SULFUR & SULFURIC ACID

CHEMICAL PROCESS TECHNOLOGY

CHE C322

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Sulfur (S)
INTRODUCTION :
Basic raw material for production of sulfuric acid.
Properties

1.
2.
o
o
o

Atomic weight 32. 07.

Bright yellow crystalline solid.
Physical state : (Solid) pure element and as sulfide and sulfate minerals.

Specific gravity- 1.803, insoluble in water, soluble in organic solvents.

Uses

3.
4.
o
o
o

80-90 % used for sulfuric acid manufacture.

Precursor to other chemicals (sulfites and sulfates)
Direct use for vulcanization of rubber

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Process Selection
CLASSIFICATION OF MANUFACTURING PROCESS
1.
Frasch process: Elemental sulfur mining
2.
Claus Process: Oxidation reduction of hydrogen sulfide
3.
Finnish process: elemental sulfur from pyrites
INDIAN SCENARIO
India is practically devoid of deposits of elemental sulfur.
Increasing demand of natural gas has given a boost to the sulfur-recovery
aspect of natural gas.
Petroleum refinery stream is also a source of H2S.
Iron pyrite (sulfides of iron) availability : Important deposits of pyrites are
those of Amjhore in Rohtas (Bihar).

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SULFUR FROM SOUR NATURAL GAS (CLAUS PROCESS)

OXIDATION-REDUCTION OF H2S
Raw material :
H2S from natural gas and petroleum refinery
AMINE ABSORPTION PROCESS FOR HYDROGEN SULFIDE REMOVAL
Sulfur recovery from sour natural gas is
conducted in two stages:
[1] Scrubbing the gas with an amine
solution (Methyl-diethanolamine MDEA)
[2] Recovery of solvent (by indirect heating)
* Process is known as sweetening of
Natural gas.
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Chemical reactions
[1] First reaction: simple combustion of H2S stream in air, carried
out in waste heat boiler to capture heat evolved as steam.
2H2S + 3O2
2SO2 + 2H2O; Ho = -247.89 Kcal

[2] Second reaction (catalytic)

4H2S + 2SO2

6S (v) + 4H2O; Ho = - 42.24 Kcal

100

Catalyst:

Al2O3 (Alumina) / Iron Oxide

Equilibrium curve

H2S

% conversion
50
100 300 500 T (C)
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Process flow sheet

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Major engineering problems

1. Two stage reactor design for exothermic SO2 oxidation

of H2S. 70-80 % conversion in first stage at 300-400 C
range followed by 250-300 C operation in second
reactor to obtain favorable equilibrium.
2. Heat exchange for molten sulfur handling.
3. Corrosion
4. Final clean up of stack gases.

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Possible solutions
Multistage operation
If the sulfur vapor from the one stage is condensed out, and the
residual gases are blended with further hydrogen sulfide and
passed over catalyst, the equilibrium conversion of 94-95% can
be obtained.
Effluent gas from a single stage may contains 2-3% SO2, which
would represent both loss of feedstock and emission problem.
Need to look at equilibrium data and catalyst for deciding
temperature range.

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SULFURIC ACID(H2SO4)

Properties
Highly
corrosive
strong
mineral acid, molecular wt :
98, MP :10.5 oC, BP : 340oC
Colorless to slightly yellow
viscous liquid
Soluble
in water at all
concentrations.
The corrosiveness of it is
mainly due to its strong
acidic
nature,
strong
dehydrating property and its
concentrated
strong
oxidizing property.

Commercially produced in

various acid strength

33.33 to 114.6 wt%

Strength over 100% referred as
Oleum

Applications
Lead acid batteries for cars
and other vehicles
Mineral processing
Fertilizer manufacturing
Oil refineries
Wastewater processing
Chemical synthesis.
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Classification of Processes
CHAMBER PROCESS
Developed first, produced acid

of concentration less than 80%

Used a homogeneous catalyst
(nitrogen oxide)
Used for producing sulfuric
acid
Virtually obsolete : corrosion of
lead, absorption of NO2 gas

CONTACT PROCESS
Yield 98% H2SO4 and higher
Originally used a supported

platinum catalyst, but later

replaced by a supported
vanadium catalyst
Far more economical process
for producing sulfur trioxide
and concentrated sulfuric acid
Current process with some
advances (DCDA)

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CONTACT PROCESS
Reactions:
[1] Sulfur is burned to produce sulfur dioxide and heat.
S(s) + O2 (g) SO2 (g)
H = -70.9 kcal
** Sulfur dioxide may also be obtained via oxidation of pyrites or from
other smelter source. Dust removal equipment add the capital cost
for these secondary sources.

[2] The second reaction, oxidation of sulfur dioxide to sulfur trioxide with
air (less exothermic, equilibrium reaction)
V2O5
SO2 (g) + O2 (g) SO3 (g)
H = -23 kcal
[3]Adsorption of formed SO3 in water
SO3(g) + H2O (l) H2SO4 (l)

H = -31 kcal
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Catalyst: (Speeds up the reaction but not consumed in reaction)

Formation of sulfur trioxide is catalyzed by 6-10% vanadium pentaoxide (V2O5)

coating.
Platinum would be a more suitable (more active) catalyst, but it is very costly
and easily poisoned.
Supported on a powdered or porous carrier

Provide large surface area

Resistance to process gases at high temperature
Examples- alumina, silica gel, kieselghur, pumice.

Promoted by alkali and/or metallic compounds

Example-potassium hydroxide

Below 400 C the V2O5 is inactive as a catalyst, and above 620 C it begins to

break down

Catalyst deactivation:

Life of modern vanadium/potassium catalyst : 5-20 years

Purification of air and SO2 is necessary to avoid catalyst poisoning (ie. removing
catalytic activities). The gas is then washed with water and dried by H2SO4
Regular screening of catalyst ( 1 year). Temperature limitation.
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Thermodynamics & Kinetics Considerations:

The equilibrium for a gas phase reaction can be expressed in partial pressures:
Kp=PSO3/(PSO2 . P1/2O2)
T(C)

400

500

600

700

800

900

Kp

397

48.1

9.53

2.63

0.915

0.384

At 400C, equilibrium conversion is 96%. But the time required for reaction (2nd)
is long, which require a large reactor and catalyst volume.
For process optimization
Multistage bed (3 or more catalyst bed)
Starting with very fast reaction rates at 550-600 C with 60-65% conversion.
Cooling of gas mixture at 400-450 C, for more favorable equilibrium
Pass over three or more beds to reached about97-98% conversion to SO3.
Air can be added at this stage to assist in displacing the equilibrium further
right.
It is expected under pressure equilibrium of the reaction more to the right
But it has not worth the additional capital cost required at high pressure
Corrosion problem
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Process Description
1.
2.
3.
4.

5.

6.

Burning an atomized jet of filtered molten sulfur in a stream of dry air (7-10 % SO2
and 11-1 4% O2).
A fire tube boiler is used to reduce gas temperature to the 400 to 240 C range,
simultaneously generating steam.
Next gas mixture sent to first catalyst bed of two-stage catalytic converter with 80%
conversion and raising temperature upto 600 C.
The conveter product is cooled to 300 C and fed to second stage, where yield
increased by 97% by operating at 400-450 C. Small amount of dry air at ambient
temperature can also be used to bring the temperature down.
The sulfur trioxide concentration at this stage is about 10% by volume. After cooling
to 150 C by water and air heat exchanger and absorbed in oleum (fed at a rate to
allow not over 1% rise in acid strength).
Final srcubbing is done with a lower strength acid (97%).

Alternatively:
5.
Hot sulfur trioxide passes through the heat exchanger and is dissolved in
concentrated H2SO4 in the absorption tower to form oleum:
H2SO4(l) + SO3 (g) H2S2O7(l)
6.
Oleum is reacted with water to form concentrated H2SO4.
H2S2O7(l) + H2O(l) 2 H2SO4(l)
**Note that directly dissolving SO3 in water is impractical due to the highly exothermic
nature of the reaction. Acidic vapor or mists are formed instead of a liquid.

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H2SO4 PRODUCTION

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H2SO4 PRODUCTION
Major Engineering problems:
1.
2.
3.
4.
5.
6.

Design of multistage catalytic convertor for a highly exothermic reactions.

( 3 or more stages)
Optimization of space velocity in catalyst chamber i.e pumping cost vs fixed
charge of reactor.
Corrosion problem : Equilibrium yield can be increased by system pressure
but increases compression cost and corrosion dictates low pressure.
Adaptation of process to various gas feeds
Yield drops due to longitudinal mixing if gas velocity is too low.
Removal of heat of absorption of SO3 in acid. Pipe coolers with water
dripping over external surface have been replaced by cast iron pipe with
internal fins to promote better heat transfer.

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Contact process for making oleum and H2SO4

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Sulphuric acid Plant

3B Economizer for Sulfuric Acid Plant

Firetube Boiler and Steam Drum for Sulfuric

Acid Plant

http://www.chanutemfg.com/sulfuricAcid.htm