Lec:18

7th May ,2015

APPLIED CHEMISTRY
CH-1012
Syed Hassan Shah
Assistant Professor
Department of Mechanical Engineering
 History
9th century: Islamic physician and alchemist
Ibn Zakariya al-Razi - heated green
vitriol FeSO4 . 7H2O and blue vitriol
CuSO4 . 5H2O dilute solution of sulfuric
acid
13th century: German alchemist Albert Magnus
17th century: German-Dutch chemist Johann
Glauber burned sulphur with
saltpeter (potassium nitrate - KNO3)
18th century: Joseph Gay-Lussac, John Glover
lead chamber process
19th century: Peregrine Phillips contact process
History of Manufacture of Sulfuric
History of Manufacture of
Acid
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 BASF was granted a patent for the use of 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).
 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
World Production of Sulfuric Acid

Canada
Mexico
Others
Japan
Latin
F-USSR
Europe
Africa
U.S.
Asia

0.0 5.0 10.0 15.0 20.0 25.0 30.0

Share (percent)
 Manufacture of H2SO4

Two basic methods:

1. lead chamber process
2. contact process
 Lead chamber process
hot sulphur dioxide SO2 gas enters the reactor called a
Glover tower mixes with nitric oxide, NO, and
nitrogen dioxide, NO2, dissolves in it
some of the sulphur dioxide forms the acid (Glover acid -
about 78% H2SO4)
mixture of gases (including sulphur dioxide and trioxide,
nitrogen oxides, nitrogen, oxygen, and steam)
lead-lined chamber, reaction with water
sulphuric acid is formed by a complex series of reactions
condensation on the walls of the chamber
(3 - 12 chambers in a series)
chamber acid (contains 62% to 68% H2SO4)
 * Called contact since the molecules of
Contact process the gases O2 and SO2 are in contact with
the surface of the solid catalyst, V2O5
- based on the catalytic oxidation of SO2
1. Solid sulfur, S(s), is burned in the air to form SO2
S(s) + O2(g) -----> SO2(g)
2. In the presence of a vanadium catalyst (vanadium (V) oxide)
production of SO3(g)
2SO2(g) + O2(g) -----> 2SO3(g)
3. SO3(g) is dissolved in 98% (18M) H2SO4, to produce
disulfuric acid or pyrosulfuric acid, also known oleum, H2S2O7
SO3(g) + H2SO4 ------> H2S2O7
SO3(g) + H2O(l) -----> H2SO4(l) (slow)
4. water is added to H2S2O7 to form H2SO4
H2S2O7(l) + H2O(l) -----> 2H2SO4(l)
Oxidation of Sulfur

1) S + O2 SO2

Sulfur
Steam

10-12% SO2

Water

Air

93% H2SO4
Primary Generation of SO2
-79% Combustion of Sulfur
-9% Recovery from Metallurgic Processes
- 5% Regeneration of Spent Acids
Process:
- Air drying tower with acid
- Sulfur is injected into burner
- Reaction Temperature 2000F
- Exothermic reaction must be cooled
- Steam recovered
Oxidation of Sulfur Dioxide

SO2 Gas
Contact Process:
-Vanadium pentoxide
Gas
catalyst Cooling

- Exothermic Rxn
- Multiple Steps with
cooling in between
- Double absorption
- Heat integration

SO3 Gas
Oxidation of Sulfur Dioxide

Because of the large effect temperature plays on the reaction, multiple catalyst
layers had to be used with cooling between each step.
Additionally, as the partial pressure of SO3 increases further reaction is limited.
This was 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

Oxidation of Sulfur Dioxide

Kinetic Effects
- Oxidation of sulfur dioxide is slow and reversible
- The reaction requires a catalyst and 426.7C temperatures
-The reaction is exothermic and sensitive to excessive heat

Equilibrium Constant (The degree at which the reaction proceeds is temp. dependent)

log Kp = 4.956 - 4.678

T

T = absolute temp. in kelvin

Kp = equilibrium constant as a function of partial pressure of gases

0.5
Kp = ( PSO3 )
PSO2 PO2
Oxidation of Sulfur Dioxide

Temperature Profile

SO2 Gas SO2 Gas

Gas
Cooling

SO3 Gas
510 C
75 C
430 C
200 C

SO3 Gas 93% H2SO4

125 C
Oxidation of Sulfur Dioxide

Temperature Profile
Oxidation of Sulfur Dioxide

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
Markets for Sulfuric Acid

The fertilizer market is the largest U.S. single use for sulfuric acid and
consumes 50-65 percent of all produced.
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 low-grade ores.
Finally, the petroleum industry uses acid as a catalyst for various reactions.
Acid Strengths
Associated End Uses

Percent
H2SO4 Uses
35.67 Storage batteries, electric utilities

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