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PREFACE

Practical training is a way to implement theoretical knowledge to practical use to


become a successful engineer. It is necessary to have a sound practical knowledge
because it is only way by which one can acquire proficiency & skill to work successfully
different industries.
It is proven fact that bookish knowledge is not sufficient because things are not as ideal
in practical field as they should be.
Hindustan Zinc Ltd. is one of the best examples to understand the production process &
productivity in particular of Zinc.
This report is an attempt made to study the overall production system & related action
of Zinc Smelter, Debari a unit a HZL. It is engaged in production of high grade zinc
metal & other by products viz. Cd, sulphuric acid etc. since 1968 by adopting Hydro
Metallurgical technology.

Company Profile
Vedanta
Vedanta is an LSE-listed diversified FTSE 100 metals and mining company, and Indias
largest non-ferrous metals and mining company based on revenues. Its business is
principally located in India, one of the fastest growing large economies in the world.
In addition, they have additional assets and operations in Zambia and Australia. They
are primarily engaged in copper, zinc, aluminium and iron businesses, and are also
developing a commercial power generation business.
Founder of this recognition is Mr. Anil Agarwal, who is chairman of this group, a simple
person without any special degree in management field but have a great experience in
this field and a sharp sight of the future conditions and requirement.
Hindustan Zinc Limited
Hindustan Zinc Limited was incorporated from the erstwhile Metal Corporation of India
on 10 January 1966 as a Public Sector Undertaking.
In April 2002, Sterlite Opportunities and Ventures Limited (SOVL) made an open offer for
acquisition of shares of the company; consequent to the disinvestment of Government
of India's (GOI) stake of 26% including management control to SOVL and acquired
additional 20% of shares from public, pursuant to the SEBI Regulations 1997. In August
2003, SOVL acquired additional shares to the extent of 18.92% of the paid up capital
from GOI in exercise of "call option" clause in the share holder's agreement between
GOI and SOVL. With the above additional acquisition, SOVL's stake in the company has
gone up to 64.92%. Thus GOI's stake in the company now stands at 29.54%.
Hindustan Zinc Ltd. operates smelters using
Roast Leach Electro-Winning (RLE)
Hydrometallurgical (Debari, Vizag and Chanderiya Smelters)
ISP pyrometallurgical (Chanderiya Lead Zinc Smelter) and

Ausmelt (Chanderiya Lead Smelter) process routes.


Zinc Smelter, Debari-Udaipur
Location 14 km from Udaipur, Rajasthan, India
Hydrometallurgical Zinc Smelter Commissioned in 1968 Roast Leach Electrowining
Technology with Conversion Process Gone through a series of debottlenecking 88,000
tonnes per annum of Zinc
Captive Power Generation 29 MW DG Captive Power Plant commissioned in 2003
Certifications BEST4 Certified Integrated Systems ISO 9001:2000, ISO 14001:2004,
OHSAS 18001:1999, SA 8000:2001
Covered Area (Ha) 22.65
Total Plant Area (Ha) 126
Products Range
(a) High Grade Zinc (HG) (25 kgs) & Jumbo (600 kgs)
(b) Cadmium Pencils (150 gms)
Sulphuric Acid + 98% concentration
Awards & Recognitions
(a) International Safety Award: 2006 by British Safety Council, UK
(b) ROSPA Gold Award for prevention of accidents
Operating Capacity (Per Year)
Zn : 80,000MT
Acid : 130,000MT
Cd : 250MT
Zinc dust : 360MT
Work force 876 Nos.
Managerial & Engineering Staff 84 Nos.
Supervisory & Technical Staff 58 Nos.
Labour 729 Nos.
(a) Skilled 154Nos.
(b) Semi-Skilled 555Nos.
Unskilled 250Nos.
Raw Material Supplies:(a) Zawar Mines
(b) Agucha Mines
Rajpura Dariba Mines
Product Buyers:(a) Tata
(b) Bhel
Steel Companies
Process Collaborators:(a) Krebs Penorrova, France Leaching, Purification, Electrolysis
(b) Lurgi, GMBH, and Germany Roaster and gas clearing
Auto Kumpu Finland RTP, Wartsila Plant
(d) I.S.C., ALLOY, U.K. Zinc dust plant, Allen Power Plant

Zinc (Zn)

Introduction
Zinc is a metallic chemical element with the symbol Zn and atomic number 30. In
nonscientific context it is sometimes called spelter. Commercially pure zinc is known as
Special High Grade, often abbreviated SHG, and is 99.995% pure.
Zinc is found in the earths crust primarily as zinc sulfide (ZnS). Zinc (Zn) is a metallic
element of hexagonal close-packed (hcp) crystal structure and a density of 7.13 grams
per cubic centimeter. It has only moderate hardness and can be made ductile and easily
worked at temperatures slightly above the ambient. In solid form it is grayish white,
owing to the formation of an oxide film on its surface, but when freshly cast or cut it has
a bright, silvery appearance. Its most important use, as a protective coating for iron
known as galvanizing, derives from two of its outstanding characteristics: it is highly
resistant to corrosion, and, in contact with iron, it provides sacrificial protection by
corroding in place of the iron.
Zinc ores typically may contain from 3 to 11 percent zinc, along with cadmium, copper,
lead, silver, and iron. Beneficiation, or the concentration of the zinc in the recovered
ore, is accomplished at or near the mine by crushing, grinding, and flotation process.
Once concentrated, the zinc ore is transferred to smelters for the production of zinc or
zinc oxide. The primary product of most zinc companies is slab zinc, which is produced
in 5 grades: special high grade, high grade, intermediate, brass special and prime
western. The primary smelters also produce sulfuric acid as a byproduct.
With its low melting point of 420 C (788 F), unalloyed zinc has poor engineering
properties, but in alloyed form the metal is used extensively. The addition of up to 45
percent zinc to copper forms the series of brass alloys, while, with additions of
aluminum, zinc forms commercially significant pressure die-casting and gravity-casting
alloys. Primary uses for zinc include galvanizing of all forms of steel, as a constituent of
brass, for electrical conductors, vulcanization of rubber and in primers and paints. Most
of these applications are highly dependent upon zincs resistance to corrosion and its
light weight characteristics. The annual production volume has remained constant since
the 1980s. India is a leading exporter of zinc concentrates as well as the worlds largest
importer of refined zinc.
Properties of Zinc (metallic) at 293K
1. Density 7140Kg./m3
2. Melting Point 693K
3. Specific Latent Heat of Fusion 10 J/ Kg
4. Specific heat capacity 385 J/Kg/K
5. Linear expansivity 31/K
6. Thermal conductivity 111 W/m/k
7. Electric Sensitivity 5.9 ohm meter
8. Temp. Coefficient of resistance 40/k
9. Tensile Strength 150 Mpa
10. Elongation 50%
11. Young modulus 110 Gpa
12. Passions Ratio 0.25

Zinc Smelting
Zinc smelting is the process of recovering and refining zinc metal out of zinc-containing
feed material such as zinc-containing concentrates or zinc oxides. This is the process of
converting zinc concentrates (ores that contain zinc) into pure zinc.
The most common zinc concentrate processed is zinc sulfide, which is obtained by
concentrating sphalerite using the froth flotation method. Secondary (recycled) zinc
material, such as zinc oxide, is also processed with the zinc sulfide. Approximately 30%
of all zinc produced is from recycled sources.
Globally, two main zinc-smelting processes are in use:
(a) Pyrometallurgical process run at high temperatures to produce liquid zinc.
(b) Hydrometallurgical or electrolytic process using aqueous solution in combination
with electrolysis to produce a solid zinc deposit.
The vast majority of zinc smelting plants in the western world use the electrolytic
process, also called the Roast-Leach-Electrowin (RLE) process, since it has various
advantages over the pyrometallurgical process (overall more energy-efficient, higher
recovery rates, easier to automate hence higher productivity, etc.).
In the most common hydrometallurgical process for zinc manufacturing, the ore is
leached with sulfuric acid to extract the Zinc. These processes can operate at
atmospheric pressure or as pressure leach circuits. Zinc is recovered from solution by
electrowinning, a process similar to electrolytic refining. The process most commonly
used for low-grade deposits is heap leaching. Imperial smelting is also used for zinc
ores.

Zinc Smelter Debari


Zinc Smelter Debari have following main plants
Fig.-1 Plants at Zinc Smelter Debari
General Process Overview
The electrolytic zinc smelting process can be divided into a number of generic
sequential process steps, as presented in the general flow sheet set out below.
In Summary, the Process Sequence is:
Step 1: Receipt of feed materials (concentrates and secondary feed materials such as
zinc oxides) and storage;
Step 2: Roasting: an oxidation stage removing sulphur from the sulphide feed materials,
resulting in so-called calcine;
Step 3: Leaching transforms the zinc contained in the calcine into a solution such as zinc
sulphate, using diluted sulphuric acid;
Step 4: Purification: removing impurities that could affect the quality of the electrolysis
process (such as cadmium, copper, cobalt or nickel) from the leach solution;
Fig.-2 General Processes In Plant
Step 5: Electrolysis or electro-winning: zinc metal extraction from the purified solution
by means of electrolysis leaving a zinc metal deposit (zinc cathodes);
Step 6: Melting and casting: melting of the zinc cathodes typically using electrical
induction furnaces and casting the molten zinc into ingots.
Additional steps can be added to the process transforming the pure zinc (typically
99.995% pure zinc known as Special High Grade (SHG)) into various types of alloys or
other marketable products.
Raw Material Handling Section(RMH)
Smelters use a mix of zinc-containing concentrates or secondary zinc material such as
zinc oxides as feed to their roasting plant. Debari smelter is characterized by a relatively
high input of secondary materials. Smelters located inland receive their feed by road,
rail or canal depending on site-specific logistical factors and the type of feedstock (eg,
secondary zinc oxides come in smaller volumes and are typically transported by road).
Concentrate deliveries typically happen in large batches (eg, 5,000 to 10,000 tonnes).
Hindustan Zinc Smelter Debari is strategically located close to the Zawar mines that
serves as a global concentrate hub and provides for an extensive multi-modal logistical
infrastructure. It is 14 kms away from Udaipur well connected by rail, road and air. Most
zinc smelters use several sources of concentrates. These different materials are blended
to obtain an optimal mix of feedstock for the roasting process.
The zinc concentrate is delivered by trucks and is discharged into two underground bins.
Several belt conveyors transport the concentrate from the underground bins to the
concentrate storage hall. A Pay loader feeds the materials into two hoppers. By means
of discharging and transport belt conveyors including an over-belt magnetic separator, a
vibro screen and a hammer mill, the materials are transported to the concentrate feed
bin. Dross material from the cathode melting and casting process will be added to the
feed material before the vibro screen. For moistening of the concentrate several

spraying nozzles are foreseen in the concentrate storage hall, as well as on the
conveying belt before the concentrate feed bin.
Fig.-3 Raw Material Handling Flow Sheet
Blended feed from the concentrate feed bin is discharged onto a discharge belt
conveyor, which in turn discharges onto a rotary table feeder. The roaster is fed then by
two slinger belts.

Roaster Plant
Roasting is a process of oxidizing zinc sulfide concentrates at high temperatures into an
impure zinc oxide, called "Zinc Calcine". This is a metallurgical process involving gassolids reactions at elevated temperatures. A common example is the process in which
sulfide ores are converted to oxides, prior to smelting. Roasting differs from calcination,
which merely involves decomposition at elevated temperatures. A typical sulfide
roasting chemical reaction takes the following form:
S + O2 SO2.
2 ZnS + 3O2 2 ZnO
SO2 + O2 SO3
CuS + 1.5O2 CuO + SO2
The gaseous product of sulfide roasting, sulfur dioxide (SO2) is often used to produce
sulfuric acid.
Approximately 90% of zinc in concentrates are oxidized to zinc oxide, but at the roasting
temperatures around 10% of the zinc reacts with the iron impurities of the zinc sulfide
concentrates to form zinc ferrite. A byproduct of roasting is sulfur dioxide, which is
further processed into sulfuric acid.
Reduction of zinc sulfide concentrates to metallic zinc is accomplished through either
electrolytic deposition from a sulfate solution or by distillation in retorts or furnaces.
Both of these methods begin with the elimination of most of the sulfur in the
concentrate through a roasting process,
Roasting Of Zinc Concentrate
Debari roasting technology is characterized by lowest operating cost, minimum waste
material, safe and simple operation at high availability and the production of useful side
products as steam and sulfuric acid. Strongest environment regulations are met for
solid, liquid and gaseous products or emissions.
Fig.-4 Process Flow Sheet In Roaster Plant
The roaster has a cylindrical bed section, a conical intermediate section, a cylindrical
enlarged top section, and a grate area of 123 square meters. The enlarged cylindrical
section enables a complete roasting of even the finest calcine particles without the
occurrence of a secondary combustion phenomenon. For process optimisation 10
secondary air nozzles are installed to be able to distribute additional roasting air above

the bed. A slight draught is maintained at the roaster gas outlet to ensure the safety of
the roaster operation.
Depending on the raw material, the roaster operates with a capacity of 15 000 - 300
000 t/y (zinc) and respectively 55 000 260 000 t/y (pyrite).
The combustion air serves both as a carrier medium for the fluid bed and as a source of
oxygen for the predominant reaction, which convert the metal sulfide to metal oxide
and sulfur dioxide. The combustion air is provided by a high pressure air fan, which is
controlled between the lower and a upper limit for a stable fluidization of the bed. The
reaction in the roaster is strongly exothermic, and the gas leaves the roaster with a
temperature of approximately 800C to 975C and an SO2 concentration of
approximately 10 % by volume, dry basis.
As combustion medium during the above described preheating diesel oil is used. The
maximum flow of diesel oil amounts to 3000 kg/h. The composition of offgas during
furnace heating is shown in below table:
The roasting process is fully automated, controlled and operated from a central control
room. Debari operates some of the worlds largest roasters, which are modelled after
those used throughout the industry.
The roasting step results in the production of calcine material (which is transported to
the subsequent leaching plant) and sulphur dioxide-rich waste gases. Waste heat boilers
remove the calcine contained in these gases as well as recovering the heat in the form
of steam that is used in the leaching plant and/or converted into electricity.
The hot dust-laden gas stream leaving the roaster is drawn into the waste heat boiler
under suction from the SO2 blower. In the boiler, the dust-laden gases are cooled down
from the roasting temperature to about 350C before entering the dust precipitation
system. Finally, the sulphur dioxide is converted into sulphuric acid in a contact process,
generating an important smelter by-product.
Debari is able to deliver the whole off-gas treatment and energy recovery system after
the roaster which includes following process steps:
Waste heat boiler
Hot Electrostatic Precipitator (ESP)
Wet Gas Cleaning
Sulfuric Acid Plant
Fluidized-Bed Roaster
In a fluidized-bed roaster, finely ground sulfide concentrates are suspended and
oxidized in a feedstock bed supported on an air column. As in the suspension roaster,
the reaction rates for desulfurization are more rapid than in the older multiple-hearth
processes. Fluidized-bed roasters operate under a pressure slightly lower than
atmospheric and at temperatures averaging 1000 C (1800 F). In the fluidized-bed
process, no additional fuel is required after ignition has been achieved. The major
advantages of this roaster are greater throughput capacities, greater sulfur removal
capabilities, and lower maintenance.
Waste Heat Boiler
The hot dust laden gas stream leaving the roaster is drawn into the waste heat boiler
under suction from the SO2 blower. The waste heat boiler is a horizontal-pass boiler,
gas-tight welded, membrane wall-type, directly connected with the gas outlet flange of
the roaster by means of a flexible fabric expansion joint.
In the boiler, the dust-laden gases are cooled down from the roasting temperature to
about 350C before entering the dust precipitation system. The waste heat boiler is a
forced-circulation-type boiler for the production of superheated steam. The convection

heating surfaces of superheaters and evaporators are combined in bundles in a


suspended arrangement.
The waste heat boiler is equipped with a membrane tubed settling (drop-out) chamber
ahead of the front convection bundles. In the settling chamber, part of the dust carried
along with the gas is separated. Since the waste heat boiler handles roasting gases
having a very high dust content, a mechanical rapping device has to be provided.
Pneumatic cylinders drive these rappers. Depending on the degree of fouling, the
rappers can be actuated by a cylinder controller from a switching cabinet. The
pneumatic cylinders are operated by compressed air, which can be taken from the plant
air system. The gas-flow velocity through the tube banks was designed to be very low to
avoid erosion. The tube banks can be easily removed for maintenance after the plant
has been taken out of operation. The rapping device is automatically actuated at certain
time intervals. The dust separating out in the boiler is collected in a chain conveyor and
fed to the rotary drum cooler. The combined system of cooling coils in the roaster,
superheated tube bundles, evaporator tube bundles, and membrane wall casing is
designed for the maximum load of the boiler. The boiler produces steam in a forced
circulation system and is equipped with two circulating pumps, one motor-driven and
one turbine-driven. Each pump is capable of handling the maximum rating of the boiler
continuously. The stand-by steam-driven circulating pump will start automatically when
the electric power supply fails or when the flow of circulating water falls below a preset
quantity. The water-steam mixture, produced in the forced circulation system, is
separated in a steam drum by means of a demister. A pressure relief system is included
to exhaust steam directly to the atmosphere via a noise damper in the event of
curtailed steam usage in the leaching plant. The steam relief system is designed for the
full waste heat boiler production of 49 metric tons per hour. The level-control valve
installed in the incoming demineralized water line controls the feedwater tank level. The
demineralized water is deaerated in the deaerator on top of the feedwater tank.
Deaeration is accomplished by means of steam from the saturated steam line. The
feedwater tank pressure is maintained by the pressure control valve. The deaerated
feedwater is preheated and fed to the steam drum via the feedwater pumps, one motordriven and one steam-driven. The steam drum level is controlled using a three-element
control system. An additive preparation and dosing station for the boiler feedwater is
included in the system.
Cooled gases leaving the waste heat boiler flow into the hot electrostatic precipitator
(ESP) for final dust removal. Cyclone
The cooled and dust loaded gas enters the two parallel cyclones for pre-dedusting with
a temperature of approx. 350 C. The gas leaves the cyclones at the top whereas the
dust is collected in the lower part of the cyclones and removed via rotary valves. Final
dedusting of the hot gas is achieved in the hot ESP. Hot gas precipitator
The gas leaving the cyclones enters a three field hot gas ESP. The ESP consists of the
discharge electrodes, the collecting electrodes, gas distribution walls, casing, roof,
hoppers, horizontal inlet and outlet nozzles, pressure relief system, rapping systems,
sealing air system for the insulators with electric heater and transformer rectifiers with
control cabinet for the electrostatic fields. The precipitator is insulated. The collected
dust is removed from the ESP via the chain conveyor and the rotary valves. Rapping
systems are installed at the gas distribution plates in the inlet cone of the precipitator
and at the discharge and collecting electrodes. At their bottom end, the collecting
electrodes run through rapping bars, so that the rap is effected at the lower side end in
the plate plane. A hammer shaft rotates at the end of each electrostatic field, lifting the

rapping hammers which drop down in a free fall when the vertical position is exceeded.
The acceleration amounts to more than 200 g (200 x 9.81 m/s2) at the total collecting
electrode area.
During start-up and shut-down the gas temperature in the precipitator can fall below the
dew point. To prevent condensation on the insulator a heating system is installed. This
heating system, consisting of a fan and a heater supplies hot air to all insulators. This
hot air prevents the penetration of gases to the insulators and also will keep the
insulators at a temperature above the dew point to prevent the formation of
condensate, which could cause electrical flash-overs.
Each discharge electrode system is supported by means of four high voltage insulators.
The discharge electrodes are tightened in tubular frames, which are vertically arranged
between the collecting electrodes. The high voltage insulators which support the
discharge electrode systems are located within box-type roof beams on top of the
electrostatic precipitator and a key-system is used to secure every door. By this way
they are protected against accidental contact to personnel.
Separate transformer-rectifier sets per each electrostatic field (= 3 fields = 3 units) are
installed. The discharge electrode systems is supplied with high voltage DC by modern
transformer rectifier sets. Each transformer rectifier set will have its own cubicle for
control and regulation. Such a transformer rectifier set (power pack) contains a high
tension transformer and semi conductor rectifier pack. Both are installed in a steel
vessel immersed in oil. The vessels of the power packs are located in the high voltage
room below the hot gas electrostatic precipitator. The optimum values of the high
voltage are controlled by a special low voltage control system.
There is a high voltage switch on top of the T/R set for manual operation for
disconnecting of high voltage supply and earthing of the discharge electrode system

Heat and Mass Balance Over Roaster Plant III


Mass Balance
Concentrate feed = 39.75 t/hr
feed in kg/hr = 39750 kg/hr
Moisture content = 10 %
Relative humidity = 0.111
Dry feed =39749.89 kg/hr
Concentrate composition
Component % Kg/hr
Zn 52 20669.94
Fe 8.5 3378.74
Lead 1.5 596.25
Copper 0.1 39.75
Suphur 30 11924.97
C 0.9 357.749
Cd 0.16 63.60
SiO2 2 795.00
Insolubles 1 397.50

Fig.-5 Calcine Balance Over Roaster Plant


1. Reactions of zinc:
Zn + S
ZnS
65.4 32 97.4
20669.94 10113.73 30783.68
ZnS + 1.5 O2
ZnO + SO2
97.4 48 81.4 64
30783.68 15170.60 25726.81 20227.47
2. Reactions of lead:
Pb + S
PbS
207.2 32 239.2
596.25 92.08 688.33
PbS + 1.5 O2

PbO + SO2
239.2 48 223.2 64
688.33 138.13 642.29 184.17
3. Reactions of copper:
Cu + S
CuS
63.5 32 95.5
39.75 20.03 59.78
CuS + 1.5 O2
CuO + SO2
95.50 48 79.5 64
59.78 30.05 49.77 40.06
4. Reactions of iron:
Fe + S FeS
Fe + S2 FeS2
Amount of Fe present in FeS 75 % = 2534.06 Kg
Amount of Fe present in FeS2 25 % = 844.69 Kg

Fe + S FeS
56 32 88
2534.06 3982.09
2 FeS + 3.5 O2
Fe2O3 + 2 SO2
176 112 160 128
3982.09 2534.06 3620.08 2896.06
Fe + S2
FeS2
56 64 120
844.69 965.35 1810.04
2 FeS2 + 5.5 O2
Fe2O3 + 4 SO2
240 176 160 256
1810.04 1327.36 1206.69 1930.71

5. Reactions of cadmium:
Cd + S
CdS
112 32 144
63.60 18.17 81.77
CdS + O2
CdO + SO2
144.00 32 128 64
81.77 18.17 72.69 36.34

6. For Silica:
SiO2
SiO2
795.00 795.00
7. For Carbon:
C + O2
CO2
12 32 44
Feed and Product rate for different components:
Concentrate Feed rate Oxides Wt of oxides Oxygen req. SO2
(kg/hr) (kg/hr) (kg/hr) (kg/hr)
ZnS 30783.68 ZnO 25726.80882 15170.5998 20227.4664

PbS 688.33 PbO 642.2906757 138.13 184.17


FeS 3982.09 Fe2O3 3620.08 2534.06 2896.06
FeS2 1810.04 Fe2O3 1206.69 1327.36 1930.71
CuS 59.78 CuO 49.77 30.05 40.06
SiO2 795.00 SiO2 795.00 0 0
C 357.75 CO2 44.00 32 0
CdS 81.77 CdO 72.69 18.17 36.34
Insolubles 397.50 397.50 0.00 0.00
Total 38955.93 32510.82 19250.36 25314.81
Oxygen Required for 38.956 tonnes of concentrate = 19250.36 kg/hr
Oxygen Required for 1 tonnes of concentrate = 494.16 kg/hr
= 346.13 m3/hr
Oxygen Required for 39.75 tonnes of concentrate = 13758.49 m3/hr
Air Required for 39.75 tonnes of concentrate = 65516.60 m3/hr
Excess air = 25 %
= 16379.15 m3/hr
CO2 = 82.1846667 m3/hr
SO2 = 8865.72238 m3/hr
Clean Air escaping from top = 68137.26 m3/hr
Total Air at furnace inlet = 81895.75 m3/hr
Gases escaping from furnace top = 77085.17 m3/hr
Calcine from top of the furnace = 75 %
= 24383.11 kg/hr
Calcine from bottom of the furnace = 25 %
= 8127.70 kg/hr
Dust removing capacity of boiler = 45 %
Dust removing capacity of Cyclone separator = 40 %
Dust removig Capacity of HGP = 15 %

Intlet outlet Underflow


Boiler 24.38 t/hr 13.41 t/hr 10.97 t/hr
Cyclone separator 13.41 t/hr 3.66 t/hr 9.75 t/hr
HGP 3.66 t/hr 0.01829 t/hr 3.64 t/hr

Heat Balance
Reactions involved :
Hf(KJ/mol)
ZnS + 1.5 O2
ZnO + SO2
Enthalpy -204.6 0 -348 -296.84 KJ/mol -440.24
PbS + 1.5 O2

PbO + SO2
-98.12 0 -218.08 -296.84 KJ/mol -416.8
CuS + 1.5 O2
CuO + SO2
-48.5 0 -155.2 -296.84 KJ/mol -403.54
2 FeS + 3.5 O2
Fe2O3 + 2 SO2
-201 0 -825.5 -593.68 KJ/mol -1218.18
2 FeS2 + 5.5 O2
Fe2O3 + 4 SO2
-355 0 -825.5 -1187.36 KJ/mol -1657.86
CdS + O2
CdO + SO2
-208.4 0 -235.6 -296.84 KJ/mol -324.04
C + O2
CO2
0 0 -393.5 KJ/mol
Total Heat of Above reactions = - 4460.66 KJ/mol

Heat Balance for Furnace:


Temp.of calcine at furnace inlet = 25 C
Temp.of calcine at furnace outlet = 920 C
t = 895 C
Calcine flyover
M = 24383.11 kg/hr
Q = 21248538.45 kj/hr
= 21248.53845 MJ/hr
Air = 68137.26 m3/hr
M = 88158.32 kg/hr
Cp = 1 kj/kg-k
Q = 102968915.5 kj/hr
= 102968.9155 MJ/hr

SO2
M = 25314.81 kg/hr
Cp = 0.645 kj/kg-k
Q = 19071167.99 kj/hr
= 19071.16799 MJ/hr
Calcine uderflow
M = 8127.70 kg/hr

Cp = 0.75 kJ/kg-k
Q = 7082846.15 KJ/hr
= 7082.84615 MJ/hr
CO2
M = 44.00 Kg/hr
Cp = 1.22 KJ/Kg-K
Q = 62698.24 KJ/hr
= 62.69824 MJ/hr
Radiation Loss
= 3%
= 40699.3869 MJ/hr

water evap.
Q=ml
= 8581320 Kj/hr
= 8581.32 MJ/hr

Total heat output = 159015.486 MJ/hr


Heat Input = 4460.66 KJ/mol
Total moles = 350.29 kmol/hr
Q input = 1562537.85 MJ/hr
Qo/p = 159015.49 MJ/hr
Q left = 1403522.37 MJ/hr

For cooling coils


Q = m*L
latent heat of vaporisation, L = 2.42 MJ/Kg
m = Q/L
M = 17399.04 Kg/hr
= 17.40 t/hr
enthalpy of liquid water, h1 = 104.86 kJ/kg at 25 C
enthalpy of superheated steam, h2 = 4398 kJ/kg at 920 C
h = 4293.14 kJ/kg
Q = mh
M = Q/h

= 9.80766316 t/hr
Heat Taken by cooling coil = 3%
Q = h*A*t H = 0.828 MJ/hr-m2-C
A = 54.98 t = 925 C
Heat retained = 97%

Heat Balance Over Waste Heat Re-Boiler:


Temp.of calcine at boiler outlet = 350 C
Temp.of calcine at boiler inlet = 920 C
t = 570 C
Calcine underflow temp. in boiler = 900 C
t = 20 C
Calcine flyover
M = 13410.71 Kg/hr
Q = 8434832.922 Kj/hr
= 8434.832922 Mj/hr
Air = 68137.26 m3/hr
M = 88158.32 kg/hr
Cp = 1 kj/kg-k
Q = 74317462.16 kj/hr
= 74317.46216 MJ/hr
SO2
M = 25314.81 kg/hr
Cp = 0.645 kj/kg-k
Q = 13764550.18 kj/hr
= 13764.55018 MJ/hr

Calcine uderflow
M = 10972.40 kg/hr
Cp = 0.75 kJ/kg-k
Q = 2398647.08 KJ/hr
= 2398.64708MJ/hr
CO2
M = 44.00 Kg/hr
Cp = 1.22 KJ/Kg-K
Q = 45252.24 KJ/hr
= 45.25224 MJ/hr
Water evap.

Q = ml
= 8581320 Kj/hr
= 8581.32 MJ/hr
Radiation Loss
=3%
=0 Mj
Heat leaving Boiler
Q entering Boiler = 1513349.34 MJ/hr
Total Q leaving from top = 105143.418 MJ/hr
Heat leaving from boiler bottm = 2398.64708 MJ/hr
Q1 retaining inside boiler = 1405807.27 MJ/hr
Air = 68137.26 m3/hr
M = 88158.32 kg/hr
Cp = 1 kj/kg-k
Q = 28475136.75 kj/hr
= 28475.13675 MJ/hr
Heat Balance Over Cyclone Separator:
Temp.of calcine at Cyclone outlet = 300 C
Temp.of calcine at Cyclone inlet = 350 C
t = 50 C
Calcine flyover
M = 3657.47 kg/hr
Q = 881414.1164 kj/hr
= 881.4141164 MJ/hr

SO2
M = 25314.81 kg/hr
Cp = 0.645 kj/kg-k
Q = 5273961.696 kj/hr
= 5273.961696 MJ/hr
Calcine uderflow
M = 9753.25 kg/hr
Cp = 0.75 kJ/kg-k
Q = 2350437.64 KJ/hr
= 2350.43764 MJ/hr
CO2
M = 44.00 Kg/hr
Cp = 1.22 KJ/Kg-K
Q = 17338.64 KJ/hr
= 17.33864 MJ/hr
water evap.
Q = ml
= 8581320 Kj/hr
= 8581.32 MJ/hr
Radiation Loss

3%
0 MJ/hr

Heat
Heat
Heat
Heat

Entering at cyclone inlet =105143.418MJ/hr


leaving from Cyclone top =MJ/hr
leaving at cyclone bottm =2350.43764MJ/hr
Entering HGP =102792.98MJ/hr

Heat Balance Over Hot Gas Precipitator:


Temp.of calcine at HGP outlet = 290C
Temp.of calcine at HGP inlet = 300C
t = 10C
Calcine flyover
M = 18.29kg/hr
Q = 3861.303327kj/hr
= 3.861303327MJ/hr
Air = 68137.26 m3/hr
M = 88158.32 kg/hr
Cp = 1 kj/kg-k
Q = 24948804.02 kj/hr
= 24948.80402 MJ/hr
SO2
M = 25314.81 kg/hr
Cp = 0.645 kj/kg-k
Q = 4620839.505 kj/hr
= 4620.839505 MJ/hr

Calcine uderflow
M = 3639.18 kg/hr
Cp = 0.75 kJ/kg-k
Q = 768399.362 KJ/hr
= 768.399362 MJ/hr

Water evap.
Q = ml
= 8581320 Kj/hr
= 8581.32 MJ/hr

CO2
M = 44.00 Kg/hr
Cp = 1.22 KJ/Kg-K
Q = 15191.44 KJ/hr
= 15.19144 MJ/hr

Radiation Loss = 3%
= 0 MJ/hr

Heat Entering HGP 102792.98 MJ/hr


Heat Leaving at HGP bottom 768.399362 MJ/hr
Heat retaining inside HGP 102024.581 MJ/hr

Gas Cleaning Plant


Gases leaving waste heat boiler are passed through cyclone to remove the calcine
particles and then passed through hot gas precipitator to remove the fine particles of
calcine by the application of electric field.
Quench Tower
In the quench tower, the hot gas is cooled by the evaporation of water. The heat of the
incoming gas (Temperature: > 300C) is used for the evaporation of water that is
sprayed into the Quench Tower. The sensitive heat of the gas is converted into water
vapor (latent heat). This type of cooling can be considered as an adiabatic process.
Adiabatic means, the process step is operated without energy exchange with the
environment. But besides this quenching, also a part of the dust and condensable
impurities in the gas will be scrubbed in the quench tower. At the outlet of the tower,
the gas contains water vapor. If the temperature is lowered, water vapor will condense.
The Quench Tower is designed as counter current flow type quencher. The gas inlet is at
the bottom part of the casing. The gas outlet is at the top of the quench tower. The
liquid is sprayed into the quench tower in counter-current flow to the gas. A part of the
spray does evaporate, but the biggest portion will be collected in the lower part of the
tower which does serve as pump tank. A side stream of the spray circuits is guided
through a settling tank for removal of suspended solids.
Excess liquid from the washing and cooling system is discharged from the quench tower
circuit via strippers.
Packed gas cooling tower
The adiabatic cooling in the quench tower does result in water saturated gas and
consequently in a high content of gaseous water in the SO2-gas. If the water vapour
would not be lowered prior to the drying tower, the concentration of the sulphuric acid
would be lower than acceptable limits. Removal of water vapour is done in a packed gas
cooling tower. The gas enters the tower from the bottom and flows upwardly through

the packing. In counter current flow to the gas, cold cooling liquid (weak acid) is
distributed over the packing. The downward flowing cold liquid does cool the SO2-gas
and water vapour is condensed. While flowing downward, the cooling liquids heats up.
The lower part of the tower serves as a pump tank. From this pump tank, the cooling
liquid is circulated via pumps and plate heat exchangers back to the liquid distribution
system. The plate heat exchangers are cooled with cooling water which is circulated via
evaporative type cooling towers.
The packed gas cooling tower is designed as cylindrical vessel made of FRP. Diameter
and packing height are calculated in a way, that filling bodies made of plastic (PP, PVC)
with a diameter of 2 inch and a specific surface of more than 90 m2/m3 are to be used.
The gas side pressure drop does not exceed 4 mbar under full gas load. The liquid
distribution system shall ensure an equal distribution of the liquid on the upper surface
of the packing. The liquid distribution system will have two feed points for cooling liquid.
The liquid distribution system will be made of FRP. Plastic pumps (material: HP PE) will
be used. The pipes will be made of FRP.
Wet gas precipitator
Final removal of dust and aerosols will be carried out in the wet electrostatic precipitator
system which consists of two stages of precipitators. Downstream of the second stage
of the wet electrostatic precipitators, the SO2-gas will be optically clean. The wet ESPs
will be of the tube type with gas flow in vertical direction. While flowing through the wet
ESP tubes, the aerosols and particles are electrically charged due to high tension and
migrate to the collection tubes.
Particles and aerosols separated from the gas will be removed continuously together
with the condensate at the bottom of the ESPs, respectively from the connected gas
ducts. The liquids will be directed to a tank, which does also serve for wet ESP flushing.
Normally wet ESPs do have a good self-cleaning. This self cleaning can be improved in
the second stage wet ESPs by the installation of a continuous spraying system But from
time to time, depending on the operating conditions, each precipitator must be flushed.
This is done with liquid, that is withdrawn from a tank and that is pumped to the
flushing nozzles installed in the top part of the wet ESPs.
All parts of the wet electrostatic precipitators in contact with the gas stream will be
made of the following acid resistant materials: Homogeneously lead lined steel PVC, PP,
FRP or FRP with PVC-lining
The materials are selected in accordance with the operating conditions and mechanical
loads to which the equipment is subjected.
Mercury Removal
For the production of sulphuric acid with a low mercury-content, so-called Norzinc
Mercury Removal Process (Calomel Process) is in foreseen. This process allows a cost
efficient removal of metallic mercury vapours from SO2-gases upstream of sulphuric
acid plants. The ingress of mercury into the sulphuric acid is prevented and a safe and
reliable production of a sulphuric acid with low mercury contents is achieved.

Acid Plant

Plant Description
The sulphuric acid plant mainly consists of 2 plant sections:
The drying and absorption section
The converter section with the gas to gas heat exchangers
Drying and Absorption Section
The drying and absorption section mainly consists of the drying tower, the intermediate
absorber, the final absorber with individual acid pumps, the acid coolers and the acid
piping. These towers are of identical construction: each tower consists of a bricklined
steel shell with a filling of ceramic Intalox saddles. The layer of Intalox saddles is
supported by a supporting structure made of acid resistant stoneware.
The irrigated acid is distributed uniformly over the packing by the irrigation system. At
the gas outlet of each tower gas filters are installed, for the drying tower a wire-mesh
filter, for the intermediate and final absorber candle type filters made of a casing
plugged with special glass wool. Most part of the acid mist and all acid droplets will be
removed from the gas by the filters.
The gas flow through the towers is countercurrent to the acid flow, i.e. the gas flows
from the bottom to the top of the tower. From the bottom of the tower(s) the acid flows
to the pump sump and is pumped from there by the acid pumps (via the acid coolers)
back to the irrigation system.
Acid transfer lines between the drying tower, the intermediate absorber and the final
absorber and injection lines for dilution water at the intermediate absorber and final
absorber enable to control the necessary acid concentration for each of the towers. The
acid cooler for the drying tower, intermediate and final absorption as well as for the
product acid system are plate-type acid coolers.
Converter system
The converter system consists of a stainless steel 4-layer converter. The arrangement of
the catalyst beds is 3 + 1, i.e. the intermediate absorption is after the 3rd layer. The
converter itself is an insulated, vertical and cylindrical vessel divided in four sections:
called layers or trays. The catalyst required for the conversion of SO2 to SO3 is arranged
on these layers.
Basic Operations in Plant
Drying tower
Column packed with ceramic packing to facilitate contact of SO2 Bearing gases with
dilute sulphuric acid
Gases leaving the Wet Gas Precipitator are passed through drying tower to remove the
moisture by spraying sulphuric acid from top and gases enter from bottom. During the
removal of moisture from the gases heat is liberated which increases the temperature of
the circulating acid.
Cooling of circulating acid is done by passing the acid through PHE(Plate heat
exchanger), where filter water is used as coolant. The concentration of circulating acid is
maintained by crossing through FAT & IAT vessel acid. This is done automatically based
on sensing of concentration of circulating acid by concentration analyzer.
SO2 Blower
Blower to circulate the sulphur dioxide bearing gases in converter through heat
exchangers and mixer
The SO2 gas blower is arranged downstream the drying tower and transports the gas
from the roaster section via the gas cleaning plant through the sulphuric acid plant. The
blower will be provided with an electric motor.

Fig.-6 Process Diagram For Acid Plant


Converter Group
After being discharged from the SO2 blower the gas will be then routed to the shell side
of heat exchanger IV. In this heat exchanger, the main part of the SO2 gas will be
preheated to a temperature of about 255C. A small part of the cold SO2 gas will be
withdrawn from the lower part of the heat-exchanger IV and routed to the tube side of
heat exchanger II where it will be preheated to a temperature of about 255C while
cooling the gas between layer II and III. Both gas streams will be collected at the
entrance of heat exchanger I. Before entering the first bed of the converter the gas will
pass first through the shell side of that heat exchanger. The gas exits this heat
exchanger at a temperature of approx. 400C and enters the first catalyst bed. Bypass
lines will be located around heat exchangers IV and I to the inlet of the first bed. These
bypass-streams will be utilized for adjusting the gas inlet temperature to the first and
third bed of the converter. The gas leaving the first pass will be cooled in the tube side
of the heat exchanger I to approx. 425C and enters the second bed. After passing
through the second bed the gas will be routed through the tube side of heat exchanger
II thus cooling the SO3 gas to approx. 433C by preheating the SO2-gas coming from
the drying tower. The gas will be fed to the third pass of the converter. After the third
layer the temperature of the gas is approx. 443 C.
The gas will be cooled will be cooled in the heat exchangers III A/B to temperature of
165 C and leaving to the intermediate absorption. After the SO3 has been absorbed in
the intermediate absorber, the gas is returned to the converter via the shell side of heat
exchanger III A and III B where it will be preheated to a temperature of approx. 400C
before entering the fourth catalyst bed The gas leaving the fourth bed at a temperature
of approx. 410C, passes through the tube side of heat exchanger IV where it will
preheat the cold SO2 gas before entering the first bed. After being cooled to 271 C, the
gas enters the economizer. The gas leaving the economizer at approx. 180C will then
passed to the final absorber where the remaining SO3 will be absorbed.
Preheater
The preheating is needed to preheat the converter system (e.g. catalyst and heat
exchangers) from cold conditions to operating conditions and low SO2 strength,
whereas during normal operation of the plant the heat released within the process
allows autothermal operation of the plant. In addition lower or varying SO2concentrations can be compensated. The separate preheater preheats air or, in start-up
phases, SO2-gas to the required temperatures.
Intermediate Absorber Section
After the SO3 gas has passed through the tube side of heat exchangers III A/B this gas
will then pass through the packed tower section in countercurrent to the acid. After
passing through the candle filter, the gas enters the shell side of heat exchangers III A/B
leaving them preheated by the hot SO3 gas at approx. 400C. As the absorption of SO3
generates heat, the circulating acid at a temperature of 87C will be cooled before
returning to the absorber distribution systems as described before. The acid collected in
the sump of the intermediate absorber will be pumped through plate type acid coolers
by the vertical intermediate absorber pump back to the absorber distribution system. A
bypass located around the cooler ensures a constant temperature of approx. 70C to
the absorber. The concentration of the circulating acid, measured downstream of the
cooler, will be maintained by the addition of 96 % acid from the SO2 drying tower and

by addition of dilution water. The level in the absorber will be controlled by transferring
98.5 % acid to the final absorption system Final Absorber Section
The SO3 gas routed from the economizer will enter the final absorption tower. The gas
at a temperature of 180C will flow through the packed tower section. 98.5 % circulating
acid will be introduced counter-currently to the SO3 gas through an acid distribution
system located in the upper part of the absorber section. After passing through the
packed bed and candle filter assembly, the gas will be routed to the tail gas scrubbing
system. As the absorption of SO3 generates heat, the circulating acid at a temperature
of 85C will be cooled before returning to the absorber. The acid collected in the pump
tank will be pumped through a plate type acid cooler by an vertical mounted final
absorber pump. A temperature-controlled bypass located around the cooler ensures a
constant temperature of approx. 75C to the absorber. The concentration of the
circulating acid, measured downstream of the cooler, will be maintained by the addition
of process water. The level in the absorber pump tank will be maintained by transferring
product acid to the to the clients storage facilities by the product acid pump. In the
product acid cooler the temperature will be reduced from approx. 85 C to 40 C.
Important Process Criteria
For the production of sulphuric acid SO2 containing gases from the zinc roasting are
used. There are four main process criteria in the production of sulphuric acid from these
kind of gases by the contact/converter process.
They are:
Gas drying and water balance
Energy/ heat balance
Conversion of SO2 to SO3
Required O2 /SO3 ratio
Gas drying and Water balance
Gas drying is an important process step in this type of contact plant. Gas drying
protects cooler parts of the plant, such as heat exchangers, against corrosion by acid
condensation. It safeguards against formation of acid mist which can be very difficult to
absorb in a later stage of the process. It also protects the catalyst from acid
condensation during plant shut-downs. Therefore, the life of the plant and also the tail
gas purity depend in large measure on a sufficient gas drying.
A substantial amount of heat - not just the heat of dilution of the sulphuric acid but also
the heat of condensation of the water - is liberated in the gas drying stage. For that
reason the circulated acid is generally cooled by indirect heat exchange before being
recycled to the dryer.
Water Balance
The water balance of contact sulphuric acid plants in general may simply be defined by
the specific amount of process water required for achieving the desired product acid
strength from the amount of SO2 converted to SO3.
In the case of cold gas acid plants (like roasting plants) the process water requirements
are usually balanced nearly completely by the water vapor content of the SO2-feed
gases entering the drying tower except for a small margin necessary for the automatic
acid strength control. Thus at a given SO3 gas concentration and SO2 conversion rate
as well as at a fixed product acid strength, the only variable that can and has to be
controlled or limited is the water vapor content of the feed gases entering the drying in
order not to exceed the water balance of the whole system.This is done in the wet gas
purification system by cooling the SO2 gases down to the dew point temperature
corresponding to the maximum allowable water vapor content.

When evaluating the required dew point temperature, it is important not only to
consider the designed suction pressure of the gas purification system but also the
external barometric pressure which depends largely on the elevation of the plant above
sea level.
Absorption of SO3
Sulphur trioxide formed by the catalytic oxidation of sulphur dioxide is absorbed in
sulphuric acid of at least 98 % concentration, in which it reacts with existing or added
water to form more sulphuric acid. The process gas leaving the converter system is
cooled, first in a gas-gas heat exchanger to a temperature of about 180C before
entering the absorber. The gas entering the absorber is therefore not completely cold
and it passes heat to the absorber acid as it passes through the absorber; by the time it
reaches the outlet it is virtually at the same temperature as the incoming absorber
acid.
A substantial amount of heat is also generated in the absorber acid from the absorption
of sulphur trioxide and the formation of sulphuric acid, and the acid temperature rises in
consequence by a margin which depends on the acid circulation rate. The acid
concentration is maintained constant by adding process water to the acid leaving the
absorber and the acid crossflow from the dryer at a rate controlled by a concentration
measuring device. The circulated acid is cooled by indirect cooling.