The process

Technology
of
Sulphuric Acid
Production
 Lecture Outline
- History of Manufacture Development
- Manufacture
- Oleum Production
- Heat Integration Issues / By-products
- Markets
- Usage in Caprolactam Manufacture
Importance of H2SO4

The leading Chemical product in

global tonnage production
globally more sulphuric acid is made
than any other compound
Both industrially and commercially
most important product
•fertilisers, paints and pigments,
detergents, plastics,metallurgy
car batteries, laboratory acid
 World Supply / Demand for
Sulfuric Acid
(thousands of metric tons, 100% H2SO4)

250,000
200,000
150,000
100,000
50,000
0
1985

1988

1991

1994

1997

2000
Annual Capacity Production
 Sulphuric Acid - End Uses

Chemicals
3% 2% 2%
Ore Leaching 5% 11%
7%

Ag. Chemicals
10% Phosphate
Fertilizers
60%

Phosphate Fertilizers Other Fert./Ag Chem.

Ore Leaching Petroleum Ref.
Rubber/Plastics Pulp & Paper
Pigments Chemicals
 Markets for Sulfuric
 The fertilizer market is the largest single use for
Acid
sulfuric acid and consumes 50-65 percent of all
produced.
 Second is the organic chemical industry. Production of
detergent, plastics and synthetic fibers are examples.
 Production of TiO2 consumes large quantities of
sulfuric acid. TiO2 is a white pigment used in paints and
plastics.
 In the metal industry, sulfuric acid is used for pickling
ferrous and non-ferrous materials and in the recovery
of copper, nickel, and zinc from low-grade ores.
 Finally, the petroleum industry uses acid as a catalyst
for various reactions and tretment of petroleum
products.
Acid Strengths
Percent
H SO Uses
2 4

Associated
35.67 End Usesbatteries, electric utilities
Storage

62.18
Normal superphosphate and other fertilizers
69.65
Normal superphosphate and other fertilizers,
77.67
isopropyl and sec-butyl alcohols
80.00 Copper leaching
Phosphoric acid, tianium dioxide, steel pickling,
93.19
regenerating ion exchange resins of utilities
98-99 Chlorine drying, alkylation, boric acid

104.50
Surfactants, nitrations, hydrofluoric acid
106.75

109.00 Explosives

111.25
Reagent manufacture, organic sulfonations,
113.50
blending with weaker acids
114.63
Sulphuric Acid production scheme
Overview of the main feedstock, consumers and
cycles of the H2SO4 economy
 Raw material of Sulfuric Acid
 Elemental sulfur mining of underground deposits
 Desulfurization of oil and gas
 By-product of metal extraction (SO2): Non
ferrous and Pyrite/Ferrous metals
 Hydrogen regeneration
Distribution of the H2SO4 production 2005
according to the SO2 source
World Sulphuric Acid Supply Trends
million tonnes
250
elemental
200 smelter
pyrites
150

100

50

0
85 90 95 0 5
 Major unit operation of H2SO4 plant
1. solid sulphur storage
2. sulphur melting
3. liquid sulphur filtration
4. liquid sulphur storage
5. air filter and silencer
6. air dryer
7. sulphur combustion, two burners with individual air supply
8. steam drum, feed-water tank, waste heat boiler
9. converter
10. intermediate absorber
11. final absorber
12. stack
13. heat exchangers, economisers and superheater.
Raw materials: Technology & Product

Raw materials

Sulfur Air H2 O
Process Technology

Sulphuric Acid
H2SO4
Three main process technologies
1. Oxidation of Sulphur to SO2

S +O2 SO2

2.Oxidation of Sulphur dioxide to SO3

2SO2 + O2 2SO3

3.Absorption of SO3

SO3 + H2O H2SO4

1.Sulphur dioxide formation:Primary Generation of SO2, 79% Combustion of
Sulfur,9% Recovery from Metallurgic Processes- 5% Regeneration of Spent Acids
Sulphur Air

SO2+N2

Sulphur and metalic sulphides Oxidation reactions

S + O2 +N2 SO2+N2

MS + O2 SO2 + MO
FeS2 + 2O2 2SO2 + FeO
CuS + O2 SO2 + CuO
ZnS + O2 SO2 + 2ZnO
 Oxidation
1) S + O
ofSO Sulfur
2 2

Sulfur
Steam

10-12% SO2

Water

Air
Process:

93% H2SO4
Primary Generation of SO2
-79% Combustion of Sulfur
- Air drying tower with acid
- Sulfur is injected into burner
- Reaction Temperature 2000°F
- Exothermic reaction must be
cooled

-9% Recovery from Metallurgic - Steam recovered

Processes
- 5% Regeneration of Spent Acids
 Sulphur trioxide formation
Oxidation of SO2
SO2
SO3 +N2
Air

2SO2 + O2 2SO3

exothermic & reversible

Sulphur trioxide formation

Step 2: Formation of SO3 the Contact Process

2SO2 + O2 2SO3 exothermic

Factors:
• Catalyst

• Temperature

• Pressure
 Sulfuric Acid

Step 2: Formation of SO3 the Contact Process

2SO2 + O2 2SO3 exothermic

Factors:
• Pressure 1-2 atmospheres

• The yield of SO3 increases as P is increased

• High pressure is costly

***These are compromise conditions***

 Sulphur trioxide formation
Oxidation of SO2 is thermodynamically
favoured by low temperatures
an exothermic process, a decrease in
temperature by removal of the heat will favour
the formation of SO3
• increased oxygen concentration
• SO3 removal (as in the case of the double
absorption process)
• increased pressure
• catalyst selection, to reduce the working
temperature (equilibrium)
• Multiple catalyst beds with intermediate
cooling
Oxidation of Sulfur DioxideSO Gas
Contact Process:
2

-Vanadium pentoxide Gas

Cooling
catalyst
- Exothermic Reaction
- Multiple Steps with
cooling in
between
- Double absorption
- Heat integration SO3 Gas
Coverter:Temperature-yield profile of the 4 bed system
Typical Catalyst Distribution

Catalyst % Catalyst Conversion %

Bed
1 19.4 56
2 25.0 87
3 26.7 99.1
4 28.9 99.7
 Because of the large effect temperature plays on the
Oxidation of Sulfur Dioxide
reaction, multiple catalyst layers are used, with cooling
between each step.
 Additionally, as the partial pressure of SO3 increases,
further reaction is limited.
 This is overcome by removing the SO3 after the third
stage to drive the reaction to completion.
SO2 Gas SO2 Gas

Gas
Cooling

SO3 Gas

SO3 Gas 93% H2SO4

 1 Single contact/single absorption process
After purification and drying, the SO2 is
convertedinto SO3 using a series of 4 catalyst
beds,containing alkali and V2O5. Afterwards,
the SO3 is absorbed in concentrated sulphuric
acid and,if necessary, an oleum absorber is
installed upstream. SO3 reacts with the water
contained in the absorber acid to yield
H2SO4. The absorber acid is kept at the
desired concentration of approximately 99 %
w/w by addition of water or dilute H2SO4.
1 Single contact/single absorption process
 Double contact/double absorption process
• A primary SO2 conversion of 85 – 95 % is achieved in the first
catalysis stage of the converter before entry into an
intermediate absorber.
• The gases iss then cooled to 200 ºC in a heat exchanger, the
SO3 already formed is absorbed in 98.5 – 99.5 % sulphuric
acid. If necessary, an oleum absorber is installed upstream of
the intermediate absorber.
• The absorption of SO3 shifts the reaction equilibrium
significantly towards the formation of more SO3. This results
in a considerably higher conversion rate, if the residual gas is
passed through the following converter beds (usually one or
two). The SO3 which is formed in the second catalysis stage is
absorbed in the final absorber.
• 2+2 double contact double absorption plant. 2+2 indicates the number of
catalyst beds before and after intermediate absorption. 3+1 represents the
alternative configuration with 4 beds, 3+2 is the normal configuration with
5 beds
 Oxidation of Sulfur Dioxide
Double contact/double absorption process

SO2 Gas
SO2 Gas

Gas
Cooling

SO3 Gas
510 C

430 C

200 C
75 C

SO3 Gas 93% H2SO4

125 C
Double contact/double absorption process
Double absorption process
 The operating lines plotted on the equilibrium
curve show that the reaction approaches the
equilibrium curve but never quite reaches it. In order
toreach equilibrium a large amount of catalyst and
residence time is required.
 The rate of reaction is not shown but plays an
important part in determining the inlet temperatures
and the amount of catalyst required. If the initial
temperature is too low, the rate of reaction is low so
more catalyst isrequired.
 The optimum reaction path is determined in
conjunction with the catalystsuppliers and is a
compromise between the amount of catalyst volume
andsize of the gas-to-gas heat exchangers.
The reaction path for the double absorption
example is not directly comparable to the
single absorption path because of the
different gas compositions.
The basic steps of reaction and cooling are
the same but the temperatures and
conversions are for 11% SO2 and 10% O2.
Despite the higher SO2 concentration, a
higher overall conversion is achieved because
of the absorption and removal of the SO3
that is formed through thefirst three
catalyst beds.
After the SO3 is removed in the
intermediate absorber the new gas
composition is effectively much lower in
terms of SO2 concentration and a
new equilibrium curve applies.
 In the example, the original equilibrium
curve is based on 11% SO2 and 10%
O2. After the intermediate absorber
the new equilibrium curve is based on
0.68% SO2 and 5.67% O2.
The lower SO2 concentration shifts the
equilibrium curve up which allows higher
conversions to be obtained.
 Oxidation of Sulfur Dioxide
Temperature Profile
Sulfuric Acid & Oleum Formation by SO3 absorption

SO3 H2 O

}
{ H2SO4 H 2 S2 O7

SO3 + H2SO4 H 2 S2 O7

SO3 + H2O H2SO4

{the direct combination of SO3 with water is too

exothermic and forms a fine mist of acid}
Sulfuric Acid & Oleum Formation
SO3 H2 O

{ H2SO4 H 2 S2 O7 }

3: Absorption of SO3
SO3 + H2O H2SO4

SO3 + H2SO4 H 2 S2 O7

{The direct combination of SO3 with water is too

exothermic and forms a fine mist of acid}
 Oleum Production
Oleum Formation (disulfuric acid)

 Sulfuric acid with additional SO3 absorbed

 20% Oleum contains 20% SO3 by weight in the oleum
 Common strengths of oleum are 20, 30, 40, 65
percent.
 To produce 20 and 30 percent oleum, only requires
an additional absorption tower.
 Oleum is used in reactions where water is excluded
SO3 + H2SO4 H 2 S2 O7 (disulfuric acid)
 8.Wet catalysis process
• Wet SO2 gases (e.g. from the burning of H2S gases or from the
catalytic conversion of H2S gases) are directly supplied into the
contact tower without previous drying. SO3 formed by the
catalytic conversion immediately reacts with the moisture of the
gases, thereby forming Sulphuric acid. The sulphuric acid is
condensed in a condenser installed after the contact tower.Process
variants enable an improved condensation and the production of
concentrated acid, for example: the Concat process is designed to
produce H2SO4 of higher concentrations from gases with a
low SO2 content. The formed H2SO4 is condensed in two steps, a
high temperature venturi condenser (this yields 93 % H2SO4) and
a condenser tower (this yields 70 – 80 % H2SO4) the Topsøe
WSA process is designed to reduce the formation of H2SO4 mist.
After the conversion of SO2 into SO3, the gases are condensed in
a falling film evaporator with glass pipes. The formation of mists
is prevented by precise temperature control.
Wet catalysis process
Pyrite roasting
Fluidised bed roasters are the preferred equipment for
pyrite roasting. They are superior to other types of
equipment in terms of process technology, throughput
rates and economy. When roasting pyrite to get SO2
gas, two by-products, iron oxide and energy, are
produced. One tonne of acid requires 0.5 tonne pyrite.
Due to the heterogeneous character of the raw
material pyrite, the SO2 content in the gases is
slightly variable over time (generally 6 – 14 %, O2 free).
The gases are always treated in three to
four cleaning steps with cyclones, bag filters,
scrubbers and electrostatic precipitators. Waste
water from the scrubbing is treated before discharge.
The clean gas is diluted with air to 6 –10 % and dried
before entering the conversion process
 Non-ferrous metal production
metallurgical processes like roasting, smelting or
sintering of ores in order to yield metals, such as Cu, Zn
or Pb. Non-ferrous metal smelting accounts for 39 % of
H2SO4 production.
Many metal sulphides when roasted during metallurgical
processes, produce gases containing SO2.
The concentration of SO2 in gases entering an acid
plant, determines the amount of gas that must be treated
per tonne of fixed sulphur
 Regeneration of spent acids
Spent acids arise from processes where H2SO4 or
oleum is used as a catalyst (alkylation,
nitration, sulphonation, etc.) or from other processes
where H2SO4 is used to clean, dry, or
eliminate water.
Spent acid from TiO2 production is reconcentrated
by applying vacuum and heating, using the
heat from the subsequent H2SO4 plant. While the
concentrated H2SO4 is recycled to TiO2
production, the precipitated metal sulphates are
decomposed.
 Catalysts
vanadium compounds, platinum and iron oxide have proven to
be technically satisfactory. At present, vanadium pentoxide is
used almost exclusively.
Commercial catalysts contain 4 – 9 % w/w vanadium pentoxide
(V2O5) as the active component,together with alkali metal
sulphate

In industrial practice, the lower temperature range is 410 – 440

ºC for conventional catalysts and 380 – 410 ºC for caesium
treated catalysts. The upper temperature range is 600 – 650 ºC,
above this, catalytic activity can be permanently lost due to
internal surface area reduction. The
average operating life for the catalyst is approximately 10 years.
Operating life is generally determined as a result of catalyst
losses during screening of the catalyst, which has to be carried
out periodically to remove dust.
 converter types
Two general converter types have been in use
extensively in the past:
•the brick-arch support and
• the cast iron beams and columns design

In conventional converters, the shell is generally

made of boiler quality steel, with internal brick lining
and mostly additional aluminium spraying to protect
the material from scaling. A great advantage of the
brick lined vessel is its high heat capacity, which
enables long shutdown times without preheating. The
disadvantage is that older brick-arches can be porous
and, hence,process gas partially bypasses the
intermediate absorber
converter types
 Energy issues
.Up to 67 %of the process waste heat, which is released
from a double contact plant on the basis of sulphur
burning, is recovered as high pressure steam from
burning gases and from the reaction heat of
the contact process.
Waste heat released from acid cooling represents about
30 – 40 % of the total process waste heat.
A thermal efficiency of 85 – 90 % can be achieved by
using waste heat released from the acid cooling for
drying processes or for the production of low pressure
steam with a special heat recovery system.
 Birr300/tone acid SULPHUR - one tonne
of byproduct
energy available SULPHURIC ACID - 3 tones

PHOSPHATE ROCK – 3 tones

PHOSPHORIC ACID one tone P2O5

PHOSPHATE FERTILIZERS 0.5 tonne

DAP - two tones
NH3
 Reaction By-products / Heat
By-products
Integration
 57 to 64% of the energy input generates steam
 Steam energy is used to drive the turbine that
supplies power to the main air blower
 Additional steam remaining is tolled internally for
other plant operations
 SO2/SO3 is vented in small amounts and is federally
regulated.

Heat Integration
 Steam is used to pre-heat and vapor from the
absorption towers used to cool
 Minimizes the cost of manufacturing to maximize
 Sulfuric Acid
properties
Viscous liquid

Dehydrating agent
Conc H2SO4 will dehydrate hydrated
copper sulphate and carbohydrate
 Sulfuric Acid

H2SO4

Describe briefly what you observe when the

following are treated with concentrated
sulphuric acid.

• sugar (a carbohydrate)

• blue copper sulphate crystals