CHEMICAL PROCESS

INDUSTRIES
EHCPA2B/EHCPI1A
Presented by:

John Kabuba Tshilenge

Department of Chemical
Engineering

Lecturer 3

July 2018
 Chapter 2. Inorganic Acids
2.1. Sulphuric Acid
• The largest producers and users of sulphuric acid are the
fertilizer manufacturers and the mining industry where sulphuric
acid is used for the reclaiming of uranium.
• In South Africa, sulphuric acid is produced from three different
raw materials:
1. Sulphur,
2. Pyrite (FeS2)
3. CaSO4.
• All three these processes involve the production of sulphur
dioxide gas as an intermediate product.
• With sulphur as raw material, sulphur is melted and burned in
air to form SO2. This process gives a rich SO2/gas mixture.
• With pyrite, SO2 is formed in a rotating oven or fluidised bed.
• This process gives a more diluted SO2 mixture.
• The CaSO4 – process gives a SO2/air mixture that compares to
that of the pyrite process.
• The production of SO2 is done in a rotating oven and requires a
lot of energy.
• The production process involves the oxidation of SO2 to SO3 via a
vanadium pentoxide catalyst, with the addition of extra air for
dilution and cooling.
• In the next step the SO3 is absorbed in concentrated sulphuric
acid and reacted with water to form H2SO4.
• Water is continually added to the 98 – 99% absorption acid to
prevent over concentration and the forming of oleum (H2S2O7).
• This process is known as the Contact-Process.
Contact Process
Contact Process
The process can be divided into five stages:
1. Combining of sulphur and oxygen
2. Purifying sulphur dioxide in the purification unit
3. Adding excess of oxygen to sulfur dioxide in
presence of catalyst vanadium pentoxide, with
temperatures of 450oC and pressure of 1-2 atm
4. Sulfur trioxide formed is added to sulfuric acid which
gives rise to oleum (disulfuric acid)
5. The oleum then is added to water to form sulfuric
acid which is very concentrated.
2.2. Phosphoric Acid

• Phosphoric acid can be made by one of two processes (Wet or dry).

• The wet process used in the manufacturing of fertilizer grade acid or
the dry process (here pure phosphor metal is an intermediate
product) used in the manufacturing of food grade acid.

2.2.1. Wet Process

• Sulphuric acid is used to replace the phosphate in the apatite ore.

• The reaction is:
CaF2.3Ca3(PO4)2 + 10H2SO4 →10CaSO4 + 2HF + 6H3PO4
• Measured amounts of apatite (phosphate rock) and H2SO4 is fed into
digesters, because the reaction is exothermic, the digester must be
cooled. The product is the same “porridge” type mixture as that formed
during super phosphate manufacture.
• The diluted phosphoric acid is separated from the CaSO4, with a
rotating pan vacuum filter. The CaSO4 filter cake is counter currently
washed, to recover more of the acid and the wash water is returned to
the digesters.
• The CaSO4 (gypsum) is a useless by-product that needs to be stored.
The diluted phosphoric acid (10 – 13% P) is concentrated in vacuum
evaporators to ± 25% P, before it is used in the manufacturing of tri-,
super-, and mono-ammonium phosphate.
 2.2.2 Dry Process

• Phosphor metal is produced in an electric oven by the following

reaction:
CaF2.3Ca3(PO4)2 + 9SiO2 + 15C → CaF2 + 9CaOSiO2 + 6P(g) + 15CO(g)
• The silica, combined with the fluorspar in the apatite, forms a layer of
molten slag, which can be tapped from the oven. The phosphor metal is
formed by the reduction of the ore with coke.
• Phosphor vapour and carbon monoxide is extracted from the oven, the
phosphor vapour is condensed at 280oC (in the absence of air and the
CO is used as fuel in the ore preparation.
• The liquid phosphor is oxidized with air to give P2O5 (±40oC).
• The P2O5 is dissolved in water to form phosphoric acid.
4P + 5O2 →2P2O5
P2O5 + 3H2O →2H3PO4
• Phosphoric acid manufactured in this way can be used as soap
phosphates, backing powder, the acid in fizzy drinks, manufacturing of
yeast, medicine in the form of hypophosphates and glyserophophates,
also as a catalyst in petroleum polymerisation and alkylation.
Wet process
2.3. Nitric Acid
• Virtually all HNO3 that is manufactured commercially is obtained
from an Ammonia Oxidation process. This process can be divided
into three major process steps:
1. Oxidation of NH3 to NO (nitric oxide)
2. Oxidation of NO to NO2 (nitric dioxide)
3. Absorption of nitrogen oxides in water to produce HNO3
Oxidation of NH3
• Ammonia is burned (oxidized) with an excess of oxygen over a
catalyst, to form nitric oxide and water. The reaction is extremely
rapid and goes almost to completion.
4NH3 + 5O2 →4NO + 6H2O
Oxidation of NO
• NO undergoes a slow homogeneous reaction with O2 (enough air
must be supplied in the first step to support both the reactions) to
yield NO2. Low temperatures favour the equilibrium of the reaction,
this is accomplished by cooling the product mixture from the first
reaction.
2NO + O2 →2NO2
Absorption of NO2
• The absorption is done with the acid itself, additional air is fed into the
tower oxidize the NO that is formed.
3NO2 + H2O + HNO3 →3HNO3 + NO
• The acid manufactured in this way is used in the fertilizer and
explosives manufacturing industry.
• It is also used in the manufacture if cyclohexanone raw material for
nylon production.
• An example of a specific process for nitric acid is the du Pont
process.
Dupont Process
Du Pont Process
The process consists of the following steps:
• Air is compressed to ±1 MPa, preheated to ± 230oC and mixed with NH3
vapour.
• The mixture, that contain 10% NH3, flows down through a stack of Pt and
rhodium gauze in a converter.
• This produces 95% NO2 at 940oC.
• A steam-superheater, a waste heat boiler and a tail gas preheater cool down
the hot product gas from the converter with the product gas emerging at
200oC.
• The gas enters a cooler-condenser that produces diluted HNO3 (40 – 45%).
• The remaining gas and the acid goes on to the absorber.
• The gas enters at the bottom of the column, the HNO3 part way up the
column and cold water (often steam condensate) at the top.
• As the gas flows up the column counter current to the acid flow, NO2
dissolves in the water forming HNO3.
• Nitric oxide is released and the oxidized with excess oxygen in the spaces
between the trays.
• Dissolved nitrogen oxide needs to be removed from the product acid.
 2.4. Hydrochloric Acid
• HCl is a gas at ordinary temperatures and pressures. An aqueous solution
of it is known as hydrochloric acid.
• Hydrochloric acid is extremely corrosive to most metals and great care must
be taken to choose the proper materials for plant construction when it is
used.
• It is used in the metal, chemical, food and petroleum industries with the
following types of applications:
• Used as a raw material in the production of Polyvinyl chlorides (PVC) and
alkyl chlorides.
• Used as a catalyst in petroleum and organic synthesis
• Used for the pickling of steel (to remove mill scale)
• Hydrochloric acid can be manufactured in any one of the following reactions:
As a by-product in the chlorination of aromatic and aliphatic
hydrocarbons.
C6H6 + Cl2 →C6H5Cl + HCl
From reacting salt with sulphuric acid.
2NaCl + H2SO4 →Na2SO4 + 2HCl
The combustion of hydrogen and chlorine From Hargreaves-type
operations.
Process
• Burning chlorine in hydrogen generates the HCl. (The purity of the
product depends on the purity of the H2 and Cl2. Those produced
during the electrolysis of caustic soda is very pure – Chapter 1)
1. The reaction is highly exothermic and spontaneously goes to
completion as soon as it is initiated.
2. The equilibrium mixture contains 4% by volume free chlorine.
3. As soon as the gasses are cooled the free chlorine and free
hydrogen combine rapidly.
4. By carefully controlling the operating conditions, a gas
containing 99% HCl can be obtained.
5. The acid is manufactured by bubbling the gas though water, into
which it dissolves.