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Comprises the companies that produce industrial chemicals. Central to the modern world
economy, it converts raw materials (oil, natural gas, air, water, metals, and minerals) into more
than 70,000 different products.
Sulfuric Acid, Hydrochloric acid, Ammonia & Nitric and others
SULFURIC ACID
• Is a colorless, odorless and highly corrosive strong acid
• Soluble in water at all concentrations
• Sometimes called “oil of vitriol”
History
• 8th Century- Jabir ibn Hayyan(Geber) discovered sulfuric acid by distilling green vitriol
• 9th Century- ibn Zakariya al-Razi (Rhases) obtained the substance by the dry distillation of
minerals
• 17th Century- German-Dutch chemist Johann Glauber prepared H2SO4 by burning sulfur with
KNO3 in the presence of steam.
• 1736- Joshua Ward, a London pharmacist, used Johann’s method to begin the first large-scale
production of sulfuric acid
• 1746- John Roebuck adapted the method in lead-lined chamber producing sulfuric acid with 50-
60% concentration
• 18th Century- French chemist Joseph Louis Gay Lussac and British chemist John Glover
improved Roebuck’s sulfuric acid to 78% concentration
• 1831- British vinegar merchant Peregrine Phillips patented a far more economical process for
producing sulfur trioxide and concentrated sulfuric acid, know as contact process
Uses
• Industrial production of chemicals
-major use of sulfuric acid (60% of total) is used for the production of phosphoric acid and for the
manufacture of phosphate fertilizers using “wet method”. In this method, phosphate rock is used and
100 million tons are processed annually. The raw material fluorapatite (Ca 5F(PO4)3) is treated with 93%
sulfuric acid to produce calcium sulfate(CaSO4), hydrogen fluoride(HF) and phosphoric acid(H3PO4).
Ca5F(PO4)3 + 5 H2SO4 + 10 H2O → 5 CaSO4 • 2 H2O + HF + 3 H3PO4
-another use of sulfuric acid is for manufacture of aluminum sulfate ( Al 2(SO4)3 ). This can react with
small amounts of soap on paper pulp fibers to give gelatinous aluminum carboxylates which help to
coagulate the pulp fibers into a hard paper surface. It is also used for making aluminum hydroxide
( Al(OH)3 ), which is used at water treatments to filter out impurities as well as to improve the taste of
the water. Al2(SO4)3 is made by reacting bauxite ( AlO(OH) ) with H2SO4.
2 AlO(OH) + 3 H2SO4 → Al2(SO4)3 + 4 H2O
• Industrial cleaning agent
-the acid is used in pickling which is a surface treatment used to remove impurities such as stains,
inorganic contaminants, rust or scale from ferrous metals, copper and aluminum alloys
• Fertilizers
-sulfuric acid is used as a dehydrating agent to prevent the soil from over hydrating, thus the plant will
be able to survive
• Catalyst
-sulfuric acid is the usual acid catalyst for the conversion of cyclohexanone oxime to caprolactam, used
for making nylon. It is also used in petroleum refining, it acts as the catalyst for the reaction of
isobutene with isobutylene to give isooctane, a compound that raises the octane rating of gasoline
• Fertilizers
-sulfuric acid is used as a dehydrating agent to prevent the soil from over hydrating, thus the plant will
be able to survive
• Electrolyte
-sulfuric acid acts as the electrolyte in lead-acid (car)batteries
Contact Process
Sulfur is burned in air to produce sulfur dioxide gas in a furnace.
S(s) + O2(g) SO2(g)
Sulfur dioxide is oxidized to sulphur trioxide in the presence of the catalyst vanadium pentoxide
(V2O5)
2 SO2(g) + O2(g) 2 SO3(g)
Sulfur trioxide is treated with water to produce sulfuric acid in a very high concentration but
when SO3 is directly dissolved in water, the reaction is highly exothermic and it will generated
mists instead of a liquid
So, sulfur trioxide gas is dissolved in a very concentrated sulphuric acid (about 98%
concentration of acid in water) producing a thick fuming liquid called oleum.
3 H2SO4(l) + SO3 → H2S2O7(l)
Oleum is then reacted with water to form concentrated H2SO4
4 H2S2O7(l) + H2O(l) → 2 H2SO4(l)
History
• 15th century, it was historically called acidum salis, muriatic acid and spirits of salt because it
was produced by Valentinus from rock salt and green vitriol (Iron II Sulfate).
• It first appeared during the Renaissance, then it was used by chemists such as Glauber, Priestly
and Davy in their research.
• Industrial Revolution, it is then used in the chemical industry as chemical reagent in the large-
scale production of vinyl chloride for PVC plastics and MDI/TDI for polyurethane.
• Industrial Revolution, demand for alkaline substances increased. A new industrial process by
Nicolas Leblanc enabled cheap large-scale production of sodium carbonate (soda ash).
Hydrogen chloride is released as by-product.
• British Alkali Act of 1863, soda ash producers were obliged to absorb the waste gas in water,
producing HCl.
• Leblanc process was replaced by the Solvay process w/o HCl as by-product.
• Since 1988, HCl has been listed as a precursor under the UN Convention Against Illicit Traffic in
Narcotic Drugs and Psychotropic Substances.
Applications
• Pickling of Steel, Fe2O3 + Fe + 6HCl 3FeCl2 + 3H2O
• Production of Organic Compounds, such as vinyl chloride and dicholoroethane for PVC,
polycarbonate, activated carbon, and numerous pharmaceutical products.
• pH Control and Neutralization
Process Flow
Methods of Preparation
• The chlorination of organic chemical or as by-product in the manufacture of organic chemicals.
• The Salt-Sulfuric Acid Production. (Manheim Process)
2NaCl + H2SO4 Na2SO4 + 2HCl
• By reacting salt, sulfuric dioxide, oxygen, and water. (Hargreaves Process)
• The combination of hydrogen and chlorine or burning of chlorine with hydrogen gas. (Direct
Synthesis)*
Industrial Preparation
Preparation of brine
Secondary brine
and primary
purification
purification
Hydrochloric Acid
Electrolysis
Production
Electrolysis
• The secondary purified brine is fed to brine head tank after cooling and is admitted to
electrolysis. Demineralized water is also admitted to the electrolysis.
• Direct current (DC) supply is connected to the anode and cathode and the current is applied to
the electrolyzed. During electrolysis, 32% concentration caustic soda is produced at the
cathode.
• Hydrogen gas is also formed at the cathode chamber and Chlorine formed at anode. Chlorine is
pumped into storage tank, hydrogen and chlorine gas goes to their respective treatment
sections.
Manufacturing
• Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride gas.
Hydrogen chloride can be generated in many ways, and thus several precursors to hydrochloric
acid exist. The large-scale production of hydrochloric acid is almost always integrated with the
industrial scale production of other chemicals.
• Hydrochloric acid is produced in the United States primarily by four basic methods:
the chlorination of organic chemicals
the combination of hydrogen and chlorine
the salt-sulfuric acid production process
as a co-product in the manufacture of silica.
Brief History
• 1774 -Ammonia was first obtained in pure form in 1774 by an English chemist Joseph Priestley.
• 1784 –A French chemist Claude Louis Berthollet decomposed ammonia into elements with the
help of electric discharge and thus identified the composition of this gas.
• 1787 -Ammonia received its official name as "ammoniac" in from the Latin name of ammonium
chloride - sal ammoniac; because that salt was obtained near the temple of Egyptian god Amon.
• 1801 -The abbreviated Russian name "ammiak" was introduced by Russian chemist Yakov
Dmitrievich Zakharov who was the first to develop the Russian chemical nomenclature system.
• 1864 -Solutions of sodium and potassium in liquid ammonia were obtained for the first time.
Uses of Ammonia
• For production of synthetic fibres
• For cleaning and dyeing of cotton, wool and silk
• For neutralization of acidic wastes, and in natural rubber production
• In soda production by Solve method
• For nitride hardening – saturation of surface layers of steel with nitrogen
• Medics use ammonia water solutions (ammonia spirit) in everyday practice: a piece of cotton
wool moistened in salt ammoniac brings the person out of a fainting fit.
• For production of nitric acid
• For production of fertilizers
• For production of various ammonium salts, urea, urotropine
• As a cheap cooling agent in industrial refrigerating plants
• Plants needs ammonia to make protein and other growth compounds, however, most plants
cannot use the N2 gas directly from the atmosphere.
• For explosives [NH4NO3]
• For pharmaceuticals [sulfonamides]
1 Desulfurization units
2 Primary reformer
3 High temperature and
low temperature shift
reactors
4 Carbon dioxide
absorber
5 Carbon dioxide
stripper (recovery of the
pure solvent,
ethanolamine)
6 Ammonia converter
7 Ammonia storage as
liquid
8 Pipeline to the
ship for export
Process Flow Diagram
Waste Management
• The Haber process maximises the conversion of nitrogen and hydrogen into ammonia by
recycling unreacted gases back into the converter for further passes over the catalyst.
• In this way, almost complete conversion is achieved.
• Because the hydrogen is recycled, the amount of hydrogen feedstock required from the
hydrogen generation process is reduced.
• Consequently the amount of raw materials, energy and waste materials involved in the
production of the hydrogen used in the Haber process is reduced.
• In some section of the production process, aqueous solutions of ammonia are produced when
gases being released to the atmosphere are purified by passing them through water.
• These solutions can also be used in the manufacture of urea.
NITRIC ACID
• is the result of a number of chemical reactions that produce a colorless corrosive and toxic
mineral acid which tends to have a yellow color when stored for any length of time, due to an
accumulation of nitric oxides. HNO3 stands for one hydrogen atom, one nitrogen atom, and
three Oxygen atoms.
Brief History
• Nitric Acid has been called Aqua Regina, which is Latin meaning "royal water", by ancient
scientists and chemists who first discovered it.
• Jabir ibn Hayyan-
The first known person to write a decription and discuss their method of sythesizing nitric acid
• Johann Rudolf Glauber was the first to make the compound Nitric Acid, with the distillation of
salt peter and sulfuric acid. The compound that he created, was later named "Glaubers Salt“.
Oxidation of ammonia
• This part of the process involves the oxidation of ammonia to nitrogen monoxide (nitric oxide):
• The main advantage of the high pressure is that it substantially reduces the size of equipment
and piping required, and hence leads to a reduced capital cost.
• Where possible, the ammonia is made on the same site. It is filtered to remove any impurities
and then mixed with filtered compressed air to give a mixture containing approximately 10%
ammonia and 90% air. The exact proportion of excess air depends on the operating pressure
and temperature of the plant.
• The mixture is then passed through one or more converters in parallel, each containing a series
of 90% platinum/10% rhodium catalyst gauzes in parallel at 975-1225 K - typically 1200 K in
a fixed bed reactor. At least 96% conversion of the ammonia takes place.
• Rhodium is added to the platinum to give the gauze strength and to reduce the loss of platinum,
an important economic factor (0.4 g loss per 1000 kg nitric acid made). This is due to 'hot spots'
occurring on the gauze.
• Recently, it has been found that knitted gauze increases the efficiency of conversion and
prolongs the life of the catalyst.
• Care has to be taken to minimise oxidation of ammonia to nitrogen by the even more
exothermic reaction, favoured by high pressure and an over-heated catalyst:
4NH3(g) + 3O2(g) 2N2(g) + 6H2O(g)
• The hot gases leaving the converters are used either to raise superheated steam or to heat the
exhaust gas from the absorption tower(s). The steam may be used to generate power in a
steam turbine which can then drive the air compressor(s).
• The hot gases leave the steam raising/heat exchange section at about 425 K.
• The gases are then passed through one or more towers to meet a stream of water, normally
flowing in the opposite direction to the gas. Here, oxidation of the nitrogen monoxide
continues and absorption occurs with the formation of nitric acid:
PHOSPORIC ACID
aka orthophosphoric acid or phosphoric(V) acid
An essential plant nutrient and is taken up by plant roots, usually as the
dihydrogenphosphate ion, H2PO4-, derived from phosphoric acid, H3PO4. The
manufacture of fertilizers that are used to rectify phosphorus deficiencies in soils
depends on the availability of supplies of phosphoric acid
is a mineral (inorganic) acid having the chemical formula H3PO4
History
200 BC- Phosphate containing materials used by the Incas of Peru (guano and bird droppings).
American Indians used fish and bones as source of fertilizer
1669- Hennig Brand was a merchant and alchemist in Hamburg, Germany who discovered
phosphorus
1770- Phosphoric acid was discovered by K. W. Scheele and J. G. Gahn in bone ash
1774- Scheele isolated phosphorus from bone ash
1777- Scheele produced phosphoric acid by the action of nitric acid on phosphorus
1840- The initial interest in manufacturing phosphoric acid for fertilizers probably seems from
Justus Von Liebig's significant book: Organic Chemistry in its Application to Agriculture and
Physiology
1842- John Bennet Lawes was agricultural scientist patented a manure formed by treating
phosphates with sulphuric acid
1872- Coignet & Cie concentrated on making superphosphates from bonemeal as well as copper
phosphate, phosphoric acid and phosphate of soda
1897- A process was developed by Stauffer Chemical Company for acidulating bones from the
Chicago stockyards to make acid for use in the manufacture of calcium leavening agents
1955- Albright and Wilson took over the Marchon Chemical Company which produced
phosphorus-based detergents by the "wet" process
Uses
Phosphorus rock called flourapatite or apatite (raw material) is dried, crushed and then
continuously fed into the reactor along with sulfuric acid
93 percent Sulfuric acid is used to make the strongest phosphoric acid possible and to decrease
evaporation costs
Calcium Sulfate or gypsum is precipitated and separated from the acid by filtration. It must be
washed thoroughly to yield at least a 99 percent recovery of the filtered phosphoric acid. After
washing, the slurried gypsum is pumped into a gypsum pond for storage.
Water is syphoned off and recycled through a surge cooling pond to the phosphoric acid
process.
Considerable heat is generated in the reactor. In older plants, this heat was removed by blowing
air over the hot slurry surface. Modern plants vacuum flash cool a portion of the slurry, and
then recycle it back into the reactor.
Wet process normally contains 26 to 30 percent P2O5. The acid is usually concentrated to 40 to
55 percent P2O5 by using 2 or 3 vacuum evaporators.
Raw materials:
Elemental Phosphorus (yellow)
air
Water
3 Major steps:
1. Combustion
the liquid elemental phosphorus is burned (oxidized) in ambient air in a combustion chamber at
temperatures of 1650 to 2760°C (3000 to 5000°F) to form phosphorus pentoxide.
2. Hydration
The phosphorus pentoxide is then hydrated with dilute H3PO4 or water to produce strong
phosphoric acid liquid (Reaction 3).
3. Demisting
Removes the phosphoric acid mist from the combustion gas stream before release to the
atmosphere. This is usually done with high-pressure drop demistors.
Concentration of H3PO4 produced from thermal process normally ranges from 75 to 85 percent.
This high concentration is required for high grade chemical production and other non-fertilizer
product manufacturing. Efficient plants recover about 99.9 percent of the elemental
phosphorus burned as phosphoric acid.
•Phosphoric acid mist (H3PO4) contained in the gas stream from the hydrator
Venturi scrubbers, cyclonic separators with wire mesh mist eliminators, fiber mist eliminators,
high energy wire mesh contractors, and electrostatic precipitators (ESP)