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Summer Training Project

MACHINE SHOP (ZINC


PLANT)
Training Period : 25-05-2015 to 07-072015
Submitted By:
Shubham Sen
Submitted To:

Department of Mechanical
Engineering

Sir Padampat Singhania


University, Udaipur

ACKNOWLEDGEMENT
I wish to acknowledge the encouragement received
from Mr. Naveen Kumar (HOD, Mechanical
engineering department, SPSU, Udaipur) & Mr.
Satish Ajmera (Training Incharge) for initiating my
interest in training.

I earnestly acknowledge my profound sense of


gratitude to Mr. Naveen Kumar.
His mastery & work helped me in covering out this work
smoothly. I am also grateful of all the workers of various
departments who have helped me to improve my
thinking as well as the practical knowledge.

Finally, I wish to add that I am indebted to god & My


parents for everything good that has happened to me.

Shubham Sen
(12ME001672)

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 in
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 of 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
technolo

Shubham Sen
(12ME001672)

TABLE OF CONTENTS
Title

Page

Acknowledgements.............................................................................................I
Training Certificate.............................................................................................II
Preface................................................................................................................III
1. Company Profile ...................................................................................01
1. Vedanta ...................................................................................................01
2. Hindustan Zinc Limited ..........................................................................01
3. Zinc Smelter Debari ................................................................................02
2. Zinc ................................................................................................................04
1. Introduction .............................................................................................04
2. Properties of Zinc ....................................................................................05
3. Zinc Smelting ..........................................................................................05
3. Zinc Smelter Debari .....................................................................................07
1. General Process Overview ......................................................................07
2. Raw Material Handling Section ..............................................................09
4

4. Roaster Plant ................................................................................................11


1.
2.
3.
4.
5.

Roasting of Zinc Concentrate .................................................................11


Fluidized Bed Roaster .............................................................................14
Waste heat boiler ....................................................................................14
Cyclone ...................................................................................................16
Hot Gas Precipitator ...............................................................................16

5. Heat and Mass Balance Over Roaster Plant .............................................19


1. Mass Balance ..........................................................................................19
2. Heat Balance ...........................................................................................26
6. Gas Cleaning Plant ......................................................................................32
1. Quench Tower ........................................................................................32
2. Packed Gas Cooling Tower ....................................................................32
Title

Page

3. Wet Gas Precipitator ...............................................................................33


4. Mercury Removal ...................................................................................34
7. Acid Plant .....................................................................................................35
Drying and Absorption Section ...............................................................35
Converter System ....................................................................................36
Basic Operations In Plant
1.
2.
3.
4.
5.
6.

Drying Tower .........................................................................................36


SO2 Blower .............................................................................................36
Converter Group .....................................................................................37
Preheater .................................................................................................38
Intermediate Absorber Section ...............................................................39
Final Absorber Section ...........................................................................39

Important Process Criteria


1.
2.
3.
4.
5.

Gas drying and Water balance ................................................................40


Water Balance .........................................................................................41
Absorption of SO3 ...................................................................................41
Energy (Heat) Balance ............................................................................42
O2 /SO2 Ratio ...........................................................................................43

8. Leaching Plant ..............................................................................................44

1.
2.
3.
4.
5.
6.
7.

Neutral Leaching .....................................................................................44


Acid Leaching .........................................................................................47
Neutralisation ..........................................................................................47
Residual Treatment Plant ........................................................................48
Magnesium Removal ...............................................................................49
Horizontal Belt Filter ...............................................................................50
Purification ..............................................................................................51

Title

Page

8. Cadmium Plant ........................................................................................52


9. Gypsum Removal.................................................................................... 53
9. Electrolysis Plant ..........................................................................................54
10. Melting and Casting ...................................................................................55
11. References ...................................................................................................56

TABLE OF FIGURES
Fig.-1 Plants at Zinc Smelter Debari .......................................................07
Fig.-2 General Processes In Plant ............................................................08
Fig.-3 Raw Material Handling Flow Sheet ..............................................10
Fig.-4 Process Flow Sheet In Roaster Plant ............................................12
Fig.-5 Calcine Balance Over Roaster Plant .............................................19
Fig.-6 Process Diagram For Acid Plant ...................................................37
Fig.-7 Process Diagram for Neutral Leaching ..........................................45
Fig.-8 Process Diagram for Acid Leaching and Neutralization ................47
Fig.-9 Process Diagram for Residual Treatment Plant ............................48
Fig.-10 Purification Plant .........................................................................52

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)
(b) Cadmium
(c) Sulphuric Acid

(25 kgs) & Jumbo (600 kgs)


Pencils (150 gms)
+ 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.

(c) Unskilled

250Nos.

Raw Material Supplies:(a) Zawar Mines


(b) Agucha Mines
(c) Rajpura Dariba Mines
Product Buyers:(a) Tata
(b) Bhel
(c) Steel Companies
Process Collaborators:(a) Krebs Penorrova, France
(b) Lurgi, GMBH, and Germany
(c) Auto Kumpu Finland
(d) I.S.C., ALLOY, U.K.

Leaching, Purification, Electrolysis


Roaster and gas clearing
RTP, Wartsila Plant
Zinc dust plant, Allen Power Plant

INTRODUCTION
10

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

11

3.

Specific Latent Heat of Fusion

10 J/ Kg

4.

Specific heat capacity

5.

Linear expansivity

6.

Thermal conductivity

7.

Electric Sensitivity

5.9 ohm meter

8.

Temp. Coefficient of resistance

40/k

9.

Tensile Strength

10.

Elongation

50%

11.

Young modulus

110 Gpa

12.

Passions Ratio

385 J/Kg/K
31/K
111 W/m/k

150 Mpa

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

12

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;

13

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;

14

15

Fi
g.-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.

16

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.

17

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.

18

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 gas-solids
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

CuS

1.5O2

SO3
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.

19

Fig.-4 Process Flow Sheet In Roaster Plant

20

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 SO 2 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.

21

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, gastight 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 forcedcirculation-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

22

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 motor-driven 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.

23

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

24

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

25

Heat and Mass Balance Over Roaster Plant


III
Mass Balance
Concentrate feed
feed in kg/hr
Moisture content
Relative humidity

= 39.75
= 39750
= 10 %
= 0.111
=39749.8

t/hr
kg/hr

Dry feed

kg/hr

Concentrate composition
Component
%

Kg/hr

Zn
Fe
Lead

52
8.5
1.5

20669.94
3378.74
596.25

Copper

0.1

39.75

Suphur

30

11924.97

0.9

357.749

Cd

0.16

63.60

SiO2

795.00

Insolubles

397.50

26

Fig.-5 Calcine Balance Over Roaster Plant

1. Reactions of zinc:
Zn

ZnS

65.4

32

97.4

20669.94

10113.73

30783.68

1.5 O2
48
15170.60

ZnO
81.4
25726.81

ZnS
97.4
30783.68

kg/hr
+

SO2
64
20227.47

kg/hr

2. Reactions of lead:
Pb
207.2
596.25

PbS

239.2
688.33

S
32
92.08

PbS
239.2
688.33

1.5 O2

PbO

48
138.13

223.2
642.29

kg/hr
+

SO2
64
184.17

kg/hr

3. Reactions of copper:
Cu
63.5
39.75

CuS

95.50
59.78

S
32
20.03

CuS
95.5
59.78

1.5 O2

CuO

48
30.05

79.5
49.77

kg/hr
+

SO2
64
40.06

4. Reactions of iron:
Fe
Fe

+
+

S
S2

Amount of Fe present in FeS


Amount of Fe present in FeS2

FeS
FeS2

75 %
25 %

27

=
=

2534.06 Kg
844.69 Kg

kg/hr

Fe
56
2534.06

S
32

FeS
88
3982.09

2 FeS
176
3982.09

3.5 O2
112
2534.06

Fe2O3
160
3620.08

Fe
56

S2
64

FeS2
120

965.35

1810.04

5.5 O2
176
1327.36

Fe2O3
160
1206.69

844.69

2 FeS2
240
1810.04

2 SO2
128
2896.06

4 SO2
256
1930.71

5. Reactions of cadmium:
Cd
112
63.60

S
32
18.17

CdS
144
81.77

CdS
144.00
81.77

O2
32
18.17

CdO
128
72.69

6. For Silica:
SiO2
795.00

SiO2
795.00

28

SO2
64
36.34

7. For Carbon:
C
12

O2
32

CO2
44

Feed and Product rate for different


components:
Concentrate

Feed

Oxides

rate
(kg/hr)

Wt of oxides

Oxygen

SO2

(kg/hr)

req.
(kg/hr)

(kg/hr)

ZnS

30783.6

ZnO

25726.80882

15170.5998

20227.4664

PbS

8
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

29

C
CdS

357.75
81.77

Insolubles
Total

CO2
CdO

44.00
72.69

32
18.17

0
36.34

397.50

397.50

0.00

0.00

38955.9

32510.82

19250.36

25314.81

3
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

Total Air at furnace inlet

m3/hr
m3/hr

81895.75

m3/hr

Gases escaping from furnace top

77085.17

Calcine from top of the furnace

Calcine from bottom of the furnace

75 %
24383.11
kg/hr
25 %
8127.70
kg/hr
=
45 %
40 %
=
15 %

=
=
Dust removing capacity of boiler
Dust removing capacity of Cyclone separator
Dust removig Capacity of HGP

Boiler
Cyclone separator

Intlet

outlet

Underflow

24.38 t/hr
13.41 t/hr

13.41 t/hr
3.66 t/hr

10.97 t/hr
9.75 t/hr

30

HGP

3.66

t/hr

0.01829 t/hr

3.64 t/hr

Heat Balance
Reactions involved :
Hf(KJ/mol)
Enthalpy

ZnS
-204.6

PbS
-98.12

CuS
-48.5

2 FeS
-201

2 FeS2
-355

CdS
-208.4

1.5 O2
0

ZnO
-348

1.5 O2
0

PbO
-218.08

1.5 O2
0

CuO
-155.2

3.5 O2
0

Fe2O3
-825.5

5.5 O2
0

Fe2O3
-825.5

O2
0

CdO
-235.6

O2

CO2

31

SO2
-296.84

KJ/mol

-440.24

SO2
-296.84

KJ/mol

-416.8

SO2
-296.84

KJ/mol

-403.54

2 SO2
-593.68

KJ/mol

-1218.18

4 SO2
-1187.36

KJ/mol

-1657.86

SO2
-296.84

KJ/mol

-324.04

Total Heat of Above reactions

-393.5

KJ/mol

- 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

Air = 68137.26 m3/hr


M = 88158.32 kg/hr

21248.53845 MJ/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

Calcine uderflow

Q = 19071167.99 kj/hr

M = 8127.70 kg/hr

= 19071.16799 MJ/hr

Cp = 0.75 kJ/kg-k
Q = 7082846.15 KJ/hr
= 7082.84615 MJ/hr

CO2

Radiation
M = 44.00Loss
Kg/hr
= 3%
Cp = 1.22
KJ/Kg-K
= 40699.3869
Q = 62698.24
KJ/hr MJ/hr
= 62.69824 MJ/hr
water evap.
Q=ml
= 8581320 Kj/hr
= 8581.32 MJ/hr

32

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
latent heat of vaporisation, L
m
M

=
=
=
=

m*L
2.42
Q/L
1739

9.04
= 17.4

MJ/Kg
Kg/hr
t/hr

enthalpy of liquid water, h1


enthalpy of superheated steam, h2
h
Q
M

=
=
=
=
=
=

Heat Taken by cooling coil = 3%


Q = h*A*t
A = 54.98
Heat retained

97%

33

104.86
4398
4293.14
mh
Q/h
9.80766316

kJ/kg
kJ/kg
kJ/kg

at 25 C
at 920 C

t/hr

= 0.82

MJ/hr-m2-C

8
= 925

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
Q

Air
M
Cp
Q

=
=
=
=

=
=
=

13410.71
8434832.922
8434.832922

Kg/hr
Kj/hr
Mj/hr

68137.26

m3/hr

88158.32
1
74317462.16
74317.46216

kg/hr
kj/kg-k
kj/hr
MJ/hr

SO2
M
Cp
Q

= 25314.81
= 0.645
= 13764550.1

kg/hr
kj/kg-k
kj/hr

8
= 13764.5501

MJ/hr

Calcine uderflow

34

M = 10972.40 kg/hr
Cp = 0.75 kJ/kg-k

CO2

Q = 2398647.08 KJ/hr

M = 44.00 Kg/hr

= 2398.64708MJ/hr

Cp = 1.22 KJ/Kg-K
Q = 45252.24 KJ/hr
= 45.25224 MJ/hr

Water evap.
Q = ml

Radiation Loss
=3%

= 8581320 Kj/hr

=0 Mj

= 8581.32 MJ/hr
Heat leaving Boiler
Q entering Boiler
Total Q leaving from top
Heat leaving from boiler bottm
Q1 retaining inside boiler

=
=
=
=

1513349.34
105143.418
2398.64708
1405807.27

MJ/hr
MJ/hr
MJ/hr
MJ/hr

Heat Balance Over Cyclone Separator:


Temp.of calcine at Cyclone outlet = 300 C
Air

Temp.of calcine at Cyclone inlet = 350 C

= 68137.26 m3/hr
M = 88158.32 kg/hr

t = 50 C

Cp = 1 kj/kg-k
Q = 28475136.75 kj/hr

Calcine flyover
M = 3657.47 kg/hr

= 28475.13675 MJ/hr

Q = 881414.1164 kj/hr
= 881.4141164 MJ/hr

SO2
M = 25314.81 kg/hr
Calcine uderflow
Cp = 0.645 kj/kg-k
M = 9753.25 kg/hr
Q = 5273961.696 kj/hr
Cp = 0.75 kJ/kg-k
= 5273.961696 MJ/hr
Q = 2350437.64 KJ/hr
= 2350.43764 MJ/hr

35

water evap.
Q = ml

CO2

M = 44.00 Kg/hr
= 8581320 Kj/hr
Heat Entering
at cyclone
inlet =105143.418MJ/hr
Cp = 1.22
KJ/Kg-K
= 8581.32 MJ/hr
Heat leaving
from Cyclone
top =MJ/hr
Q = 17338.64
KJ/hr
Radiation Loss
Heat leaving
cyclone bottm
= at
17.33864
MJ/hr =2350.43764MJ/hr3%
Heat Entering HGP
=102792.98MJ/hr
0 MJ/hr

Heat Balance Over Hot Gas Precipitator:


Temp.of calcine at HGP outlet = 290C
Temp.of calcine at HGP inlet = 300C
t = 10C

Air

68137.26

= 88158.32

Cp

= 1

Calcine flyover
M = 18.29kg/hr
SO2
Q
= 3861.303327kj/hr
M = 25314.81 kg/hr
= 3.861303327MJ/hr
Cp = 0.645 kj/kg-k

m3/hr
kg/hr

kj/kg-k

Q = 4620839.505 kj/hr

24948804.02 kj/hr

= 4620.839505 MJ/hr

= 24948.80402 MJ/hr

Calcine uderflow
M
=
3639.18 kg/hr
Cp

0.75 kJ/kg-k

768399.362 KJ/hr

Water evap.
Q = ml

768.399362 MJ/hr

CO2
M

44.00 Kg/hr

Cp

1.22 KJ/Kg-K

15191.44 KJ/hr

15.19144 MJ/hr

8581320 Kj/hr

8581.32 MJ/hr

Radiation Loss =

3%

= 0 MJ/hr

36

Heat Entering HGP

102792.98

Heat Leaving at HGP bottom

768.399362 MJ/hr

Heat retaining inside HGP

102024.581

MJ/hr
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

37

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 SO 2-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 SO 2-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 m 2/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,

38

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 SO 2-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.

39

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.

40

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 4layer 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

41

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 SO 2 gas will be preheated to a
temperature of about 255C. A small part of the cold SO 2 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

42

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 SO 2-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 SO 3 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 SO 2 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 SO 2 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 SO 2concentrations 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

43

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 temperaturecontrolled 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

44

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 SO 2-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 SO 2 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

45

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.

Energy (Heat) Balance


The SO2 gases leaving the wet gas cleaning system enter the acid plant at temperature of
max. 38C in this case for reasons of the water balance. After removing the rest
water content in the dryer, the process gases must be heated up to the required
converter inlet temperature of min 396C. This is achieved by indirect heat exchange with the
available sensible gas heat released from the SO2 oxidation in the converter.
The main objective in designing such a cold gas plant is the attainment of autothermal
operation conditions which becomes primarily a question of the required gas heat
exchanger surface depending on the feed gas SO2 concentration.
The reaction heat in a double catalysis plant based on roaster gases is released from: The
catalytic oxidation:
SO2

O2

SO3

The sulphur trioxide absorption and sulphuric acid formation:

46

SO3

H2O

H2SO4

H2SO4 +

SO3

H2S2O7

H2S2O7

H2O

2 H2SO4

The dilution to acid production strength of 98.5 % H2SO4 and the condensation heat for
the water content of the gases entering the drying tower system. Sulphuric acid thus
produced is stored in acid storage tanks of capacity 6500 MT each. Finally gases are
discharged through chimney to atmosphere

O2 /SO2 Ratio
For the conversion of SO2 to SO3 the proportion of O2 volume to SO2 volume in the feed gas
to the converter, called O2/SO2 ratio, is an important factor for the conversion rate.The design
of the contact plant is based on a gas composition which is calculated on the basis of analyses
of the roaster gases be processed. However, in practice other gas compositions may occur and
their different water content may lead to substantial fluctuations in the gas composition.
Considering the SO2 concentration determined for the design of the double catalysis plant,
this may often mean an essential shifting of the expected O 2/SO2 ratio towards lower values.
On the other hand, the O2/SO2 ratio of the gases has a decisive influence on the final
conversion efficiency achievable in the contact plant.

LEACHING PLANT
Leaching is a widely used extractive metallurgy technique which converts metals into soluble
salts in aqueous media. Compared to pyrometallurgical operations, leaching is easier to

47

perform and much less harmful, because no gaseous pollution occurs. The only drawback of
leaching is its lower efficiency caused by the low temperatures of the operation, which
dramatically affect chemical reaction rates.

Neutral Leaching Of Zinc Calcine


The first neutral leaching step is the most important section of the leaching plant, because
approx. 70% of the total dissolved Zn is dissolved in this leaching step. The main target is to

leach the zinc oxide from the calcine and oxidize the ferrous iron to the ferric state. In
addition to being an important zinc leaching step, the neutral leaching step is also an
important purification step. Impurities like Fe, As, Sb, and Ge are precipitated in the last
tanks of neutral leaching.
Neutral leaching consists of following main process equipment:

One 35 MT capacity calcine hopper


Seven 680 MT capacity calcine storage silos
Three screw conveyors, and five reddller conveyors
One classifier and ball mill
Nine 45 m3 leaching reactors and first reactor is called Ready for calcine
Two 16 m diameter thickners
Two 70 m3 thickner overflow tanks.

Calcine conveying
Calcine from roaster plant is taken through bucket elevator. There are two bucket elevator.
This calcine is transferred to calcine hopper. When calcine hopper is full, calcine is diverted
to storage silos through reddler conveyors to any of the seven silos depending on the level of
calcine present in each of them.

Neutral leaching
The ready for calcine(RC) and remaining leaching pachukas (Reactor) are all covered and
equipped with agitators and stacks. Pachukas are equipped with injectors for oxygen gas.
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Execpt RC and the eight leaching pachukas are arranged in a cascade and are interconnected
with an overflow launder, so that the solution fed to the first tank flows by gravity to all the
tanks and to the classifier without pumps. Also , the launder system enables the bypass of any
single pachuka.
Fig.-7 Process Diagram for Neutral Leaching
Calcine from calcine hopper is fed through a screw conveyor and reddler conveyor. Ready for
calcine solution is prepared continuously in RC tank and in case of breakdown of RC tank
first pachuka is used for ready for calcine.
The main acid bearing solutions ,which is used to leach the calcine added into the neutral
leach step is the spent elecrolyte from cell house whith approx. 180 g/l free H 2SO4 along with
ball mill slurry and occasionally conversion overflow acid overflow also can be added. In
addition MnO2 (To control the ferrous content) KMnO4 are to be added in RC tank. The
dosing of MnO2 is carried out by a magnetic vibrator.
The solution mixture from the RC tank, with a free acidity of about 100-120 g/l H 2SO4
pumped to the pachuka. The acidity is lowered in the leaching tank series by calcine addition
in two steps.

The basic chemical reactions in the neutral leaching process are:


ZnO

H2SO4

ZnSO4 +

H2O

CuO

H2SO4

CuSO4 +

H2O

CdO

H2SO4

PbO

H2SO4

CdSO4 +

PbSO4 +

H2O

H2O

In addition to the reactions above , MnO2 reacts in the first leaching pachukas
2 FeSO4 + 2 H2SO4 + MnO2 Fe2 (SO4)3 +MnSO4 + 2 H2O
Where as in the last leaching pachukas oxygen is reacting and iron hydroxide is precipitated
2 FeSO4 + 2 H2SO4 + O2

+ ZnO

Fe2 (SO4)3 + ZnSO4


+ 2 H2O

Fe2(SO4)3 + 3 ZnO + 3 H2O

2 Fe(OH)3

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3 ZnSO4

4 Fe(OH)3

+ Sb/As/Al/Ge-complex

Fe-OH-Sb-As-Ge-Complex

Acid Leaching
The main task of the acid leaching step is to dissolve the remaining zinc oxide, which was not
dissolved during Neutral leaching and to reach a zinc oxide leaching efficiency of more than
97%.
The main chemical reactions in weak acid leaching are:
ZnO

H2SO4

ZnSO4

H2O

MeO +

H2SO4

MeSO4

H2O (Me = Cu, Cd etc.)

Fig.-8 Process Diagram for Acid Leaching and Neutralization

Neutralization:
Neutralization is used to remove the impurities Sb, As , Al and Ge by neutralizing the over
flow from acid leaching thickner and jarosite precipitation thickners with calcine before
sending it to neutral leaching.

Residual Treatment Plant(RTP):


The conversion process main function is to simultaneously leach the zinc ferrite and
precipitate the iron as ammonium or sodium jarosite. The conversion process comprise the
following main equipment.

Five 300 m3 conversion reactors


Two 18 m diameter thickners
Two 70 m3 thickener overflow tank
One 20 m3 condensate tank
Two (NH4)2SO4 /Na2SO4 preparation tank

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Fig.-9 Process Diagram for Residual Treatment Plant

The five conversion reactors are arranged in a cascade and are interconnected with an
overflow launder. The solution flows by gravity from the first conversion reactor down the
cascade through all reactors into the thickner of ccd system without the need of pumping.
Each reactor is covered and equipped with an agitator, a vent stack and steam heating
elements.
The weak acid leaching underflow is pumped through a flow indicator and controller into the
launder before the first conversion process in order to compensate for the sulphate losses.
MnO slurry from ZE plant is pumped in to inlet and is added to oxidize ferrous ion.the
temperature of all reactors is kept at 95-100. Ammonium sulphate or sodium sulphate diluted
with condensate water is added at outlet for formation of jarosite.

Magnesium Removal
The magnesium removal is required to maintain minimum magnesium in process solutions.
For the separation of Zn from the Mg, lime milk is used.
The magnesium plant consists of following main equipment

One continuous vaccum drum filter


Two magnesium reactors 20 m each
Two lime preparation reactors

The lime milk solution is prepared in the lime milk tank. The Ca(OH) 2 is fed from lime bin
into the precipitation tank and the COF is fed using pump.Alternatively the feed can be
filtrate from the jarosite filtration step. The lime milk is circulated to the precipitation tanks
using pump.The neutralization process is continuous and dimensioned for about four hours
retention time.The precipitation tanks are run at pH 6.8-7.5. Zinc is precipated together with
which is not a desired situation.In pH 8 Zn is almost totally precipated and Mg has started to
precipitate. The zinc concentration will be below 10 mg/l after neutralization. Samples will be
taken and analyzed once/shift and correction in lime feed made if too much zinc is going
through.

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The reactions will be


ZnSO4

Ca(OH)2

+ 2 H2O

Zn(OH)2 + CaSO4 .2H2O

MgSO4 +

Ca(OH)2

+ 2 H2O

Mg(OH)2 + CaSO4 .2 H2O

H2SO4

Ca(OH)2

2 H2O

+ CaSO4 .2H2O

The slurry from reactor is fed to drum under vaccum. The MgSO 4 is filtered out and cake is
retained over the cloth which is re pulped with COF and charged in reactors through
pumpfrom where it is pumped to ETP.

Horizontal Belt Filter


In the section the jarosite and leach residue slurry is filtered and washed on horizontal
vacuum belt filters to maximize water soluble zinc recovery. This section comprises of the
following main equipment

Two vaccum belt filter units(one is stand by)


One cake slurry re pulping tank

The underflow slurry of door is pumped with pump to HBF over head tank. For proper
vaccum control each horizontal belt filter will be equipped with its own water ring type
vaccum pump system.
The jarosite cake is separated on polypropylene filter cloth repulped with ETP water and
pumped to ETP via HBF slurry tank. Speed of the belt input slurry flow to HBF and wash
water quantity is controlled by the concerned C/H in the HBF control room. Vacculm pipes
are connected beneath the mother belt and filter water is used for the vaccum sealing purpose.
Mother liquor (collected in the feed zone and drying zone)

Purification
The neutral solution contains several impurities like copper, cadmium, cobalt and nickel.
Becide these major impurities also small amounts of arsenic and antimony can be analyzed in
the solution. Before the solution can be sent to the electrowinning these impurities habe to be
removed in the purification plant. The main reagent in the purification plant is the Zinc dust.
The basic reaction is that of cementation of those metals, whose positions in the
electromotive series for sulphates are below that of Zinc.
The purification of the neutral solution will be carried out in three steps.

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1. Pre filtration (cold filtration) of neutral over flow


2. Hot purification for removing of copper, cadmium , cobalt and nickel as major
impurities
3. Second step or polishing step to ensure top quality of purified solution.
In pre-filtration step suspended solids present in NOF tank are removed. Main impurities are
removed in hot purification. These process is based on antimony purification process. In this
process solution is passed through a spiral heat exchanger so that its temperature become 8082 C. This solution is passed through a reactor cascade and another reagent Zn dust is added.
To improve the reactivity of Zinc dust potassium antimony tartrate (PAT)is added. For
removing organic impurities charcoal solution is also fed. Reactor outlet is passed through a
cascade of filter press where impurities are removed as Cu-Cd Cake. Cu-Cd cake is sent to
the Cd plant for further purification. Filtrate is processed in polishing step. Here the solution
is again passed through Reactor and filter press cascade and remaining amount of Cd which
may be slipped during hot purification is also removed.
After polishing step solution is almost pure solution of zinc sulphate containing a small
amount of gypsum which is removed in gypsum removal plant.
Fig.-10 Purification Plant

Cadmium plant
Following are the main stages in the production of purified cadmium sulphate solution:

Enrichment of Cu-Cd cake


Enriched Cu-Cd cake leaching and Cu removal as Cu-cement
Cadmium cementation
Leaching and purification of Cd sponge
Iron and cobalt purification of solution before sending to zinc circuit

Gypsum Removal
The gypsum removal system will be necessary to remove gypsum from hot neutral solution
before it is taken to the cell house in order to reduce gypsum precipitation in electrolytic
cells, piping, launders and cooling towers. The neutral solution that is saturated with gypsum

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will be cooled in three atmospheric cooling towers from 86C to 34C. This causes
crystallization of gypsum from the solution still remains saturated with gypsum. The gypsum
will be then removed in a thickener. Spent acid will be fed for pH adjustment and flocculent
(1 g/l aqueous solution) into the thickener. The thickener overflow will be taken to the
purified solution storage tanks. The underflow will be pumped to the jarosite step.
Prior to be directed to the cooling towers the pH of the solution will be adjusted to 4.9 to
prevent formation of basic zinc sulphates. The pH adjustment is made in the filtrate collecting
tank of the polishing purification step by adding a controlled amount of spent electrolyte.
The solution is fed to the top of the tank through nozzles. The falling solution meets the air
produced by the fan and solution will cool down when water is evaporated. The cooled
solution is collected on the bottom of the tower and leaves the tower trough an overflow box,
which is provided with temperature control and level detection. The overflow from the
thickener flows by gravity via the launder to the selected purified solution storage tank. In
this whole process, a part of gypsum, about 157 kg/h is removed from the solution.

Electrolysis Plant
Zinc is extracted from the purified zinc sulfate solution by electrowinning, which is a
specialized form of electrolysis. The process works by passing an electric current through the

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solution in a series of cells. This causes the zinc to deposits on the cathodes (aluminium
sheets) and oxygen to form at the anodes. Sulfuric acid is also formed in the process and
reused in the leaching process. Every 24 to 48 hours, each cell is shut down, the zinc-coated
cathodes are removed and rinsed, and the zinc is mechanically stripped from the aluminum
plates.
Electrolytic zinc smelters contain as many as several hundred cells. A portion of the electrical
energy is converted into heat, which increases the temperature of the electrolyte. Electrolytic
cells operate at temperature ranges from 30 to 35C (86 to 95F) and at atmospheric pressure.
A portion of the electrolyte is continuously circulated through the cooling towers both to cool
and concentrate the electrolyte through evaporation of water. The cooled and concentrated
electrolyte is then recycled to the cells. This process accounts for approximately 1/3 of all the
energy usage when smelting zinc
The electrolysis phase uses large amounts of electrical energy and is responsible for the high
proportion of the energy-cost in the overall smelting process (typically about one third of
total plant cash costs). Hence, cell house productivity (and electrical current and energy
efficiency in particular) is a crucial driver in overall plant efficiency. Debari runs some of the
industrys largest and most efficient cell houses.

MELTING AND CASTING

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Cathode melting will be carried out in two identical electric induction furnaces. The furnaces
will have a guaranteed average melting rate of 22 tonnes per hour of zinc cathodes
(maximum ~ 24 tonnes per hour). The melting rate is infinitely variable between 0% and
100% of the maximum melting rate and is controlled by the automatic control system to
match the rate that molten metal is removed (pumped) from the furnace.
Each furnace is equipped with a still well equipped with one or more molten metal pumps.
The pump delivers molten zinc to a launder system feeding the casting machine. Each
furnace feeds a single casting line. In addition, provision is made to pump molten zinc from
one of the furnaces to the zinc dust production plant.
In addition to cathode bundles, the furnace chutes are designed to receive metallic zinc from
the dross separation plant and metallic zinc skims from the casting machines. This material
is fed to any chute (normally one dedicated chute) from forklift transported to hoppers that
have been raised to the charging floor by the freight elevator (lift). The required amount of
nh4cl to enhance the melting of this material is manually added to each hopper prior to
dumping in the charge chute.
When cathode zinc is melted, a layer of dross comprised mainly of zinc oxide entrained
molten zinc droplets is produced. This dross must be removed from the furnace once in every
24 hours by manually skimming the dross from the surface of the bath in a process called
drossing. This process consists of opening one of the doors on the side of the furnace,
manually spreading a few kg of NH4Cl onto the dross layer, manually agitating the dross
layer with a steel rake and finally using the rake to drag the dross through the open door
of the furnace into a forklift tote bin. During the drossing process, the furnace is operated
under conditions of increased ventilation to contain the fumes and dust that are generated by
the agitation and dross removal processes. The totes of furnace dross are transported by lift
truck to the dross cooling area, to await treatment in the dross separation plant.

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REFERENCES

Plant Operating Manuals Zinc Smelter Debari, Udaipur


McCabe, Smith, Harriott Unit Operations of Mechanical Engineering McGraw-Hill

International Editions.
http://www.hzlindia.com/index.aspx

[Viewed on 10-06-2015]
http://www.vedantaresources.com/default.aspx Offical Website of Vedanta Resources

Official Website of Hindustan Zinc Limited

[Viewed on 10-06-2015]

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