Introduction

The basic purpose of chemical industry is to convert raw materials into useful products for the
society. For example, crude oil sourced from oil reservoirs cannot be used as it is. Refineries
convert the crude oil, through several chemical and physical processes, into products that we
use in our daily life. Petrol, diesel, lube oils, LPG are a few products of the refineries. There are
about 10 basic raw materials such as oil, natural gas, coal, available in nature. These are
converted base chemicals, which are then transformed to intermediate chemicals. Final
products are made from the based and intermediate chemicals. Below Figure shows chemical
industry “tree.”

Adapted: Chemical Process Technology, Moulijn et al., 2nd ed, 2013

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Bulk chemicals are manufactured by continuous processes; fine chemicals, specialty chemicals
and pharmaceuticals are often made by batch processes due to low volumes of production,
seasonal requirements and flexibility to make several products. The continuous processes are
easier to control than batch processes because the former operate at steady state; the former
are more economical than the latter due to economies of scale. Table below shows the bulk
and fine chemicals manufactured.

Bulk chemicals Fine and specialty chemicals

pharmaceuticals
Chemical Production in kg/year Chemical Production in kg/year
Sulfuric Acid 3.25 x 1011 α-interferon ~10
Ethane 2.4 x 1011 Streptokinase ~10
Propane 1.4 x 1011 Insulin ~104
Chlorine 9.7 x 1010 Penicillin 5 x 107

Chemical engineering/technology is orchestration of science [chemistry, physics and

mathematics], engineering, economics, safety, environment to make a product from a raw
material. As engineers, we need to ensure that raw materials and energy resources are
conserved and not wasted (excessive use of raw materials and energy); pollution standards of
the time are adhered to; quality of the products is maintained; safety of equipment and
personnel is given due importance.

You have taken several core courses in chemical engineering curriculum such as material and
energy balances, fluid mechanics, thermodynamics, reaction engineering, separation processes
and economics. This course (CL 306: Chemical Processes) unifies all the previous courses, draws
upon the fundamentals and applications learnt in those courses to develop a flowsheet to make
a chemical from a given raw material. Figure in the next page shows connection between the
core courses and CL 306.

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  Overall balances
 Raw material
 Heat exchangers
needs
Material and  Distillation Heat and mass
 Energy needs
energy  Absorption transfer
balances  …
 Extraction
 …

Reaction
engineering
 Pumps/fans/blower CHEMICAL  Reactor selection
s  Reactor design
Fluid mechanics PROCESSES
 Pressure drop  RTD
 Piping design  …
 Instrumentation
 Equilibrium
…  Costing, taxes
 Efficiencies  P, PI, PID  Rate of return
 Sizing of  Instrumentation  Pay back period
compressor  Control valves  Select from
 Refrigeration  … alternatives
 Equilibrium  …
constant
 … Process control

Thermodynamics Economics

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General scheme for manufacture of a chemical

Raw material Energy in and out

Unit operations
Other chemicals

Energy in chemicals in
and out and out
Reactor

Unit operations
Energy in
and out
recycle
Products

Production process for any bulk chemical (it is applicable for fine chemicals also) can be
roughly divided into three sequential steps: raw material preparation, reaction and
downstream separation. Usually raw materials are physically processed in one or several
unit operations to make them suitable for reaction. Examples of physical treatment of raw
material

 Coal needs to be pulverized for burning/ gasification

 Limestone is crushed and ground in cement manufacture
 H2S is removed from natural gas
 Benzene is dehydrated before further processing to make ethylbenzene

The raw material is converted into product in a reactor. The reaction could be
heterogeneous or homogeneous; exothermic or endothermic; liquid phase or vapour phase.
In a typical chemical plant, reactor operates at high temperatures. As a result, side products
are inevitably produced. Catalyst may improve selectivity toward the desirable component
but will not eliminate side products. There are a few exceptions, however. Downstream of
reactor, therefore, product is separated from the side-products in one or many unit
operations (only physical separations happen, no chemical changes occur). Unreacted
reactant(s) are recycled to the reactor to enhance conversion. Most of the production cost
is due to raw materials.

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 Learning Outcomes for Sulphuric Acid Process

 Write all the chemical reactions for the process

 List the raw materials needed to make sulphuric acid commercially
 Explain why oxygen is supplied in the form of air and not as pure oxygen, even
though nitrogen plays no part in the process
 Compare fixed bed reactor and shell-and-tube type reactors for oxidation of SO2
 Draw a reactor configuration for achieving 99.7% conversion of SO2 to SO3 and
explain how it works
 Explain the choice of pressure for the process; discuss the pros and cons of high and
low pressures
 Draw a process flow diagram for the entire process and explain this diagram

Sulphuric Acid Process

Sulphuric acid is by far the largest volume chemical produced. For this reason, it is also
called the king of chemicals. Major uses for sulphuric acid are in: manufacture of fertilizers,
alkylation step in crude oil refining, copper leaching, making of lead-acid storage battery in
motor vehicles as an electrolyte etc.

The reactions involved in the commercial manufacture of sulphuric acid are:

Oxidation of sulphur to SO2

S (l) + O2 (g) SO2 (g)

Oxidation of SO2 to SO3

SO2 (g) + 0.5 O2 (g) SO3 (g)

Absorption of SO3 to form H2SO4

SO3 (g) + H2O (l) H2SO4

Sulphur is oxidized to SO2 first; then, SO2 is further oxidized to SO3; the generated SO3 is
absorbed in water to produce H2SO4; if SO3 is absorbed in H2SO4, oleum [H2S2O7] is
produced.

The raw materials needed for the production of H2SO4 are: ___________________________

How much sulphur is required to make 300 tons per day of H2SO4?

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Sulphur is typically obtained from petroleum refineries where it is made from processing of
crude oil. If sulphur content is < 0.5 wt %, the crude is called sweet; if it’s between 1.0-2.0
wt %, it is termed sour; some crudes may have sulphur content > 4.0 wt % also.

Assuming 100 % conversion for the above reactions (reaction 2 can never go to 100 %
completion, why?),

Draw a block diagram for the production of H2SO4. Block diagram shows the sequential
arrangement of operations needed for the production of a chemical. Each block indicates
one operation with inlet and outlet streams. Be sure to write the components of these
streams in the diagram.

Let’s study each of the blocks in detail starting with oxidation of sulphur. By this study we
seek to get insights into the sulphuric acid process and draw a detailed block diagram later.
The insights drawn here could help us with understanding of other chemical processes.

Sulphur oxidation

Refineries supply sulphur as a yellow solid. Sulphur is recovered from crude oil as hydrogen
sulphide (H2S) from which sulphur is produced.

Which of the below options is appropriate for oxidizing [burning] sulphur to SO2? Think
about pros and cons of each of the two options.
BURNER
S
Option A: Grind it to fine powder, mix it with air.
air
S

Sulphur burns in air at the outlet of the burner to produce SO 2. Initial ignition is necessary.
The flame sustains itself after the ignition.

Option B: Melt it by heating it 15 degrees above its melting point (115 oC), atomize it by
passing the melt through a burner to produce small droplets of sulphur and then burn the
droplets with air. Here 15 is arbitrary; it could be few degrees higher or lower. However, it
cannot be too high.

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Select an option for supply of O2 to oxidize of sulphur. Again compare pros and cons of the
two below options. Hint: think about O2 separation from air, size of downstream equipment,
if oxygen is separated etc.

Option A: O2 through the supply of air

Option B: Pure O2 after separating air into N2 and O2

Air Drying

Air used to burn sulphur and oxidize SO2 to SO3 needs to be bone dry (what’s this? Find out).
Rashtriya Chemical and Fertilizers (RCF) Limited, located in Chembur, Mumbai produces
sulphuric acid. In the monsoon months of June-September, air in Mumbai is usually
saturated with moisture.

List a few methods below to dehumidify air

At what temperature and pressure would air be dehumidified? Be qualitative not

quantitative in your answer. Indicate high or low for temperature and pressure.

The bone dry air converts [oxidizes] molten sulphur to SO2. Speculate the outlet
temperature of the stream emerging from sulphur oxidizer. Remember: this reaction
involves burning of sulphur and its conversion to SO2 is complete.

Now, draw a detailed block diagram consisting of two units: absorption tower and sulphur
oxidizer. Write the components of all inlet and outlet streams and the operating conditions
of the units.

SO2 oxidation

The next step in the process is catalytic oxidation of SO2 to SO3 according to the below
reaction. The catalyst is vanadium pentoxide [V2O5] on an inert carrier or support such as
silica/alumina. The carrier materials offer high surface area on which the catalyst is
dispersed and deposited. Distributing the catalyst over the support enhances its activity by
exposing its surface to the reactants.

SO2 (g) + 0.5 O2 (g) SO3 (g)

This reaction is reversible and exothermic. Consequently, conversion of SO 2 is limited by

equilibrium. The reaction has certain limitations on temperature: it occurs at temperatures
> 425 oC, below this temperature, the rates are negligible; temperatures > 620 oC are
detrimental to the vanadium pentoxide [V2O5] catalyst.

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Our goal for this oxidation is to obtain upwards of 99 % conversion to ensure that the raw
material, sulphur dioxide, is completely utilized and exceedingly low levels of unreacted SO2
are released into the atmosphere through the vent gas. Remember: SO2 is a pollutant that
can cause acid rain.

We wish to select a reactor and its configuration to achieve our goal factoring in the
constraints elucidated above. Before this selection, let’s understand the effect of
temperature on the rate of reaction of SO2 and its equilibrium conversion.

Recall Le Chatlier’s principle for reversible and exothermic reactions.

According to Le Chatlier’s principle, what temperatures and pressures favour high

equilibrium conversion of SO2? High or low? Explain. Be qualitative.

Draw the following graphs: i) equilibrium conversion of SO2 oxidation versus temperature
and ii) rate of forward reaction versus temperature. From these plots, identify and write the
conflicting effects of temperature?

Now, let’s discuss the features of different types of reactors used for heterogeneous
systems. By heterogeneous here we mean reactants are in gaseous form that react on a
solid catalyst. You might have studied these reactors in CL 324 course. After description of
the features, we wish to discuss applicability of these reactors to oxidation of SO 2 to choose
the best possible reactor to achieve our goals explained earlier.

i) Fixed bed reactor

Reactants in

Products out

Catalyst is dumped in reactor [cylindrical vessel] and held in place by a supporting plate at
the bottom. The reactor is insulated so there is no heat exchange either with surroundings
or with any coolant. If the reaction is exothermic, heat is released as the reactants traverse
through the reactor. As this heat stays with reactants and the products, their temperature
rises. As a consequence, the reaction rates rise leading to further increase in temperature
of reactor contents. However, the reducing concentration of reactants lowers the rates,
which eventually plateaus to a low value.

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 ii) Shell-and-tube-type reactor

Reactants in

Steam
out

Steam
in

Products out

Catalyst is filled in tubes measuring few inches in diameter. Such tubes are arranged as
shown above. The reactants in the form of gas enter the tubes and react on the catalyst
particles in the tubes. If the reactions are exothermic, heat is released as reaction proceeds.
This heat is removed by circulating a coolant in the shell side, on the outside of the tubes.
Typical coolant is water, which is converted to steam as it leaves the reactor. As heat is
removed continuously, the reactor is operated under near-isothermal conditions. As the
reaction progresses, the rates fall as the concentration of reaction decreases and
temperature remains nearly same.

Compare features of fixed bed reactor and shell-and-tube type reactor configurations in a
Table. Include temperature, rate, equilibrium conversion, ease of construction in your
comparison.

Let’s now generate a discussion on these reactors for the reaction, SO2 + 0.5 O2 SO3

Fixed bed reactors achieve high rates by allowing the temperature of reactor contents to
rise. However, with rising temperatures, the equilibrium conversion that can be attained
decreases. The reactor effluents exit the reactor at a higher temperature than the
temperature at which they entered and an equilibrium conversion corresponding to this exit
temperature. Clearly, this conversion is far less than 100 %.

The equilibrium limitation on conversion of SO2 is overcome by using multiple fixed bed
reactors with interstage cooling. The stream emerging from the first bed is cooled and then
passed through the second bed of catalyst. In this bed, the temperature rises again because
of reaction. The effluent of second bed are cooled and then fed to the third bed.

As we keep using more beds of catalyst, SO2 concentration keeps dropping after every bed
and lowering the reaction rates. After three beds, the reaction is pushed forward by
removing SO3 by dissolving it in aqueous H2SO4 to produce concentrated H2SO4. The outlet
stream of the absorber is passed through fourth bed to achieve an overall conversion of SO2

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upwards of 99 %. The effluents of this bed are passed through another absorber to mop up
SO3, again in aqueous H2SO4 to produce concentrated H2SO4.

Which reactor configuration is used to oxidize SO2? What strategy is used to overcome the
limitations of this configuration? Show the strategy on a plot of equilibrium conversion
versus temperature and explain it.

Draw a flowchart that achieves 99.7 % conversion of SO2 to SO3. This flowchart should have
four catalytic beds and two absorption towers. Include cooling and heating operations
wherever necessary.

Use the following symbols for the flowchart: for fixed bed, for cooler,

for heater and Absorption for absorption tower

The sulphuric acid we discussed is called ‘Double Contact Double Absorption [DCDA]’
process because of two absorption towers and ‘two contacts’ with catalyst [first three beds
is ‘one’ contact and the fourth bed is ‘second’ contact]

A friend of yours suggests a completely different idea to achieve high conversion of SO2. The
flowchart given below summarizes this idea. Give your opinion on this idea.

Idea: Effluents of reactor bed are separated, SO3 is absorbed in water to form H2SO4, and
unconverted SO2 is recycled. To operate the process continuously a portion of the recycle
stream is purged because the fresh feed stream contains N2, an inert gas. Think: fraction of
N2 in the fresh feed stream and the fraction of recycle that needs to be purged. Can the
challenge of 99.7% conversion be achieved with the purge?

Recycle Purge

Fresh feed H2SO4

Absorption
Reactor bed H2O

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A typical temperature profile in a four-bed SO2 converter is shown below. Inter-stage
cooling is not shown here.
SO2, O2, N2

710 K
865 K Conversion = 65%

85% 710 K
770 K
705 K
94%
720 K
695 K
99.7%
5% 700 K SO3, SO2, O2, N2

In the previous question, you have drawn a flowchart for obtaining 99.7 % conversion for
SO2. This flowchart has coolers and heaters. Based on the flowchart and the values of
conversion and temperatures indicated in the above figure, show that heat integration is
possible in the flowchart. By heat integration, heat is exchanged between the available hot
and cold streams without any adding any stream to the process to the extent possible. If
heat is available after heat integration, this additional heat could be used to generate
steam. If heat is needed after heat integration, an additional heat source is necessary.

Draw a detailed process flow diagram for the production of sulphuric acid using ‘Double
Contact Double Absorption’ process.

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