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Uses of sulfuric acid

The fertilizer market is the largest single


user for sulfuric acid.
Second is the organic chemical
industry. Production of 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 lowgrade ores.
Petroleum industry uses acid as a
catalyst for various reactions.

Acid strengths
Associated end uses
Percent
H2SO4
35.67

Uses
Storage batteries, electric utilities

62.18
Normal superphosphate and other fertilizers
69.65
77.67

Normal superphosphate and other fertilizers,


isopropyl and sec-butyl alcohols

80.00

Copper leaching

93.19

Phosphoric acid, tianium dioxide, steel pickling,


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
113.50
114.63

Reagent manufacture, organic sulfonations,


blending with weaker acids

About 220 million tonnes of sulfuric acid are produced/consumed per year.

World production of sulfuric acid, % by region (January 2012)

Sulfuric acid
Sulfuric acid is made from SO2, O2 and water.
SO2 comes from:
burning molten elemental sulfur with dry air
smelting and roasting metal sulfide minerals
decomposing contaminated (spent) sulfuric acid catalyst
Sulfur burning is far and away the largest source.
SO2 in the gas is made into sulfuric acid by
catalytically oxidizing it to SO3
reacting this SO3 with the H2O() in 98.5 mass% H2SO4(),
1.5 mass% H2O()

History of manufacture of sulfuric acid


One of the oldest industrially applied processes. Discovered by a
Persian alchemist in the tenth century.
Saltpeter and sulfur were mixed in a glass container and burned in a
moist atmosphere. Acid was collected from the condensed vapors.
In England, 1746, the lead chamber reactor was invented. This
invention allowed for higher production rates (<78%).
In England, 1831, a patent was filed that described the oxidation of
sulfur dioxide over a platinum catalyst, the Contact Process. This
new process increased yields of reaction from 70 to above 95%.
In 1913, vanadium pentoxide as a catalyst for the Contact Process
By the 1930s, vanadium pentoxide was becoming the dominate catalyst
used because of insensitivities to poisons and lower cost.
In 1960 a patent application was filed by Bayer using the so called
double-catalyst process (double absorption).

Lead chamber and tower processes


Industrial sulfuric acid production began in the eighteenth century with
the burning of sulfur in the presence of KNO3 and steam.
This developed into the lead chamber and tower processeswhich
used nitrogen oxides to form an aqueous catalyst for SO2 oxidation.
4 NO(g) + O2(g) + 2 H2O(l) 4 HNO2(l)
4 HNO2(l) + 2 SO2(g) 2 H2SO4(aq) + 4 NO(g)
The overall acid making reaction with this catalyst was:
SO2 + 0.5O2 + H2O H2SO4
NOHSO4 catalyst
The lead chamber and tower processes were used in the twentieth
century.
Unfortunately, their H2SO4 strength was limited to below about 70
mass% H2SO4. Above 70% H2SO4, the product acid contained stable
nitrosyl hydrogen sulfate which made it unsuitable for many purposes.

Contact process
Three Step Process
1) S + O2

SO2

2) SO2 + 1/2O2

SO3

3) SO3 + H2O

H2SO4

Plant

Drying
H2O + H2SO4 H2SO4.H2O
To avoid:
(a) accidental formation of H2SO4 by the reaction of H2O(g) with the
SO3 product of catalytic SO2 oxidation
(b) condensation of the H2SO4() in cool flues and heat exchangers
(c) corrosion.

FLEXERAMIC structured packing

Oxidation of Sulfur

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

Sulfur
Steam
10-12% SO2
Water
Air

Process:

93% H2SO4

- Air drying tower with acid


Primary Generation of SO2

- Sulfur is injected into burner

-79% Combustion of Sulfur

- Reaction Temperature 2000F

-9% Recovery from Metallurgic Processes


- 5% Regeneration of Spent Acids

- Exothermic reaction must be cooled


- Steam recovered

Oxidation of Sulfur Dioxide


SO2 (g) + 1/2O2 (g) SO3 (g)
Contact Process:
-Vanadium pentoxide catalyst
- Exothermic Reaction

H = 99 kJ.mol-1

SO2 Gas

Gas
Cooling

- Multiple Steps with cooling in


between
- Double absorption
- Heat integration

SO3 Gas

Lechatelier principle is usually taken into account in deciding how to optimize the equilibrium. This
states that when an equilibration system is subjected to stress, the system will tend to adjust itself
in such a way that part of the stress is relieved.

Maximizing SO3
Removal of heat a decrease in temperature will
favor the formation of SO3 since this is an exothermic
process
Increased oxygen concentration
Removal of SO3 (as in the case of the double
absorption process)
Raised system pressure
Selection of the catalyst to reduce the working
temperature (equilibrium)
Increased reaction time

Oxidation of Sulfur Dioxide


Because of the large effect temperature plays on the 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

Kinetic Effects
- Oxidation of sulfur dioxide is
slow and reversible

Gas
Cooling

-The reaction requires a catalyst


and 426.7C temperatures
-The reaction is exothermic and
sensitive to excessive heat
SO3 Gas

SO3 Gas

93% H2SO4

Oxidation of sulfur dioxide

Absorption
Catalytic oxidations SO3 product is
made into H2SO4() by contacting
catalytic oxidations exit gas with
strong sulfuric acid. The reaction is:
SO3 + H2O H2SO4
H2SO4() is not made by reacting
SO3(g) with pure H2O(). This is
because Reaction is so exothermic
that the product of the reaction
would be hot H2SO4 vaporwhich is
difficult and expensive to condense.

Efficiency of the absorption


The H2SO4 concentration of the absorbing liquid (98.599.5%)
The range of temperature of the liquid (normally 70C120C)
The technique of the distribution of acid
The raw gas humidity (mist passes the absorption
equipment)
The mist filter
The temperature of incoming gas
The co-current or counter-current character of the gas
stream in the absorbing liquid

Single absorption contact sulfuric


acid plant

1.6 O2/SO2 ratio to the converter

Oleum Production
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.
%H2SO4 = 100 + 18/80 * % oleum
20% oleum is equivalent to 104.5% H2SO4
Oleum is used in reactions where water is excluded
SO3 + H2SO4

H2S2O7

(disulfuric acid)

Double absorption contact sulfuric


acid plant

0.5 O2/SO2 ratio to the converter


98.5% sulfuric acid in an absorption tower to remove sulfur trioxide (SO3)
Double absorption plants are more complex, more difficult to start-up and
operate in compliance within emission regulations

Double absorption contact sulfuric acid plant

Reaction By-products/Heat Integration


By-products
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 the profit.

Production Considerations
Metal corrosion is a big issue in the manufacture of sulfuric acid.
Special alloy metals must be used to guard against excessive
corrosion.
Nickel, chromium, molybdenum, copper, an silicon are the
most important elements that enhance corrosion resistance of
alloys.

Important variables for corrosion


Concentration of the acid
Temperature of service
Speed of flow in pipes and equipment
Alloy element make-up

Recent developments
The three main recent developments in sulfuric acid making have
been:

improved materials of construction, specifically more


corrosion-resistant materials

improved SO2 oxidation catalyst, specifically V, Cs, K, Na,


S, O, SiO2 catalyst with low activation temperatures

improved techniques for recovering the heat from reactions


(process intensification)