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Chemical Industries

 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

Production of Sulfuric Acid


• There are two methods to produce sulfuric acid
1. Lead-chamber process
 one of the sulfuric acid production method which gives only about 50-60%
concentration of the acid
2. Contact process
 a catalytic method for producing sulfuric acid
in higher concentrations
Lead-chamber Process
 Sulphur is burned with air to produce sulfur dioxide gas in the combustion chamber. Due to
excess air burning, oxygen and nitrogen are present along with sulfur dioxide. By means of
filters, solid particles are filtered leaving out clean gas mixture.
 Now sulfur dioxide is passed from the combustion chamber and will now go through the
Glover’s tower. Glover tower is brick made chamber which are acid resistance. When the hot
sulfur dioxide enter the Glover’s tower, it mixes with nitric oxide(NO) and nitrogen dioxide(NO 2)
 Some of the sulfur dioxide forms a concentrated acid, the Glover acid(about 78% H 2SO4)
 Mixture of gases including sulfur dioxide and trioxide, nitrogen oxides, nitrogen, oxygen and
steam are passed to an air cooler to bring the temperature down which is maintained for the
feed of the lead chambers. A parallel set of lead chambers are setup where the walls and roof of
chamber is fitted with lead sheets. Low pressure steam and filtered water are introduced at the
top of the chamber through spray nozzles. The acid thus formed condenses on the wall and
collected as a chamber acid which is a dilute sulfuric acid.
 The unabsorbed gases from lead chamber are ready to enter the Gay-Lussac’s tower where
dilute concentration HNO3 used to react the upcoming gases of nitrosyl sulfuric acid. The
reaction take place in the tower would be HNO3 + NO.HSO4 → 2NO2 + H2SO4. The oxides of
nitrogen are absorbed by the Glover acid forming nitrosyl sulfuric acid.
Process flow diagram – Lead-chamber Process

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)

Process flow diagram – Contact Process


HYDROCHLORIC ACID
• A monoprotic acid formed by: HCl + H20 H3O+ + Cl-
• A clear, colorless solution of hydrogen chloride (HCl) in water
• It is highly corrosive, strong mineral and is found naturally in gastric acid.
• Has numerous smaller-scale applications, including household cleaning, production of gelatin
and other food additives, descaling, and leather processing.
• About 20 million tonnes of HCl are produced worldwide annually.

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

Preparation of brine and primary purification


• Sodium chloride or salt is fed into the saturator using bucket elevators, where it gets mixed with
water.
• This solution water required concentration goes to precipitation tank where chemicals like
Barium carbonate, sodium carbonate and caustic soda are added to remove sulphates, calcium
and magnesium impurities.
• The solution then goes to the clarifier where the precipitators are allowed to settle.
• The clarified brine is passed through Ansthracite filters. In the filtered brine solution chlorine
content is completely removed by adding bisulphate. Caustic soda is also added to make the pH
in between 8.5-9.5. Brine is to be admitted to the secondary purification system only after the
desired purity level is attained.

Secondary brine purification


• The system consists of four ion exchange filters. The primary purified brine is passed through
the ion exchange filters where it undergoes on Exchange process.
• Ion exchange materials are insoluble acids and bases, which when converted to salt remains
insoluble.
• The most popular ion exchange materials are synthetic organic polymers. These ion exchange
materials are used in columns in which the solution containing ionic impurities like calcium and
magnesium.
• These impurities come in contact with the resin usually through downward flow through the
resin bed. The saturated resin is then regenerated to its original state by using acid and alkali
solution. The regenerated resin is then reused. The purity of the feed brine in the membrane
cell process affects the performance and life of the membrane.

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.

Hydrochloric acid production


• The unit consists of the HCl synthesis unit, Steam Ejector, HCl Collecting Tank. The synthesis of
HCl is performed by combustion of H2 and Cl2 gas. Both the reaction and absorption heat in
water are highly exothermic. The reaction is;
½ H2 + ½ Cl2 →HCl (g) ∆ ¿ + 1667 kJ/mol
• For optimum combustion and low free chlorine content in acid, the gases are burnt with about
10% excess volume flow of hydrogen and the content of free chlorine can so be reduced. The
HCl gas which contains inerts and the previously mentioned excess of hydrogen is absorbed in
de-mineralized water in the falling film absorber to produce hydrochloric acid of max.33% w/w.
• The acid flows by gravity to the HCl Collecting Tank. The unabsorbed gas from the oven is sent
to the secondary absorption and the remaining HCl gas is absorbed in counter flow to the de-
mineralized water.
• The heat generated during the combustion and absorption is eliminated from the jacket cooled
graphite blocks by cooling water. The de-mineralized water, which is used for the absorption of
the HCl gas, is fed to the top of the oven from where it flows by gravity via the pickings to the
falling film absorber of the synthesis.
• The quantity is controlled according to the concentration of the produced hydrochloric acid and
assures constant quality over the full load range of the unit.

Design Features of HCL synthesis furnace


• The construction material of the HCl Furnace is Diabon, which is an impregnated graphite
material and it consists of a combustion chamber and a graphite burner, and a isothermal falling
film absorber, which are built as an integral part of the wall of the combustion chamber.
• Absorber and combustion chamber are incorporated in a steel shell. It serves as a cooling jacket.
That unit is protected with a diabon bursting disc due to over-pressure (max. 1.3 bars) initiate
the discharge of the hydrogen chloride vapors at the top of the unit.
• Rupture disc absorbs explosions and the steel shell will resist to even more violent explosions.
The unit is connected to the cooling water circulation system. The maximum allowable cooling
water pressure is 0.4 bars.

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.

The Chlorination of Organic Chemicals or as a Byproduct in the Manufacture of Organic


Chemicals
• The majority of hydrochloric acid produced today (greater than 90%) is a by-product from the
manufacturing of organic compounds. The particular types of compounds that hydrochloric acid
is actually recovered from during manufacturing are known as organochlorine compounds.
• The largest volume production of hydrochloric acid is a by-product of the formation of
chlorinated and fluorinated organic compounds, chloroacetic acid, and PVC. These production
processes very often also consume large quantities of HCl
• In the chemical reactions, hydrogen atoms are replaced by chlorine atoms, whereupon the
released hydrogen atom recombines with the spare atom from the chlorine molecule, forming
hydrogen chloride. Fluorination is a subsequent chlorine-replacement reaction, producing again
hydrogen chloride.
R-H + Cl2→ R-Cl + HCl
R-Cl + HF → R-F + HCl
• The resulting hydrogen chloride gas is either reused directly, or absorbed in water, resulting in
hydrochloric acid of various grades. The HCl resulting from these processes is most commonly
referred to as co-product or by-product acid.
The Salt-Sulfuric Acid Production (Manheim Process)
• The Mannheim process is an important method for the manufacture of hydrogen
chloride and sodium sulfate from sodium chloride (table salt) and sulfuric acid in which case the
Na2SO4 is known as salt cake:
2 NaCl + H2SO4 → Na2SO4 + 2 HCl
By Reacting Salt, Sulfur Dioxide, Oxygen, and Water (Hargreaves Process)
• The Hargreaves process was once a popular process for making potassium sulphate. It is still
used today (sometimes).
• Potassium chloride is reacted with concentrated sulphuric acid to give potassium sulphate and
hydrogen chloride. This reaction takes place spontaneously because sulphuric acid is a stronger
acid than hydrochloric, so it displaces hydrogen chloride from the salt.
The Combination of Hydrogen and Chlorine or Burning of Chlorine with Hydrogen Gas (Direct Synthesis)
• The large scale production of hydrochloric acid, as a desired primary finished product, is almost
always integrated in a large scale chlor-alkali facility. In the chlor-alkali industry, salt solution is
electrolyzed producing chlorine (Cl2), sodium hydroxide, and hydrogen (H2). The pure chlorine
gas can be re-combined with the hydrogen gas, forming hydrogen chloride gas.
Cl2 (g)+ H2(g) → 2 HCl
• The reaction takes place in what is commonly referred to as an acid burner. The resulting
hydrogen chloride gas is absorbed in demineralized water, resulting in hydrochloric acid. The
product resulting from this process is often called burner grade HCl.
• It accounts 5-10% of the total product of hydrochloric acid
Emissions and control
• Concentrated hydrochloric acid (fuming hydrochloric acid) forms acidic mists
 Both the mist and the solution have a corrosive effect on human tissue, with the potential to
damage respiratory organs, eyes, skin, and intestines irreversibly. Upon mixing hydrochloric acid
with common oxidizing chemicals, such as sodium hypochlorite (bleach, NaClO) or potassium
permanganate (KMnO4), the toxic gas chlorine is produced.
WASTE TREATMENT
• Due to the corrosive nature of hydrochloric acid, problems can arise in both the handling and
disposal of empty containers. Care must be taken in rinsing drums and drum disposal so as to
avoid any repercussions that could occur. To assist customers in solving this problem, Pressure
Vessel Service uses the mini-bulk system. This system eliminates the use of drums by providing
custom chemical tanks which distribute to the point of use.
AMMONIA AND NITRIC ACID
Ammonia
• Is a colourless, pungent gas composed of nitrogen and hydrogen. It is the simplest stable
compound of these elements and serves as a starting material for the production of many
commercially important nitrogen compounds.

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]

Annual Production of Ammonia


• Ammonia ranks second, to sulfuric acid, as the chemical with the largest tonnage.
• It is being increasingly made in countries which have low cost sources of natural gas and coal
(China and Russia account for ca 40%).
• The largest plants produce about 3000 tonnes a day and there are plans to build plants that
produce 4000-5000 tonnes a day, which would mean that the total world output could be
managed with 100 such units.

Production of Ammonia – Raw Materials


• Ammonia is formed from the reaction of nitrogen with hydrogen.
• The following is an example of production:
STEP 1: CH4(g) + H2O(l) CO(g) + 3H2(g)
STEP 2: CO(g) + H2O(l) CO2(g) + H2(g)
• Carbon dioxide is then removed so the H2 can reaction with nitrogen.

Production of Ammonia – Haber Process


• Ammonia is manufacture using the Haber process, which employs an iron/iron oxide catalyst.
The reaction is exothermic.
N2(g) + 3H2(g) 2NH3(g)
• By using Le Chatelier’s principle you can predict the way in which temperature and pressure will
alter the equilibrium yield of ammonia.
• If the pressure exerted increases the system moves to decrease the pressure by moving the
position of the equilibrium to the side with fewer particles. Therefore increased pressure will
lead to an increase in the amount of ammonia.
• Since the forward reaction is exothermic, the position of equilibrium will lie further to the right
and the equilibrium yield of ammonia will increase at low temperatures.
• The rate of reaction will be faster as the temperature increases, as the pressure increases or if a
catalyst is used.
An ammonia plant in
Western Australia:

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.

Health and Safety


• In gaseous form it is an extreme irritant to the eyes, respiratory system and other parts of the
body.
• Areas need to be well ventilated and safety clothing must be worn.
• Because ammonia is a gas at room temperature, in the event of a spill, it can usually be allowed
to disperse after ensuring safety of people who are downwind.

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“.

Uses of Nitric Acid


• Commonly used in industry and agriculture
• Used in woodworking to ‘age’ wood (in very diluted forms).
• Used as an inexpensive process to identify and assess the purity of gold, particularly in low-
grade alloys.
• Used to etch metals
• Highly used in making fertilizers
• Highly used in the manufacturing of explosives
• It is a component of solid rocket fuels, and acts as an oxidizer
• Used as chemical reagent to identify various other metals

PROCESS FLOW DIAGRAM


Manufacture of nitric acid
Nitric acid production involves two stages:
a) Oxidation of ammonia
b) Absorption of the resulting nitrogen oxides

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.

Absorption of the nitrogen oxides


• The gases are further cooled, to below 315 K.
• Air is added and the gases compressed again (7-12 atm typically). The temperature rises to
around 435 K and necessitates further cooling to about 310 K. The additional compression and
the cooling aid the reactions, moving the following equilibria to the right:

• 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

• Rust inhibitor • Component of home cleaning products


(chelant)
• Food additive
• Soft drinks
• Dentistry
• Proccessed food
• Electrolyte
• Detergents
• Dispersing agent
• Skin care products
• Industrial etchant
• Activated Carbon production
• Fertilizer feedstock
Manufacture of Phosphoric Acid
1. Wet Process
 Used in fertilizer production
2. Thermal Process
 Has much higher purity and is used in the manufacture of high grade chemicals,
pharmaceuticals, detergents, food products, beverages, and other non-fertilizer products.

Wet Process Acid Production


CaF2*Ca3(PO4)2 + 10H2SO4 + 20H2O

6H3PO4 + 10CaSO4*2H2O + 2HF↑

 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.

Emissions and Control


• Gaseous fluorides such as silicon tetrafluoride (SiF4) and hydrogen fluoride (HF)
 Precipitated with the gypsum, Leached out with the phosphoric acid product, Vaporized in the
reactor or evaporator
 Scrubbers

Thermal Process Acid Production


CaF2*3[Ca3(PO4)2] + 15C + 9SiO2

9CaSiO3 + CaF2 + 6P (g) + 15CO (g)
P4 + 5O2 → 2P2O5
2P2O5 + 6H2O → 4H3PO4

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)

Prospects of a Chemical Engineer


• working closely with process chemists and control engineers to ensure the process plant is set
up to provide maximum output levels and efficient running of the production facility
• designing plant and equipment configuration so that they can be readily adapted to suit the
product range and the process technologies involved, taking environmental and economic
aspects into account;
• setting up scale-up and scale-down processes including appropriate changes to equipment
design and configuration;
• assessing options for plant expansion or reconfiguration by developing and testing process
simulation models;
• optimising production by analysing processes and compiling de-bottleneck studies;
• applying new technologies;
• researching new products from trial through to commercialisation and improving product lines;
• ensuring that potential safety issues related to the project operator, the environment, the
process and the product are considered at all stages.
• Examples of work activities in specific sectors include:
• undertaking small and intermediate-scale manufacturing and packaging activities in
pharmaceutical product development for clinical trial purposes;
• developing new methods of safe nuclear energy production, including projects such as
conceptual design, simulation and construction of test rigs, and detailed design and
operations support.
• designing, installing and commissioning new production plants, including monitoring
developments and troubleshooting