properties
Atomic weight of zinc is 65.38, specific gravity is 7.14; melting point and boiling point are 419 °C and
907 °C respectively. The relatively high corrosion resistance of zinc makes it useful as a protective coating
(galvanizing) on steel. Zinc, being electro-negative to iron, is slowly corroding zinc by corrosive media,
leaving the iron undamaged and protects iron. If the coating is damaged at any point, its protective
properties remain unaffected, since base sections of iron are not attacked. On cast condition, zinc possesses
a tensile strength of 3.15 to 7.87 kg/mm2; after cold work that is increased to 18.9–25.2 kg/mm2.
Zinc dissolves in strong acids (like HCl, H2SO4) with an evolution of hydrogen. Zinc oxide (ZnO)
is a fine crystalline white powder obtained by oxidation of zinc vapour in the air. Zinc oxide is a non-
fusible substance which volatilizes at a temperature above 1800 °C without melting. Reduction of zinc
oxide can be done by carbon at the temperature 950 °C.

3.5 Applications
After cold work, tensile strength is drastically increased; hence, zinc is not used where high stresses are
likely to be encountered; but it can be used for ordinary applications such as roofing, metal linings, dry
batteries etc. By rolling, the metal is easily worked to make foil, due to ductility of zinc.
High purity zinc (99.99%) is used for manufacturing of die casting parts, wire, foil and anodes. High
grade zinc (99.95%) is used for production of wire, zinc oxide, and high grade brasses. Foundry grade
zinc (98.5%) is used for making sheet and strip by rolling; foundry work for brass and other alloys castings.
Zinc (98%) is used for galvanizing, formation of zinc dust and brass. Zinc acts as an alloying element in
brass and bronze. The bulk of the metal is consumed as an alloying element of brass and in the form of
galvanized steel sheet.
Chapter Two Materials Engineering Assist. Lect. Nagham Altimime
Extraction of Non-Ferrous. Materials Extraction Methods 1st Year / 2nd. Semester
Metals

Small articles are exposed to zinc dust at elevated temperatures (350–400 °C); zinc diffuses at the
surface, and this method is known as sherardizing. This process is used for steel windows. Springs,
aeroplane components, bolts, nuts and small castings of intricate design can be made from zinc and its
alloys. Almost any metal may be applied by spraying, since zinc has a low melting point (420 °C) and
corrosion prevention property, hence being used to a greater extent than any other metal. Anti-corrosion
paints based on metallic zinc powder form, a convenient alternative to metal spraying.
On account of low melting point and prevention of corrosion, zinc is used to spray on the other metals.
Zinc in the form of wire or powder is loaded into a pistol, where it is melted and atomized by compressed
air; then is projected at the target object. The main applications of sprayed zinc coating are for steel
bridges, ships, storage tanks etc.
The copper-zinc alloys can be divided into two main groups: (a) first group contains 30–37% Zn, which
has adequate ductility and strength for cold deformation into sheets and wire; (b) second group contains
37–45% Zn, which is much less plastic when cold and is therefore worked above 500 °C. The zinc die-
cast alloys contain small amounts of Al, Cu and Mg. The most widely used of these zinc die-casting alloys
contain up to 4% Al with small amounts (0.02%) of Mg.
Zinc oxide is used for high grade pigments and pharmaceutical use. Zinc oxide is extensively used in the
manufacture of oil and other types of paints owing to its white colour and high covering power.