Production Process of Sulfuric Acid

GROUP 10 Hrutwick Sawant 2018A1PS0650G

Nikita Sahu 2018A1PS0654G
Manleen Kaur Gujral 2018A1PS0657G
Yogen Borkar 2018A1PS0659G
Yukti Toshniwal 2018A1PS0666G
ABOUT SULPHURIC ACID
● Sulphuric Acid, also known as oil of vitriol, is a mineral acid with chemical
formula H2SO4.
● It is a colourless, odourless, viscous liquid, soluble in water, having strong acidic
nature.
● At high concentrations, it acts as dehydrating agent besides exhibiting oxidising
properties.
● Being hygroscopic, it readily absorbs water vapour from the air.
● It can cause severe chemical and thermal burns upon contact as it decomposes
proteins.
● Anhydrous H2SO4 is a very polar liquid, having a dielectric constant of around
100. It has a high electrical conductivity, caused by dissociation through
protonation of itself.
INDUSTRIAL APPLICATIONS
● Used in production of industrial cleaning agent, chemical industry, fertilizer
manufacture and wastewater management.
● Sulphuric acid is also used as an electrolyte in Lead-acid batteries and in
dehydrating a compound.

CURRENT MARKET:
● The global sulfuric acid market is projected to reach USD 11.10 billion by 2021,
at a CAGR of 2.87% during the forecast period.
● Furthermore, this market is projected to reach 278.33 million tons, at a CAGR
of 2.20% from 2016 to 2021.
● Increase in the production of nutrient rich food crops and steady demand for
sulfuric acid due to its diversified applications are the key factors driving the
global sulfuric acid market.
Market Survey
MARKET OF SULPHURIC ACID IN INDIA
● The demand for sulphuric acid in India is projected
to reach 25,391 thousand tonnes by 2030 due to
the rise in the usage of the acid in fertilizers and
other specialty and bulk chemicals such as nitric
acid, hydrofluoric acid, and titanium dioxide.
● Demand for fertilizers, especially phosphate
fertilizers, is anticipated to increase significantly
due to the rise in production of cereals and oilseeds
such as wheat, rice, cotton, and soya bean due to
the growth in global population.
● In terms of consumption, fertilizer segment
consumed around 60% of manufactured sulfuric
acid.
MARKET SURVEY
BCG Matrix
● Growth rate is predicted at 2.87% CAGR by
2021. This is averagely about half of the growth
rate of other major chemicals produced.
● Sulphuric acid production is the largest produced
chemical and is nearly equal to the production of
next three largest produced chemicals
● In BCG Matrix, Sulphuric Acid Industry must lie
around the region of Cash Cow (having high
market share but less growth rate). So, this unit
will produce steady cash flow. Therefore it is
quite viable for setting up the unit.
MARKET SURVEY
Porter’s Five Forces-

1) Rivalry - High number of existing companies, so high Rivalry.

2) Bargaining power of suppliers - large number of suppliers - suppliers do
not have control
3) Bargaining Power of Buyers - large number of buyers - buyers do not
have control
4) Threat of new Entrant - easy to start - high threat
5) Threat of Substitute Product - no alternative available - Less threat
MARKET SURVEY

Market Drivers Market Restraints

Steady demand - easy prediction Environmental Regulations

Growing demand in various new Surplus Market

industries
Volatility in raw material prices
Increase in production of food
crops - used in fertilizer
REACTION DETAILS
● Combining of Sulphur and oxygen
S(l) + O2 (g) → SO2(g)
● Reacting of Sulphur dioxide with sulphur trioxide in presence of V2O5
SO2 +½ O2(g) ⇌ SO3(g)
● Combining of Sulphur trioxide with Sulphuric acid to form Oleum
SO3(g) + H2SO4(l) → H2S2O7(l)
● Water is added to oleum and 98% sulphuric acid is formed
H2S2O7(l) + H2O(l) → 2H2SO4(l)
REACTION DETAILS (CATALYSIS)
● Reacting of Sulphur dioxide with sulphur trioxide in presence of V2O5
SO2 +½ O2(g) ⇌ SO3(g)
● Step 1: Oxidation of SO2 to SO3 by V5+

2SO2 + 4V5+ + 2O2- → 2SO3 + 4V4+

● Step 2: Reduction of
4V4+ + O2 → 4V5+ + 2O2-
Reaction details (Catalysis)
Multiple mechanisms
Existing
Production
Processes
EXISTING PRODUCTION PROCESSES #1
Modified Lead Chamber process
● It is able to treat gases with a low content of sulphur dioxide, 0.5-8 %, but
also gases containing a mixture of sulphur dioxide and nitrogen oxides. The
process is potentially useful for cleaning the off-gases from power plants and
ore roasting plants.
● The conversion efficiency of this process is almost 100% for sulphur dioxide
contents between 0.5 to 8 %
EXISTING PRODUCTION PROCESSES #2
Pressure Contact Process
● In these processes the sulphur dioxide conversion and the sulphur
trioxide absorption are both carried out at high pressure, because the
oxidation of sulphur dioxide is favoured by high pressure.
● Even higher conversion ratio, 99.80-99.85 % is reported for this type of
process.
EXISTING PRODUCTION PROCESSES #3
Wet Contact Process
● This process has been employed to treat off-gases containing at least 10%
hydrogen sulphide. The hydrogen sulphide in the treated off-gas is first burnt
to sulphur dioxide and water (steam) and the sulphur dioxide is then converted
to sulphur trioxide which together with the formed steam yields sulphuric
acid.
● The conversion efficiency, regarding sulphur dioxide, of the Wet Contact
Process is normally about 95-98 %
EXISTING PRODUCTION PROCESSES #4
Single Contact Process
● The sulphur trioxide is absorbed in sulphuric acid in absorbers where it is
converted to sulphuric acid by the water in the sulphuric acid. The absorbing
acid is kept at the constant desired concentration of approximately 99 % by the
addition of water or dilute sulphuric acid
● If the concentration of sulphur dioxide in the feed gas is between 6 and 10 %,
the conversion efficiency is about 98 %
EXISTING PRODUCTION PROCESSES #5
Double Contact Process
● In this process there is a primary converter followed by an intermediate
absorber, a secondary converter and a final absorber.
● Feed gas should have a concentration of Sulphur dioxide at 9-12%, then
the Conversion efficiency of 99.6% can be achieved.
SELECTION OF PROCESS
● Compared to the lead chamber process, contact process gave a better output
concentration of product, better operating conditions leading to minimal
operating cost, less heat requirement and relatively lower impact on the
environment.
● Hence Contact Process was chosen over Lead Chamber Process
● Now in contact process, there were sub-categories among which Double Contact
Double Absorption Process was chosen due to its better overall efficiency and
productivity. This was mainly because the conversion efficiency depended on the
arrangement of contact beds and time of contact which was enhanced in the case
of DCDA because of the intermediate absorption.
Selected Process:
Double Contact Double
Absorption Process (DCDA)
 Significance of each unit operation on an industrial level
Unit 1: Sulphur Burning

● Large heat content is required to melt the

Sulfur. Theoretically the temperature must be
S (s) Burner
over 10000C.
● The melting of Sulfur is performed separately
SO2(g) without contact of the air for oxidation into SO2
S (l) ● The molten Sulfur is supplied to a reactor
(sprayed) along with a countercurrent flow of
Reactor dry air to enable the oxidation reaction and
(Furnace) produce Sulfur Dioxide

Dry air
Unit 2: Air Drying
● The air must be filtered and dried to avoid contamination with dust, moisture etc.
● The contamination does the poisoning of the catalyst is possible, which can cause a notable reduction in
the conversion efficiency and high utility cost during the operation other than extra cost of replacement of
catalyst.
● Oleum (disulphuric acid) is selected as the dehydrating medium for air drying.

Unit 3: Gas Cleaning unit (SO2)

● At this point processes deviate from each other.
● SO2 created from burning molten sulphur contains ash particles which need to be removed to ensure that
there are no flaws in further heat exchangers and converted unit.
● There are multiple ways to do this
○ Bag filter
○ Electrostatic precipitators
○ Scrubber
○ Cyclone
● We choose to use electrostatic precipitators because they are effective in removing even the small particle
with greatest efficiency. These are also cheaper and durable than other methods.
Unit 4: Catalytic converter

● The reaction in the converter is an

exothermic reaction. Where temperature
SO2
will rise.
● However the optimum temperature for
maximum conversion is 4500 C
● Therefore a catalyst is necessary. There
are two possible options Platinum and
SO2 Vanadium(V) oxide.
Catalytic From
intermediate
● The use of V2O5 is preferred here because
converter absorption tower of the following reason:
SO2 +SO3 ○ Low tendency for contamination
To intermediate
absorption tower
○ The lower cost of acquisition and
operation.
○ Better operation for large scale
production plants.
Dry air SO3
Unit 5: Intermediate Absorption Tower
● An intermediate double absorption column is inserted in the process to gain high conversion efficiency from
SO2 to SO3.
● SO3 is fed to main absorption tower and sulphuric acid in fed from the storage tanks and outlet we get is
Oleum in sent to their designated storage tanks.
H2SO4

SO2
To catalytic converter

Intermediate
Absorption tower

SO2 +SO3
From catalytic converter

H2S2O7
Unit 6: Main Absorption Tower
● SO3 reacts with Sulphuric acid and produces oleum.
● The usual absorption tower in the contact process is to be selected.
● The exothermic absorption might require a heat exchanger to be installed to maintain the temperature of
the absorption and prevent formation of excess sulphuric mist.
Residue air
out

H2SO4

Main Absorption
Tower

SO2

H2S2O7
Unit 7: Flue gas treatment
● Flue gas that leaves the main absorption tower contains oxides of sulphur as well as nitrogen. A scrubber is
required to treat these gasses before they are discharged.
● This is called flue gas desulphurisation.

Unit 8: Oleum Tank

● Oleum produced in the plant needs to be stored somewhere.
● This tank will act as the starting point for distribution of oleim for air drying unit.

Unit 9: Dilution Tank:

● Oleum is converted to Sulphuric acid in dilution tanks.
● The flow rate on water depends on factors like concentration and flow rate of oleum
● The Sulfuric acid streams fed to main and intermediate absorption tower originates from the tank
● Tank contain agitators which facilitate mixing and homogenisation.
● The final product from the dilution tank is 98% sulphuric acid.
 FLOWSHEET FOR THE SELECTED
METHOD
S (s) FILTER

MELTER SCRUBBER
S (l) SO2 SO2

SO2 H2SO4
CATALYTIC INTERMEDIAT
REACTOR
REACTOR SO3 E ABSORBER
DRY AIR SO3 MAIN
ABSORPTION
H2SO4 + H2S2O7 TOWER
AIR FILTER DRYER
WATER H2S2O7
OLEUM
DILUTION
TANK
H2SO4 TANK
H2SO4
H2SO4
KEY SHORTCOMINGS IN THE LEAD
CHAMBER PROCESS
● Availability of raw materials - Taking in Sulphur in its elemental liquid form is a great challenge in itself. The
process of recovering elemental forms from its compounds needs to be addressed to maximise the efficiency of
the plant.
● Availability of manpower of skilled and unskilled job requirements of the plant. The availability of human
resources and a potential team to manage it at the site location is one of the biggest contributors to plant
efficiency.
● Capital Cost Increase due to Multiple Absorbers - The use of multiple absorber towers and units to increase the
efficiency of the process might add to the capital costs. An economic tradeoff will be introduced at this point
which needs to be analysed and the proper set of alternatives need to be chosen.
Material Balance
Unit 1 - SULFUR
MELTER:
Basis: 100 moles S(solid) per unit time Elemental Sulfur

Assumptions:

1. Raw material is received as elemental

sulfur.
Sulfur losses
MELTER during melting
2. Load of unconverted Hydrogen Sulfide
in the Sulfur input as a percentage of
total input load is 1%.
3. Percentage provision for losses during
melting of Sulfur is 1%
Molten Sulfur
MASS BALANCE ON SULPHUR MELTER

Stream (INPUT) Molar flow rate (mol/time) Flow rate (g/time) w/w

Sulphur 99.06 3169.865 99%

Hydrogen Sulphide 0.94 32.01883 1%

Total 100 3201.88 100%

Stream (Loss) Flow rate (g/time) w/w

Sulphur 3169.865* (1/100) 99%

Hydrogen Sulphide 32.01883* (1/100) 1%

Stream (Output) Molar flow rate (mol/time) Flow rate (g/time) w/w

Sulphur 98.07 3138.166 99%

Hydrogen Sulphide 0.93 31.69865 1%

Total 100 3169.86 100%

Unit 2 - REACTOR

Molten sulphur in
Molten S
Component Molar flow rate Flow rate (g/time) %w/w
(mo/time)

Molten S 98.07 3138.166 99

H2S 0.93 31.69865 1

Reactor
SO2
(Furnace)

Dry air in
Component Molar flow rate Weight (g/time) %w/w
Dry air (mol/time)

O2 147.14 4708.536 21

N2 546.53 15302.74 78

Ar 7.01 280.27 1
MASS BALANCE ON REACTOR

Streams Out

Molten S Component Molar flow rate Flow rate %w/w

(mole/time) (g/time)

N2 546.53 15302.74 68.34

SO2 97.09 6213.57 27.75

Reactor
SO2
(Furnace) O2(unreacted) 16.66 533.07 2.38

Ar 7.01 280.27 1.25

Pure S(solid) 0.980677 31.38166 0.14

Dry air H2S 0.14
0.932313 31.69865

Total 669.2 22392.73 100

 Unit 3 - CATALYTIC CONVERTER + INTERMEDIATE
ABSORPTION TOWER
Assumptions
1. 80% of the H2SO4 is coming back in Oleum
SO2 2. 20% of the SO3 produced is producing Oleum
3. 80% of the SO3 produced goes to Main Tower

Component Molar flow Flow rate %w/w

(INPUT) rate (g/time)
(mol/time)
Catalytic
converter + N2 546.53 15302.74 68.34
Intermediate H2S2O7
SO2 97.09 6213.57 27.75
Absorption
Tower O2(unreacted) 16.66 533.07 2.38
H2SO4
Ar 7.01 280.27 1.25

Pure S(solid) 0.980677 31.38166 0.14

H2S 0.932313 31.69865 0.14

Dry air SO3
Total 669.2 22392.73 100
 TO MAIN ABSORPTION TOWER

Input (Dry air) Molar flow rate Weight Flow rate Output Molar flow Weight flow
(mol/time) (g/time) rate(mol/time) rate (g/time)

SO3 77.66961 6213.569

O2 200.0689 6402.203
N2 1289.639 36109.9
N2 743.1129 20807.16
Ar 16.53384 661.3535
Ar 9.527089 381.0835
O2 168.1837 5381.878

Input (H2SO4) Molar flow rate Weight Flow rate Output Molar flow Weight flow rate
(mol/time) (g/time) rate(mol/time) (g/time)

H2SO4 97.08701 9514.527 H2S2O7 77.66961 13825.19

H2O 8.049515 144.8913 H2SO4 77.66961 7611.622

 Input Molar Weight
Unit 4 - MAIN ABSORPTION Flow Rate
(mol/time
Flow Rate
(g/time)

TOWER
)
Input Molar Flow Weight Flow SO3 77.66961 6213.569
Rate Rate (g/time)
(mol/time) N2 1289.639 36109.9
Residue
air out H2SO4 78.8524 7632.912 Ar 16.53384 661.3535
(diluted)
H2SO4 O2 168.1837 5381.878

Output (Oleum) Molar Flow Rate Weight Flow Rate

(mol/time) (g/time)
Main Absorption
SO2 H2S2O7 77.66961 13825.19
Tower
H2SO4 14.03754 1375.679

Output (Tail gas) Molar Flow Rate Weight Flow Rate

(mol/time) (g/time)
H2S2O7 N2 1289.639 36109.9

Ar 16.53384 661.3535

O2 168.1837 5381.878
Energy Balance
UNIT 1: Furnace (Reactor)
Assumption:
Work done by shaft, fans, pumps, neglected
Total heat for SO2= -26927.63271 kJ/unit time
INPUT : MOLTEN SULFUR

Stream Temperature (℃) Sulfur-120 ℃ Air-150 ℃

Stream Pressure (atm) 1

Species Molar Flow Rate Sp. Enthalpy (kJ/mol) kJ/time

(mol/time)

Molten Sulfur 98.06768687 2.699 264.6846869

Filtered Dried Preheated Air to furnace 952.7088532 4.31653 4112.396346

Energy from Combustion of S -26927.63271

Energy from combustion of fuel 183.66 18011.11137

Total -4539.440304
OUTPUT : SO2 with Other Gases

Stream Temperature (℃) 1127

Stream Pressure (atm) 1

Species Molar Flow Rate (mol/time) Sp. Enthalpy (kJ/mol) kJ/time

Sulfur Dioxide with other gaseous 669.1915796 -8.43251472 -5642.967846

components

Provision for losses, errors due to 1103.527542

neglecting terms

Total -4539.440304
 UNIT 2:
Catalytic Converter +Intermediate Absorption Tower
Assumption: H+C will be -7273.5 kJ/unit time

INPUT: SO2 Stream Pressure (atm) 1

Species Molar Flow Rate Sp. Enthalpy kJ/time Temperature

(mol/time) (kJ/mol) (℃)

SO2 97.08701001 18.868 1831.837705 432

INPUT : 98% Stream Pressure (atm) 1

H2SO4 Species Molar Flow Rate Sp. Enthalpy kJ/ time Temperature
(mol/time) (kJ/mol) (℃)

H2SO4 36.22869881 5.7 206.5035832 67

INPUT : Filtered Dried Air

Stream Pressure (atm) 1

Input of Filtered Dried Air

Species Molar Flow Rate Sp. Enthalpy kJ/time Temperature (℃)

(mol/time) (kJ/mol)

Filtered dried air 952.7088532 0.02897 27.59997548 30

SO3 -7528.515104 25

Generation of Oleum ( Energy 521.41

Released from the generation of
Oleum-Energy consumed by
Absorption of SO3 in H2SO4)

Heating H
OUTPUT

Stream Pressure (atm) 1

Streams Molar Flow Rate Sp. Enthalpy (kJ/mol) kJ/time Temperature (℃)
(mol/time)

SULFUR TRIOXIDE 77.669608 6.505 505.240800 437

1

Oleum 91.70714506 19.923 1827.08145 97

1

Cooling C

Total Input Energy -4941.16384 kJ/time

Total Output Energy 2332.322251 kJ/time

Net -7273.486092 kJ/time

UNIT 3: Main Absorption Tower

INPUT

Stream Pressure (atm) 1

Species Molar Flow Rate Sp. Enthalpy kJ/time Temperature

(mol/time) (kJ/mol) (℃)

H2SO4 36.22869881 5.7 206.50358 67

32

SO3 77.669608 6.505 505.24080 187

01

SO3 feed ( air ) 1474.356928 13.38414 19732.999 187

53

Total Input 20444.74392 kJ/time

OUTPUT

Stream Pressure (atm) 1

Streams Molar Flow Rate Sp. Enthalpy kJ/time Temperature

(mol/time) (kJ/mol) (℃)

Oleum 91.70714506 19.923 1827.081451 97

Air 1474.356928 10.4460026 15401.1363 87

Total Output 17228.21775 kJ/time

Energy difference between input and output= 3216.526163 kJ/time

This energy will comprise of the heating and cooling requirements)
Economic
Potential
Economic Potential Calculations
Raw Material Cost: S → ₹ 380.2139 / kmol

Miscellaneous materials (plant supplies): Assuming it to be 1% of the Capital Costs

Utilities: (From Aspen) → ₹16,28,22,634.40 (≈16.28 Crores)

Product Value: ₹980/kmol

Economic Potential= (Product value- Raw material Value)= ₹ 198636.71/ hr

Green engineering
and safety
measures
Safety and Environmental aspects of Sulfuric Acid
Production
● SAFETY ISSUES -
○ Inhalation of acid is fatal.
○ Massive burns can be caused on exposure to skin.
○ Sulphur burns in air and can lead to ignition, leading to spark and flames.
● ENVIRONMENTAL ASPECTS -
○ The ratio and emission of effluents in the exhaust stream needs to be monitored carefully
depending on the plant site.
○ If it goes over the permissible limit, effluent disposal needs to be introduced along with all the
necessary special facilities.
○ The Wellman–Lord process is a regenerable process to remove sulfur dioxide from the exhausts
without creating a throwaway sludge product.
○ Our exhaust stream is highly concentrated in terms of sulfur dioxide, thus Wet regenerative
process (specifically Wellman Lord Process) is highly preferred and recommended.
ASPEN
Simulation
Main Flowsheet
ASPEN SIMULATION
❏ Basis - 100 mol/sec or 360 kmol/hr.
❏ Global method - ELECNRTL, Vapour phase calculations - Peng-Robinson
❏ Unit Operations and reactions used:
❏ Approaches dropped:
❏ Adding the SO3 absorption column

equation to the Global Chemistry.

❏ Liquid in the absorption towers
replaced with pure water.
Process Intensification
❏ 1 catalytic convertor - Gave only a conversion of 30%, thus 3 step conversion
used - gave 99% conversion to SO3.
❏ Regular dry air feed changed to O2 enriched air (30% v/v) for sufficient
conversion to SO2.
❏ Compressor added and inlet temperature changed to a lower value so that feed
pressure to Absorber 1 becomes more than the stage pressure.
❏ Water input reduced to 50% for increasing absorption.
❏ Excessive water countered by regulating the liquid flow rate. Outlet of Absorber
1 ought to be dried before entering Convertor 4.
 Conclusions and Recommendations
● On analysing the processes along with their shortcomings, we narrowed down
the most feasible and efficient manufacturing process which was Double
Contact Double Absorption Process.

● We compared our shorthand results with the Aspen results and we realised it
was more or less consistent if we take into account the real conditions.

● The group recommends that a comprehensive pinch analysis be conducted to

further optimize utility consumption of heating and cooling .

● Allocating the heat removed from the converter by cooling water for process to
process heat exchanger alone, can almost reduce cooling utility up to a 28-
30%.
Conclusions and Recommendations
● Due to the range of exothermic reactions involved the energy recovery potential is high in
a plant of this nature.

● Available literature in this regard indicates the following breakdown of recoverable energy
in various sections of the plant (Louie, 2005).

● The burner and the converter energy recoverable segments can be roughly considered as
high grade energy that could be used for process heating and power generation while the
remainder is mostly low grade that could be used for minor heating applications such as
water heating, inline heating of process lines such as molten Sulfur transfer lines etc.
Conclusions and Recommendations (Contd.)
● We get SO2, SO3 and H2SO4 as the major components in the exhaust, with a very
high percentage of SO2. This SO2 can be recovered depending upon the economic
tradeoff between the worth of SO2 recovered and the cost (initial and operating)
of Recovery Unit Operation.
If we recover SO2 ( when cost of recovery is less than the worth of SO2
produced), then we have two options:
External Buyer: Sulfuric acid is followed by refrigerating agent and bleaching
agent (Paper industry) application. Food preservative is one of the leading
application segments of the sulfur dioxide market. This provides extra revenue.
Internal Buyer: We send this recovered sulfur dioxide back to the stream before
the catalytic converters as a recycle part.
This choice will depend upon the market availability of elemental Sulfur and
Sulfur dioxide.
Thank you!