Column1 Column2

sulfuric acid: is a dense clear liquid

Uses: making fertilizers, leaching metallic

ores, refining petroleum and for
manufacturing a myriad of chemicals
and materials

statistices Worldwide, about 180 million tonnes of

sulfuric acid are consumed per year
raw material SO2 gas.SO2 is obtained by:
for sulfuric (a) burning elemental sulfur with air
acid (b) smelting and roasting metal sulfide
minerals
(c) decomposing contaminated (spent)
sulfuric acid catalyst.

table outside table

sulfuric acid f Sulfuric acid is made from these gases

by:
(a) catalytically reacting their SO2 and
O2 to form SO3(g)
(b) reacting (a)'s product SO3(g) with
the H2O(f) in 98.5 mass% H2SO4, 1.5
mass% H2O sulfuric acid.
Industrially, both processes are carried
out rapidly and continuously,
title sulfuric acid formation
1.1 catalytic Oxidation
of SO2 to SO3:
outside table

1.1.1 catalyst At its operating temperature, 700-900 K, SO2

oxidation catalyst consists of a molten film of
V, K, Na, (Cs) pyrosulfate salt on a solid
porous SiO2 substrate. The molten film
rapidly absorbs SO2(g) and O2(g) - and
rapidly produces and desorbs SO3(g)

1.1.2 Feed gas drying Eqn. (1.1) indicates that catalytic oxidation
feed gas is always dry*. This dryness avoids:
(a) accidental formation of H2SO4 by
reaction of H2O(g) with the SO3(g) product
of catalytic SO2 oxidation
(b) condensation of the H2SO4 in cool flues
and heat exchangers
(c) corrosion,
The H2O(g) is removed by
cooling/condensation and by dehydration
with H2SO4(l),
title 1.2 H2SO4 Production
1.3 Industrial
Flowsheet
Fig. 1.4 is a sulfuric acid
manufacture flowsheet. It shows:
(a) the three sources of SO2 for acid
manufacture (metallurgical, sulfur
burning and
spent acid decomposition gas)
(b) acid manufacture from SO2 by
Reactions (1.1) and (1.2).
(b) is the same for all three sources
of SO2. The next three sections
describe (a)'s three
SO2 sources.
title 1.4 sulphur burninng

About 70% of sulfuric acid is made from elemental sulfur.

All the sulfur is obtained as a byproduct from refining
natural gas and petroleum. The sulfur is made into SO2
acid plant feed by: melting the sulfur spraying it into a hot
furnace burning the droplets with dried air.

Very little SO3(g) forms at the 1400 K flame temperature

of this reaction, The product of sulfur burning is hot, dry
SO2, O2, N2 gas. After cooling to -700 K, it is ready for
catalytic SO2 oxidation and subsequent H2SO4-making.
1.5 Metallurgical Offgas
SO2 in smelting and roasting gas
accounts for about 20% of sulfuric acid
production. The SO2 is ready for sulfuric
acid manufacture, but the gas is dusty.
If left in the gas,the dust would plug the
downstream catalyst layers and block
gas flow. It must be
removed before the gas goes to
catalytic SO2 oxidation.
It is removed by combinations of:
(a) settling in waste heat boilers
(b) electrostatic precipitation
(c) scrubbing with water (which also
removes impurity vapors).
After treatment, the gas contains ~1
milligram of dust per Nm3
of gas. It is ready for
drying, catalytic SO2 oxidation and
H2SO4 making.
1.7 Sulfuric Acid Product
Most industrial acid plants have three flows of sulfuric
acid - one gas-dehydration flow and two H2SO4-
making flows. These flows are connected through
automatic control valves to:
(a) maintain proper flows and H2SC>4 concentrations
in the three acid circuits
(b) draw off newly made acid.
Water is added where necessary to give prescribed
acid strengths

Sulfuric acid is sold in grades of 93 to 99 mass% H2SO4

according to market demand. The main product in cold
climates is -94% H2SO4 because of its low (238 K)
freezing point . A small amount of oleum (H2SO4 with
dissolved SO3) is also
made and sold (BASF, 2005).
Sulfuric acid is mainly shipped in stainless steel trucks,
steel rail tank carsand double-hulled steel barges and
ships. Great care is
taken to avoid spillage
title: 1.10 Summary
About 180 million tonnes of sulfuric acid are produced/consumed per
year. The acid is used for making fertilizer, leaching metal ores, refining
petroleum and for manufacturing a myriad of products. Sulfuric acid is
made from dry SO2, O2, N2 gas. The gas comes from:
burning molten elemental sulfur with dry air, Chapter 3
smelting and roasting metal sulfide minerals, Chapter 4
decomposing contaminated (spent) sulfuric acid catalyst, Chapter 5.
Sulfur burning is far and away the largest source.
The SO2 in the gas is made into sulfuric acid by:
(a) catalytically oxidizing it to SO3(g), Chapters 7 and 8
(b) reacting this SO3(g) with the H2O(^) in 98.5 mass% H2SO4, 1.5
mass% H2O
sulfuric acid,
Column1 Column2
Proposal description

Activity Collaboration between the Pakistan ordinance factory

(POF) and the university of Engineering and
technology Peshawar in order to improve in the
chemical process of the sulphuric acid production
plant.

title of the proposal Design and development of Oleum and Sulphuric Acid
Manufacturing Plant having double absorption system
utilizing the existing single absorption-based plant.

main problem SOx emissions

vision to develop knowledge, technology, and capability to
manufacture/improve our chemical process
industries.

phase 1 project(short): A slight process modification will be introduced to

reduce the SOx emissions in the overall composition
of the tail gas
problem with the plant The main issue with the new acid plant is that it emits
large amount of SOx into the environment, i.e. SOX
are not perfectly absorbed in an acid absorption
column. Essentially SO3 is absorbed in a concentrated
sulphuric acid solution to produce oleum. The exact
chemical composition of sulphur oxide gases emitted
from the acid absorption column was not known to us
but one can assume that it would be SO2 gas as it
may not easily absorb in concentrated sulphuric acid
solutions. On the other hand, water can absorb SO2
gas easily. Beside SOx, we should be aware that large
amount of air mixture containing oxygen and nitrogen
is also present in overall gaseous compositions.

Moreover, the humidity of The Wah city is usually

high whereas SOx gases are stable in the troposphere
(0-10km) region. This coexistence of both SOx and
moisture in the atmosphere is infectious to the local
population and vegetation. Thus an immediate
process modification is needed in the exiting acid
plant in order to limit the SOx emissions. The current
production capacity (10 metric tons per day) is
enough for the current defense needs however it was
also agreed that sulphuric acid is in high demand and
thus the management may consider proposals to
increase the acid production capacity
reasons for the sox emissions
1) The first issue is with the sulphur combustion. Every effort
is made to inject a clean dried air to the combustion zone for
the oxidation of sulphur (S + O2 → SO2). In reality it is not
possible to clean air from all types of particulates and
gaseous substances. This may cause slippages in oxidation
process forming different type of sulphur oxide gases

2) Moreover, un burnt sulphur also exist in a system.

In any case, the whole set of gaseous species passes over
three bed catalyst packing to produce SO3 gas
as much as possible. The main problem might be in the
catalytic converter as it produces less SO3. It is
very common that the active sites of vanadium oxide
catalyst are being held by the passive species. The
third catalyst bed of the converter is always under stress and
here the deterioration of the conversion sites is much
quicker.

3) Finally,
the third concern is that all these gases passes through an
absorption column to absorb SO3 in sulphuric
acid solution. Since it contains a mixture of gases therefore
the proper absorption is not possible.
Therefore, the unabsorbed gases end up into the
atmosphere.
solutions
1) Increasing the concentration of the oxygen in an air feed
in order to expand the sulphur burning. The high
concentration of oxygen means that there will be less
nitrogen in a gas feed. The rate of burning will improve and
also the volume percent of SO2 in a gaseous mixture will be
much higher when a normal air is used for combustion. The
catalyst bed in a catalytic converter will have more chance of
interaction with SO2. We believe that overall more SO3 will
be formed when high concentration of oxygen is used for
combustion

2) The rate of SO3 formation can be increased by altering the

shape and size of the catalyst
presently being used in the third bed of the catalytic
converter. The size of the cylindrical
catalyst which is also used in the previous two beds of
converter is comparatively small to
catalyst being used in private sector sulphuric acid industries
of Pakistan. The load of
volumetric flow rate to the surface areas of the catalyst has
usually enormous and thus increases
the rate of chemical reactions. In short more SO3 will be
formed in a catalytic converter and
absorption for making oleum will be possible with less
emission of SO2 in the atmosphere.

3) Installation of an independent water absorption column

can absorb the leaving SOx gases. The
actual absorption capacity needs to be determined.
Sulfurous acid (SO2 absorption in water) has
many applications and can sold out in an open market.
title and abstract outline summarize optimization repitition limitation
author targets and s
pattern
Optimizat introduction: The process is Multi-variable The.op.timization
ion Current designed to give optimization was targets were to
studies in legislation a conversion of performed for maximize the
sulfuric imposes sulfur dioxide to several production amount of energy
acid tighter sulfuric acid of rates, produced, and
productio restrictions to over 99.7%. This corresponding to minimize the total
n reduce the is achievable in the amount of amount of SOn
Author: impact of practice due to sulfur fed into the released in
Anton A. process the intermediate plant (nominal atmosphere (i.e.
Kiss, a industry on absorption value and + 5- not absorbed in
Costin S. environment. (after the fourth 10% changes). Five the final absorption
Bildea, b This work bed of catalyst) key variables were column). The
Peter J. T. presents the that changes the identified and conversion profiles
Verheijen dynamic gas composition, manipulated in the reactor for
b simulation thus shifting accordingly changes
and the equilibrium to carry out the of + 10% in the
optimization curve to higher optimization: the feed flow rate are
results for an conversions amount of air fed given in Figure 6
existing into the sulfur (left). Increasing
sulfuric acid burner, the energy
plant. flow rates of air fed production is
literature into converter pass equivalent to
gap:Operation 3 and 4, and split maximizing the
al problems fractions (by-pass) amount of SO2
may occur for converted into
when the cold streams products. A flat
process is entering the gas- optimum is
disturbed due gas heat expected, since the
to production exchangers (FEHE1 heat generated in
rate changes and FEHE2). In the reaction is
or both the one that is
catalyst optimizations the recovered. As the
deactivation, cold streams conversion of the
the non-linear should not be split process is almost
response of to bypass the heat 99.85%,
the plant exchangers. any further
leading to increase is
method research results conclusion
gap

dynamic The dynamic

simulatio model developed
n+ in this work
optimizati provides reliable
on results that are in
excellent
agreement with
the data available
from the real
plant, the relative
error
being typically less
than 1%. Along
with minor
benefits in energy
production
the amount of SOx
emissions could be
significantly
reduced by ~40%
just by
optimizing
operating
parameters such
as feed flow rates
or split fractions.
Besides
controllability,
operability and
optimization
studies the plant
model
coded in gPROMS
is also useful for
operator training
and scenario
assessments.