CHEMICAL TECHNOLOGY-V SEM

MODULE-II

MANUFACTURING OF ACIDS
&
FERTILIZERS
CHEMICAL TECHNOLOGY-V SEM

CONTENTS
ACIDS
1. SULPHURIC ACID (DCDA PROCESS)
2. NITRIC ACID
3. PHOSPHORIC ACID (WET PROCESS)
FERTILIZERS
4. AMMONIA
5. UREA
6. SUPERPHOSPHATE (SSP, TSP)
7. AMMONIUM SULPHATE
 PRODUCTION OF SULFURIC ACID (DCDA POCESS)

Almost all sulfuric acid is manufactured by the contact process.

Pure 100% H2S04

Mol. Wt. - 98.08
M.P. - 10.50 C
B.P. - 3370 C
Density - 1.840 gm/mL (liquid)
Solubility - Miscible with water in all proportions
Viscosity - 26.7 cP (2000C)

SO3 soluble in H2SO4 to give varying percentage of oleum.

Raw materials
▫ Sulfur
▫ Pyrites
▫ CuS ,ZnS, PbS, MoS2
▫ H2S Sources
▫ Sulfur source

Chemical reactions

Three Step Process

1) S + O2 SO2 ΔH = - 71.2 kcals
2) SO2 + ½ O2 SO3 ΔH = - 46.3 kcals
3) SO3 + H2O H2SO4 ΔH = - 31.1 kcals
Sources of raw material

The sources of sulfur and sulfur dioxide are as follows

• Sulfur from mines
• Sulfur or hydrogen sulfide recovered from petroleum desulfurization
• Recovery of sulfur dioxide from coal or oil-burning public utility stack gases
• Recovery of sulfur dioxide from the smelting of metal sulfide ores
2PbS + 3O2 2PbO + 2SO2
• Isolation of SO2 from pyrite
Process

• The process can be divided into five stages:

• combining of sulfur and oxygen
• purifying sulfur dioxide in the purification unit
• adding excess of oxygen to sulfur dioxide in presence of catalyst vanadium
pentoxide, with temperatures of 450 °C and pressure of 1-2 atm
• sulfur trioxide formed is added to sulfuric acid which gives rise to oleum
(disulfuric acid)
• the oleum then is added to water to form sulfuric acid which is very
concentrated.
 Oxidation of Sulfur

Process:
• Air drying tower with acid
• Sulfur is injected into burner
• Reaction Temperature 2000°F
• Exothermic reaction must be cooled
• Steam recovered
Kinetic Effects:
• Oxidation of sulfur dioxide is slow and reversible
• The reaction requires a catalyst and 426.7°C temperatures
▫ The reaction is exothermic and sensitive to excessive heat
• Equilibrium Constant (The degree at which the reaction proceeds is temp.
dependent)
Purification unit

• This includes the dusting tower, cooling pipes, washing tower, drying
tower, arsenic purifier and testing box. Sulfur dioxide has many impurities
such as vapours, dust particles and arsenous oxide. Therefore, it must be
purified to avoid catalyst poisoning . In this process, the gas is washed
with water, and dried by sulfuric acid. In the dusting tower, the sulfur
dioxide is exposed to a steam which removes the dust particles. After the
gas is cooled, the sulfur dioxide enters the washing tower where it is
sprayed by water to remove any soluble impurities.
• In the drying tower sulfuric acid is sprayed on the gas to remove the
moisture from it. Finally, arsenic oxide is removed when the gas is
exposed to ferric hydroxide.
Overall flow chart
Oxidation of Sulfur
1) S + O2 SO2

Sulfur
Steam

10-12% SO2
Water
Air

93% H2SO4 Process:

- Air drying tower with acid

Primary Generation of SO2 - Sulfur is injected into burner

-79% Combustion of Sulfur - Reaction Temperature 2000°F
-9% Recovery from Metallurgic Processes - Exothermic reaction must be cooled
- 5% Regeneration of Spent Acids - Steam recovered
Oxidation of Sulfur Dioxide

SO2 Gas
Contact Process:
-Vanadium pentoxide catalyst
Gas
- Exothermic Reaction Cooling

- 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 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

Gas
Cooling

SO3 Gas

SO3 Gas 93% H2SO4

Temperature Profile

SO2 Gas SO2 Gas

Gas
Cooling

SO3 Gas
510 C
75 C
430 C
200 C

SO3 Gas 93% H2SO4

125 C
DCDA

• The next step to the Contact Process is DCDA or Double Contact Double
Absorption. In this process the product gases (SO2) and (SO3) are passed
through absorption towers twice to achieve further absorption and
conversion of SO2 to SO3 and production of higher grade sulfuric acid.
• SO2-rich gases enter the catalytic converter, usually a tower with multiple
catalyst beds, and are converted to SO3, achieving the first stage of
conversion. The exit gases from this stage contain both SO2 and SO3 which
are passed through intermediate absorption tower
• where sulfuric acid is trickled down packed columns and SO3 reacts with
water increasing the sulfuric acid concentration. Though SO2 too passes
through the tower it is unreactive and comes out of the absorption tower.
• This stream of gas containing SO2, after necessary cooling is passed
through the catalytic converter bed column again achieving up to 99.8%
conversion of SO2 to SO3 and the gases are again passed through the final
absorption column thus resulting not only achieving high conversion
efficiency for SO2 but also enabling production of higher concentration of
sulfuric acid.
• The industrial production of sulfuric acid involves proper control of
temperatures and flow rates of the gases as both the conversion
efficiency and absorption are dependent on these.
• 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.
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.
• Oleum is used in reactions where water is excluded
• SO3 + H2SO4 H2S2O7 (disulfuric acid)
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
Comparison of vanadium and platinum catalyst

Aspect Vanadium catalyst Platinum catalyst

Conversion Higher Lower and decrease
with use
Investment Initially less, 5% High, Lower life and
replacement is highly fragile
required per year Catalyst
poisoning Relatively immune to Poisoned, especially by
poison arsenic
Handling of SO2 Less (7-8 %) High (8-10 %)
Requirement per 1000 14 kg catalyst mass 189 gms
kg containing 7-8 % V2O5
(100% acid)/day
Uses

• The largest single use is in the fertilizer industry.

• Mostly in production of phosphoric acid, which in turn used to manufacture
fertilizers such as triple superphosphate, mono and diammonium phosphates.
• Used for producing superphosphate and ammonium sulfate.
• Used as an acidic dehydrating reaction medium in organic chemical and
petrochemical processes
• In the inorganic chemical industry
• In the metal processing industry
• Certain wood pulping processes in the paper industry require sulfuric acid,
used in textile and chemical fiber processes and leather tanning
• In manufacture of explosives, detergents and plastics
• In production of dyes, pharmaceuticals
PRODUCTION OF NITRIC ACID (OSTWALD POCESS)
Properties of Nitric Acid

Properties

Molecular formula HNO3

Molar mass 63.01 g mol−1

Appearance Colorless liquid

Density 1.5129 g cm−3

Melting point -42 °C, 231 K, -44 °F

Boiling point 83 °C, 356 K, 181 °F (68% solution boils

at 121 °C)
Solubility in water Completely miscible
Acidity (pKa) -1.4

Refractive index (nD) 1.397 (16.5 °C)

Dipole moment 2.17 ± 0.02 D

Methods of Production

1. Ammonia oxidation process(Ostwald process)

2. NaNO3  H 2 SO4 Process (CHILLI-SALT PETER's METHOD)
3. N 2 Fixation from air (Wisconsin process)
4. Nitrogen fixation by nuclear fission fragments.

Raw materials

• N 2 from synthesis Ammonia process

• Filtered air
• Platinum –Rhodium make up catalyst
• Water
Reactions involved in the Ostwald’s process

Main reactions
1. Oxidation of NH3 to NO
NH3 + 5/4O2 NO + 3/4H2O ∆H= -54Kcal

2. Oxidation of NO to NO2
2NO + O2 2 NO2 ∆H= -27.2Kcal
3. Absorption of NO2 in water
2NO2 + H2O HNO3 + HNO2
4. Concentration of HNO3
Side reactions
NH3 + 3/4O2 1/2N2 + 3/2H2O ∆H =-75.7Kcal
NH3 1/2 N2 + 3/2H2

NH3 + O2 1/2N2 O + 3/2H2O

NH3 + 3/2NO 5/4N2 + 3/2H2O ∆H= -107.9Kcal

Process flow sheet
Process description

• Compressed air is mixed with anhydrous ammonia, fed to a shell and tube
converter designed so that the preheater and a steam heat recovery
boiler-superheater are within the same reactor shell.
• The converter section consists of 10-30 sheets of Pt-Rh alloy in the form of
60-80 mesh wire gauge packed in layers inside the tube.
• Gas passes downward with a velocity designed to give a contact time of
about 2.5  10 4 sec in the catalyst zone at 8000C.
• Product gases from the reactor, containing 10-12 % NO, are sent trough
heat recovery units, a quench unit for rapid cooling to remove a large
fraction of the product heat , and into the oxidizer- absorber system.
• Air is added to convert NO to NO2 at the more favourable low temperature
(40-500C) environment of the absorption system.
 • The equipment in the absorption train may be a series of packed or sieve
tray vertical towers or a series of horizontal cascade absorbers.
• The product from the absorption system is 57-60 % HNO3 solution which can
be sold as is or with different concentrations.
• Concentrated of nitric acid to 95% can be done by one several methods,
1. Concentration by H2SO4
2. Concentration by Mg(NO3)2
• Advantages of Mg(NO3)2 process are:-
1. Operating costs about behalf of those encountered with H2SO4
concentration.
2. Capital requirements are only 70% as great.
3. Acid quality and yield is improved.
Platinum-Rhodium catalyst

Properties of platinum

Atomic number:- 78, Atomic weight:-195.09 g./mol

Density:-21.45 gm/cm3, Melting point:-1769°C

Boiling point:- 3827°C, Thermal conductivity :-73 Watt/meter/°c

Tensile strength:- 14kg/mm2

Chemical properties

1. It has the third highest density behind osmium and iridium.

2. Platinum is unaffected by air and water but will dissolve in hot aqua regia,

in hot concentrated Phosphoric and Sulphuric acid in the molten alkali.

3. It is as resistant as gold to corrosion and tarnishing. Indeed, platinum will

not oxidize in air no matter how strongly it is heated.

Pt-Rh catalysts used
in Ostwald process
Hot Pt wire
over NH3 solution
Properties of Rhodium
Rhodium:- is silver white metal
Melting point:-1966°C
Boiling point:-4500°C
Density:- 12.41 gm/cm3
Special properties
High electrical and Heat conductivity. That means heat and electricity
pass through rhodium easily
Chemical properties
Is relatively in active metal. It is not attacked by the strong acids. When
heated in air, it is combined slowly with O2.
Major Engineering Problem

• Plants should be operated at low or atmospheric pressure

• Alloying platinum with rhodium
• To form NO should be at high temperature
The reasons for elevated pressure are:-
1. High reaction rates and lower volumes in both oxidation and absorption
equipment
2. Higher acid strength
3. Lower investments costs
The disadvantages of higher pressures:-
1. Lower oxidation yields
2. Higher catalyst losses unless good filtering procedures are used
3. Higher power requirements if power recovery units are not specified.
Uses of nitric acid

• Nitric acid plays a significant role in the manufacture of various products

such as:
▫ Explosives like trinitrotoluene (T.N.T.) nitro glycerine, cotton etc.
▫ Fertilizers such as calcium nitrate, etc.
▫ Dyes, perfumes, etc. from coal tar products.
• It is used in the purification of silver, gold, platinum etc.
• Nitric acid is used in etching designs on copper, brass, bronze ware etc.
• It is used as a laboratory reagent.
Nitric acid General information

• Non-flammable under normal conditions, but may ignite other flammable

materials .
• Highly reactive.
• Releases toxic and irritating fumes when heated In the event of fire
involving nitric acid, use fine water spray and liquid-tight chemical
protective suit with breathing apparatus .
• Gas-tight protective suits with breathing apparatus are required for
fuming nitric acid.
• Exposure can occur through ingestion, inhalation, or absorption through
the skin or eyes.
• Short-term inhalation may result in a dry throat and nasal passages,
cough, chest pain, shortness of breath, headache and difficulty breathing.
• Long-term inhalation may lead to the development of lung diseases.
• Short-term ingestion can cause burns to the lips, tongue, mouth, throat
and stomach.
• Swelling of the airways can cause difficulty breathing .
• Nitric acid or nitric acid solutions are not considered to cause cancer .
Manufacturing Process of H3PO4

Wet Process (Strong acid)

Thermal Process (Strong acid)

Electric Furnace Reduction Process

The modern manufacturing methods of phosphoric acid are following:

1. Using phosphate rock and blast furnace
2. Using phosphate rock and electric furnace
3. Oxidation and hydration of phosphorous
4. Wet process or from sulfuric acid and phosphate rock
Manufacturing Process of H3PO4 (wet process)

Wet Process (Strong acid):

• The wet process is according to the acids (sulfuric acid, nitric acid or
hydrochloric acid) used to decompose the phosphate rock.
• The process using sulfuric acid is the most common among all particularly
for producing fertilizer grade phosphoric acid.
• The wet process phosphoric acid, also called as green acid.
• Depending upon the hydrate forms of calcium sulfate produced during the
wet process, it is classified as anhydrate, hemi hydrate and dihydrate.
• The hydrate form is controlled mainly by temperature and acid
concentration.
Properties:

 Phosphoric Acid:
• Molecular formula : H3PO4
• Molecular weight : 98 gm/mole
• Melting point : 42.4ºC
• Boiling point : 213ºC
Raw Materials:

• The high grade of imported ore is necessary to avoid solubilization of

mined rock impurities such as aluminium, silicon, iron oxide, and alkali
minerals.

• The only other raw material required is strong sulphuric acid which comes
from a contact sulphuric acid plant located at or near the phosphoric acid
plant.
Chemical Reaction:

• Ca10F2(PO4)6 + 10H2SO4 + 10nH2O → 10CaSO4.nH2O + 2HF + 6H3PO4

phosphoric acid today is produced from phosphatic ores mined in various

parts of the world. The phosphate minerals in both types of ore are of the
apatite group, of which the most
Fluorapatite Ca10(PO4)6(F,OH)2
Francolite Ca10(PO4)6–x(CO3)x(F,OH)2+x
Fluorapatite predominates in igneous phosphate rocks and francolite
predominates in sedimentary phosphate rocks.

• Anhydrate CaSO4
• Hemi hydrate CaSO4.1/2H2O
• Dihydrate CaSO4.2H2O
Quantitative requirements:

 Basis:
• 1 ton of phosphoric acid (100%)
• Phosphate rock(32% P2O5) = 2.5 tons
• Sulfuric acid(93-98%) = 2 tons
 Plant capacity:
• 100-150 tons/day of 100% H3PO4
Flow Sheet:
Process Description:

• Sulfuric acid on reaction with phosphate rock along with precipitation of

calcium sulfate results into the formation of phosphoric acid.
• The process is simple and requires grinding of phosphate rock reacting
with dilute phosphoric acid.
• so that, melt is produced which in a reactor is mixed with concentrated
sulfuric acid for 4 to 8 hrs in the temperature range of 75-80°C.
• Lot of air is required to control the temperature.
• The gypsum-phosphoric acid slurry goes to a travelling pan vacuum filter
where the 40% acid is removed and the cake washes the water.
• The gypsum can either be dried for use in plaster, paints, and cements, or
reacted with ammonium carbonates to give ammonium sulphate and
calcium carbonate.
• Resulting gases includes HF and P2O5 which in the absorption tower is
separated and finally treated to give fluorosilicates and dilute phosphoric
acid.
• The main product in the liquid form which is phosphoric acid and calcium
sulfate is filtered and washed.
• The dilute acid is concentrated in a single effect evaporator to any grades
>50% acid.
• gypsum and phosphoric acid are separated and after minor purification
the phosphoric acid is concentrated into the evaporator.
• Throughout the plant, corrosion resistant materials of construction must
be used. The most common ones are structural carbon or nickel alloy for
evaporator heat exchangers; rubber or carbon-brick for reactor linings;
polyester-fiber glass in pipes, ducts, and small vessels. Yield of phosphoric
acid based on phosphorus content of raw material is 95% .
Major Engg. Problems:

 Process design:
• Fineness of grind
• Temperature
• Control of sulphuric acid
 Material of construction:
• Reaction tank constructed of steel and lined with acid-proof brick.
• All air vent systems are PVC coated steel.
• Storage tanks of rubber-lined steel.
Uses:

• Used for preparation of hydrogen halides

• Used as a "rust converter”.

• Food-grade phosphoric acid is used to acidify foods and beverages such as

various colas.

• Used in many teeth whiteners to eliminate plaque.

• As a chemical oxidizing agent for activated carbon production

• As a cleaner by construction trades to remove mineral deposits,

cementitious smears, and hard water stains.

• As a pH adjuster in cosmetics and skin-care products.

• As a dispersing agent in detergents and leather treatment.

PRODUCTION OF ACETIC ACID
 Acetic acid, CH3COOH is an organic compound which also written as
CH3CO2H or C2H4O2.

• It is a colourless liquid in undiluted form is called as glacial acetic acid.

•Andreas Libavius in the sixteenth century described a procedure for

preparation of glacial acetic acid through the dry distillation of certain metal
acetates like copper (II) acetate and compared the produced glacial acetic
acid with vinegar.

 The presence of water in vinegar has such a profound effect on acetic acid's
properties that for centuries chemists believed that glacial acetic acid and the
acid found in vinegar were two different substances.
MANUFACTURE

Acetic acid can be manufactured by following methods

1. Methanol carbonylation
2. Acetaldehyde oxidation
3. Ethylene oxidation
4. Oxidative fermentation
5. Anaerobic fermentation
Methanol carbonylation

Raw material

Basis: 1000 kg acetic acid by methanol Carbonylation (95 % yield)

Methanol 510 kg
Carbon monoxide 445 kg

Reaction

CH3OH + CO CH3COOH
FLOW DIAGRAM OF ACETIC ACID
PROCESS FLOW DIAGRAM OF ACETIC ACID
Manufacture process

• Rhodium catalyzed carbonylation of methanol is carried out in presence of

iodine as activator.
• Methanol and carbon monoxide were charged into carbonylation reactor at
partial pressure between 10 – 15 bar while the temperature is maintained at
1750C.
• The exhaust gas from the reactor is coming out from the top and introduced
into gas scrubber where gases coming out from purification section are also
scrubbed using methanol and then recycle to reactor.
• Reactor used in carbonylation of methanol is bubble column reactor.
• This reactor provides excellent mass and heat transfer.
• In this reactor gas is sparged from the bottom of the reactor.
• Design of the sparger controls the bubble size distribution in the column.
• While remaining mixture from the reactor is heated in flash tank where
vapour is transferred to crude column for distillation while liquid coming
out from bottom is recycled to reactor.
• In crude acetic acid column, light end are vaporized and send to light
ends column where they are removed.
• Liquid coming out from bottom is again heated in flash tank and acetic
acid - water mixture is taken out from side cut and charged in to
dehydration column where methanol is introduced.
• After dehydration, liquid mixture from bottom of column is charged into
acetic acid column where acetic acid is obtained as product.
• Waste acid are removed using stripping operation.
Oxidative fermentation by Monsanto process

• Given sufficient oxygen, these bacteria can produce vinegar from a

variety of alcoholic foodstuffs. Commonly used feeds include apple
cider, wine, and fermented grain, malt, rice, or potato mashes. The
overall chemical reaction facilitated by these bacteria is:

C2H5OH + O2 → CH3COOH + H2O

A dilute alcohol solution inoculated with Acetobacter and kept in a

warm, airy place will become vinegar over the course of a few months.
Industrial vinegar-making methods accelerate this process by improving
the supply of oxygen to the bacteria.
• One of the first modern commercial processes was the "fast method"
or "German method", first practiced in Germany in 1823. In this
process, fermentation takes place in a tower packed with wood
shavings or charcoal. The alcohol-containing feed is trickled into the
top of the tower, and fresh air supplied from the bottom by either
natural or forced convection. The improved air supply in this process
cut the time to prepare vinegar from months to weeks.

• The production of acetic acid by the Monsanto process utilises a

rhodium catalyst and operates at a pressure of 30 to 60 atmospheres
and at temperatures of 150 to 200°C. The process gives selectivity of
over 99 per cent for the major feed-stock ethanol
The major units comprising a commercial-scale Monsanto methanol operating plant,
which uses a rhodium based catalyst. The technology uses three distillation
columns to sequentially remove low boilers (methyl iodide and ethyl acetate).
water; and high boilers (propionic acid) and deliver high purity acetic acid product
Present Technologies

o ACEO bio-acetic acid pilot plant in Burghausen has already been up and
running for the past six months and uses following processes. ACEO
Process - involves a biomass feedstock being converted to ethanol (using
yeast) and producing acetic acid via gas phase oxidation process

o Fermentation to Butanediol - Ferments biomass feedstock using bacteria

to butane 2,3 diol, which could be then dehydrated to produce methyl
ethyl ketone (MEK) or directly produce acetic acid via gas phase
oxidation. Acetic acid from MEK is also possible via gas phase oxidation.

o Homoacetate Fermentation - Ferments biomass feedstock to

acetate/acetic acid using bacteria.
Wacker Aceo process
PRODUCTION OF AMMONIA

• Ammonia or azane is a compound of nitrogen and hydrogen with the formula

NH3. It is a colourless gas with a characteristic pungent smell.
• Ammonia contributes significantly to the nutritional needs of terrestrial
organisms by serving as a precursor to food and fertilizers.
• Ammonia, either directly or indirectly, is also a building-block for the
synthesis of many fertilizers, pharmaceuticals and is used in many commercial
cleaning products.
• Although in wide use, ammonia is both caustic and hazardous.
• In 2006, worldwide production was estimated at 146.5 million tonnes.
Ammonia

• Gaseous ammonia was first isolated by Joseph Priestley in 1774 and was
termed as "alkaline air".
• Claude Louis Berthollet ascertained its composition in 1785.
• The Haber-Bosch process to produce ammonia from the nitrogen in the air
was developed by Fritz Haber and Carl Bosch in 1909 and patented in
1910.
• Prior to the availability of cheap natural gas, hydrogen as a precursor to
ammonia production was produced via the electrolysis of water or using
the chloralkali process.
Ammonia

• Ammonia, as used commercially, is often called anhydrous ammonia.

• This term emphasizes the absence of water in the material.
• Because NH3 boils at −33.34 °C (−28.012°F) at a pressure of 1 atmosphere,
the liquid must be stored under high pressure or at low temperature.
“Household ammonia” or “ammonium hydroxide” is a solution of NH3 in
water.
• The concentration of such solutions is measured in units of the Baumé scale
(density), with 26 degrees baumé (about 30% w/w ammonia at 15.5 °C) being
the typical high-concentration commercial product.
• Household ammonia ranges in concentration from 5 to 10 weight percent
ammonia.
Properties

• Molecular formula : NH3

• Molecular weight : 17.031 gm/mole
• Appearance : Colourless gas
• Odour : Strong pungent
• Boiling point : -33.340C
• Melting point : -77.730C
• Density : 681.9 kg/m3 at −33.30C (liquid)
• Solubility : Soluble in water
Manufacturing Processes

(a) Haber and Bosch Process

(b) Modern method/ Killogg ammonia process

(c) Modified Haber Bosch process

Process Description

• The method was first developed by Haber and Bosch therefore known as
• Haber and Bosch Process.
• The manufacture of ammonia is carried out by passing mixture of pure
• hydrogen and nitrogen in the proportion of 3:1 by volume under pressure
• (100-1000atm depending on conversion required).
• Both the gases are sent through filter to remove compression oil and
• additionally through the high temperature guard converter in which CO and
• CO2 are converted to CH4, and also removal of traces of H2O, H2S, P and As.
• The relatively cool gas is added along the outside of converter tube walls to
• provide cooling.
• Carbon steel is used as material of construction for pressure vessel and
internal tubes.
• The preheated gas flows next through the inside of the tube which
contains promoted iron catalyst at 500-5500C.
• The NH3 product, with 8-30 % conversion depending on a process
conditions, is removed by condensation, first with water cooling and then
NH3 refrigeration.
• The unconverted N2-H2 mixture is recirculated to allow an 85-90 % yield.
• Cost is greatly influenced by the pressure, temperature, catalyst, purity
of raw materials and most importantly heat recovery and reuse.
• For achieving quality material at lower cost modification in Haber and
Bosch Process are initiated.
Reaction

N2(g) + 3H2(g) 2NH3(g) ΔH = - 22.0 kcals

Step 1 - Hydrogen production

Hydrogen is produced by the reaction of methane with water. However,

before this can be carried out, all sulfurous compounds must be removed
from the natural gas to prevent catalyst poisoning. These are removed by
heating the gas to 400oC and reacting it with zinc oxide:
ZnO + H2S → ZnS + H2O
Following this, the gas is sent to the primary reformer for steam reforming,
where superheated steam is fed into the reformer with the methane. The gas
mixture heated with natural gas and purge gas to 770oC in the presence of a
nickel catalyst. At this temperature the following equilibrium reactions are
driven to the right, converting the methane to hydrogen, carbon dioxide and
small quantities of carbon monoxide:
CH4 + H2O →3H2 + CO
CH4 + 2H2O → 4H2 + CO2
CO + H2O → H2 + CO2

This gaseous mixture is known as synthesis gas.

Step 2 - Nitrogen addition

The synthesis gas is cooled slightly to 735oC. It then flows to the secondary
reformer where it is mixed with a calculated amount of air. The highly
exothermic reaction between oxygen and methane produces more hydrogen.
Important reactions are:
CO + H2O → CO2 + H2
O2 + 2CH4 → 2CO + 4H2
O2 + CH4 → CO2 + 2H2
2O2 + CH4 → 2H2O + CO2
In addition, the necessary nitrogen is added in the secondary reformer. As
the catalyst that is used to form the ammonia is pure iron, water, carbon
dioxide and carbon monoxide must be removed from the gas stream to
prevent oxidation of the iron. This is carried out in the next three steps.
Uses

Ammonia is major raw material for fertilizer industries

It is used during the manufacture of Nitro compounds, Fertilizers e.g. urea,
ammonium sulfate, ammonium phosphate etc.
It is also used in manufacture of Nitric acid, Hydroxylamine, Hydrazine,
Amines and amides, and in many other organic compounds.
It is also used in heat treating, paper pulping, as explosives and
refrigerants.
PRODUCTION OF UREA
General Information

1) Urea (NH2CONH2) or carbamide is an organic compound has two —NH2

groups joined by a carbonyl (C=O) functional group.
2) Urea serves an important role in the metabolism of nitrogen containing
compounds by animals and is the main nitrogen containing substance in the
urine of mammals.
3) Urea was first discovered in urine in 1727 by Herman Boerhaave, though
this discovery is often credited to Hilaire Rouelle.
4) Friedrich Wöhler synthesized urea from an inorganic precursor in 1828.
5) It was the first time that the molecule found in living organisms could be
synthesized in the laboratory without biological starting materials.
6) Due to this discovery, Wöhler is considered as the father of organic
chemistry by many scientists.
General Information

1) Urea has the highest nitrogen content available in a solid fertilizer (46%). It is
easy to produce as prills or granules and easily transported in bulk or bags
with no explosive hazard.
2) It dissolves readily in water. It leaves no salt residue after use on crops and
can often be used for foliar feeding.
3) Urea is an acceptable fertilizer for rice and preferable to nitrates for flooded
rice because of the reduction of nitrates to N2O and/or nitrogen (in anaerobic
conditions) which is lost to the atmosphere.
4) Also, rice can utilize the ammonium form of nitrogen efficiently.
5) Hydrolysis and nitrification (in aerobic conditions) are rapid in tropical, sub-
tropical and warm climates, Urea can be sprayed on leaves and can also be
mixed with insecticides or herbicides for soil application.
6) A urea ammonium nitrate mixture with herbicide is also used for weed
control.
Disadvantages

1) When applied to a bare soil surface, urea hydrolyzes rapidly result into
loss of significant quantity of ammonia by volatilization. Such losses vary
from soil to soil and are greater for urea in a pellet form rather than in
solution form.
2) It is phytotoxic due to rapid hydrolysis of urea in soils can cause injury to
the seedlings by ammonia.
3) The fertilizer grade urea may contain toxic biuret which is formed during
urea manufacture by an excessive temperature rise. Above 2%
concentration of biuret in urea is harmful to plants.
Feed grade urea is sometimes referred to by the number 262 which is the
product of its nitrogen content (42 %) multiplied by 6.25, the latter being the
factor used by chemists to convert nitrogen to its protein equivalent.
Properties

Molecular formula : CH4N2O

Molecular weight : 60.06 gm/mole
Appearance : White granules
Odour : Odourless
Bulk density : 673-721 kg/m3
Angle of repose : 300
Melting point : 132-1350C
Density : 1.32 gm/ml
Solubility : Solubility in water, ethanol, glycerol
Moisture : 1% by wt. (Max.)
Properties

1) It is highly soluble in water and practically non-toxic (LD 50 is 15 gm/kg

for rat).
2) Dissolved in water, it is neither acidic nor alkaline.
3) As soon as urea dissolves in the soil, it forms around it a zoning layer of
high pH and ammonia concentration turning the soil to be acidic and
toxic at the same level.
4) Urea is high moisture absorbent therefore it should be stored in sealed
and well enclosed bags.
Raw materials

Basis: 1000 kg prilled urea

Item Once Through Partial recycle Total Recycle

NH3 1150 kg 880 kg 600 kg
CO2 1470 kg 910 kg 770 kg
Power 210 kWH 165 kWH 145 kWH
Steam 1800 kg 2000 kg 2400 kg
Cooling water 120000 kg 70000 kg 110000 kg
Sources of raw material

1) Ammonia can be synthesized by Haber – Bosch or Modern process.

2) CO2 shall be obtained from any source.

Reaction

CO2 + 2NH3 NH2COONH4 ΔH = - 37,021 Kcal

NH2COONH4 NH2CONH2 + H2O ΔH = + 6.3 kcals

Urea is always made in an ammonia plant because it produces CO2 as by
product, which can be used directly without further treatment.
Two reactions are involved in the manufacture of urea.
First ammonium carbonate is formed under pressure by highly exothermic
reaction between carbon dioxide and ammonia followed by the endothermic
decomposition reaction.
While the former reaction under pressure, reaches to almost completion
and the decomposition reaction incomplete.
Unconverted carbon dioxide and ammonia, along with undecomposed
carbamate, must be recovered and reused.
The synthesis is further complicated by the formation of a dimer called
biuret, NH2CONHCONH2.H2O which must be kept low because it adversely
affects the growth of some plants.
Liquid ammonia, gaseous carbon dioxide and recycle materials charged in
the heat exchanger-reactor at the pressure of 14 MPs at 170 - 1900C to form
carbamate, with most of the heat of reaction carried away as useful process
steam.
The carbamate decomposition reaction is both slow and endothermic.
The mixture of unreacted reactants and carbamate flows to the
decomposer.
The stoichiometric ratio of CO2/NH3 conversion to urea is essentially about
55 %, but by using an excess of CO2 (or NH3) the equilibrium can be driven as
high as 85 %.
The reactor must be heated to force the reaction to proceed.
CO2 is introduced at process pressure followed by stripper.
All the unreacted gases and undecomposed carbamate to be removed from
the product, the urea must be heated at lower pressure (400 kPa).
The reagents are reacted and pumped back into the system.
Evaporation and prilling or granulating produces the final product.
Overall, over 99 % of both CO2 and NH3 are converted to urea, making
environmental problems to minimum.
Carbamate is highly corrosive to both ordinary and stainless steel, but
with oxygen present, 300 series stainless steel resist it very well, so some
air is introduced along with CO2 reagent to reduce system corrosion.
Developments in urea process technologies

a) Montedison's IDR process

Montedison's process employing two specially designed stripping columns.
Ammonia and CO2 are used as the stripping agent in 1st and 2nd column
respectively.
The reactor constructed in two sections having perforated trays and also
a down comer meant for circulation solution.
High NH3 to CO2 ratio results in increased conversion efficiency and lower
carbamate recycle duty of the plant.
Excess NH3 is removed by CO2 stripping instead of distillation as
practiced in conventional total recycle processes, minimizing the energy
requirement.
b) TEC-ACES process
This is typically CO2 stripping process employing higher ratio (4:1) of NH3 to
CO2, and higher synthesis pressure leading to high conversion efficiencies as
compare to total recycle process.
Stripping is carried out in a two stage stripper constructed of special steel.
The upper part of the stripper is a tray column for the removal of excess
ammonia whereas the lower part is a falling film exchanger for the stripping
action.
c) Stamicarbon stripping process
Consumption of steam is decrease by employing a pool condenser of new
design featuring high resistance time and direct heat exchange between
condensing vapours from stripper and the stripped urea solution; and an
evaporator of improved design which allows better utilization of multiple
effect principle in heat transfer.
d) Ammonia casale's SRR process
Split reaction recycle (SRR) process of ammonia casale is specifically
developed for revamping plants based on stripping technology of either
snamprogetti or stamicarbon and includes installation of secondary high
pressure section consisting of feed pump, reactor, supplementary
decomposer and separator which extend the urea formation reaction.
The operating conditions are same as traditional ones.
The new secondary section added to the synthesis loop can be
prefabricated on skid mounted units and can be erected at site without any
modification on the layout of the existing synthesis section.
The raw material and utilities requirement for different processes for
synthesis and purification of urea are tabulated

Item Unit Process

A B C D

Ammonia Kg 570 570 570 570

CO2 Kg 740 740 740 740

Steam Kg 900 800 660 790

Power KWH 140 140 16 21

Water m3 3.1 2.4 3.1 3

Granulation

Now a day, granular urea has gained importance since it minimize air
pollution and granules has higher strength larger sizes and is more
compatible with other granular fertilizers.

Following commercial processes are available for granulation of urea:

 Pan granulation and falling curtain granulation process of Tennessee Valley

Authority (TVA)
 High temperature pan granulation (GTPG) process of Norsk Hydro.
 Fluidized bed granulation process of Hydro Agri Licensing & Engineering.
 Fluidized bed granulation process of TEC.
Major Engineering problems

Autoclave variables
The objective of autoclave reaction is to produce the optimum economic
yield. The conditions which affects rate of reactions are temperature,
pressure, NH3/CO2 ratio and feed rate. The urea production rate can be
varied as follows
 Increase with increasing pressure
 Increase with temperature to maximum at 175-1800C, then falls of sharply.
 The operating pressure should be above the dissociation pressure
(dissociation pressure is 180 atm at 190°C) for the carbamate.
 Use no excess ammonia.
Reasons for not operating at maximum temperature and pressure without
excess ammonia
 Increased pressure increases capital and operating cost of compression
and reaction equipment.
 At higher temperature urea decomposed to biuret, which is
detrimental to germinating seeds and toxic to animals.
 The above process conditions enhance corrosion rates to machinery
Carbamate decomposition and recycle
 It is optimized by short residence times in a stripping column operating at
low pressure and high temperature.
 Later should be below 1100C if hold up time exceeds 1-2 seconds to avoid
biuret formation.
 Use of millisecond contact time in a flash evaporator allows 1400C
operating temperatures in the high recycle design.
 Main difference in competing processes is in the recycle design.
 Since conversion is only 40-50 % per pass, the unreacted off gases must be
recirculated or used economically elsewhere.
 Recompression of off gases is virtually impossible because of corrosion
and formation of solid carbamate in compressors.
 A solution is formed and pumped into the autoclave.
Production of granular urea (Prilling)
Problem again is biuret formation. Vacuum drying of 80% urea to > 99% and
spraying to air cooled and solidify must be done just above the melting
point of urea and with a minimum residence time.
Heat dissipation in the autoclave
The exothermic heat of reaction can be removed by coils, wall cooling, or
by adding excess reactant to provide sensible heat pick up.
Corrosion
It can be minimized by use of the corrosion resistant metals and maintaining
the proper reaction conditions. High cost silver or tantalum liners are used
in the autoclaves with titanium, stainless (321SS) and aluminum alloys used
in other parts of the plant. Minimum temperature and pressure with excess
NH3 are desirable to reduce the severe corrosion rates.
Uses

As a fertilizer.
As a protein food supplements for ruminant.
As an ingredient in the manufacture of resins, plastics, adhesive, coatings.
Textiles anti-shrink agents and ion exchange resins.
In melamine production.
It is an intermediate in the manufacture of ammonium sulfamate,
sulfamic acid and pthalocyanines.
PRODUCTION OF SUPERPHOSPHATE
General Information

Superphosphate, Ca(H2PO4)2, also refereed as single superphosphate (SSP),

is the first chemically manufactured commercial fertilizer.
John B Lawes named as superphosphate.
Single superphosphate is produced as a combination of rock phosphate and
concentrated sulfuric acid.
Approximately equal amounts of the two ingredients are thoroughly mixed,
dried and cured.
Chemically, SSP contains monocalcium phosphate and calcium sulfate.
The hardened mass is either ground or granulated.
The monocalcium phosphate of single superphosphate dissolves in the soil
moisture and the roots absorb phosphoric acid in that form.
The rest of the solution of monocalcium phosphate precipitates in the
soil pores and forms different phosphate compounds which are water-
insoluble and do not leach out.
A compound like dicalcium phosphate dissolves in carbonic acid in water
and becomes available to plants, but the insoluble tri-calcium phosphate
remains fixed in the soil.
Where soil is markedly acidic i.e., rich in active iron and aluminum
monocalcium phosphate gets converted into insoluble phosphate
compounds
2Ca(H2PO4)2 + Fe2O3 2FePO4 + 2CaHPO4 + 3H2O
Because iron and aluminum phosphates are insoluble, phosphorus does
not available to the plant.
That why SSP does not use in acidic soils unless it is limed.
If single superphosphate is applied just before sowing, plants get enough
supply of phosphorus at their critical growing stages.
Single superphosphate is not suitable for top dressing because of its slow
movement.
Sometimes, single superphosphate is mixed with lime or dolomite in order to
increase its effectiveness.
The production of single superphosphate is on the rise in tropical countries,
like India.
SSP compared to various sulfur-containing fertilizers like DAP and TSP,
significantly increases the grain yield of many agronomical important crops
like wheat, chickpea and groundnut.
SSP is compatible to mix with (NH4)3PO4, (NH4)2SO4, NH4Cl, KCl and K2SO4.
Mixtures of SSP with materials containing free lime or CAN or urea should not
be stored for long as they cause reversion of water-soluble phosphate.
In order to get the maximum benefits, single superphosphate should be
applied to soils deficient in phosphorus as well as sulfur.
The time, place and the quantity of application are critical.
SSP is the principal phosphate fertilizer due to
The production process is simple, requires little skill and small
investment
It sets a standard of comparison for other phosphate fertilizers
It supplies two secondary nutrient elements, namely, sulfur and
calcium
Despite these advantages, single superphosphate has a low phosphorus content
(16 to 22 % P2O5), and 6 to 10% moisture content which sometimes make SSP
production uneconomical.
Properties

Molecular formula : CaH4(PO4)2

Molecular weight : 234.05 gm/mole
Elemental analysis : 16% P2O5 (7% P), 12% S, 21% Ca, 4% phosphoric acid
Appearance : White, Gray or brown granular
Odour : Odourless
Boiling point : 2030C
Melting point :1090C
Density : 2.22 gm/ml
Solubility : Solubility in water, HNO3 and HCl
Angle of repose : 260
Critical humidity : 93.7 % at 300C
Raw Materials

Basis: 1000 kg Superphosphate (den process)

Calcium phosphate = 625 kg
Sulfuric acid = 320 kg
Water = 90 kg
Electricity = 0.2 kWH
Labour = 0.1 man-hr

Sources of raw material

Phosphate rock can be obtained and purified as described in Phosphoric

Acid Process.
Sulfuric acid can be obtained by contact process.
Reactions

Ca3(PO4)2 + 2H2SO4 + 4H2O CaH4(PO4)2 + 2(CaSO4.2H2O)

CaF2 + H2SO4 + 2H2O CaSO4.2H2O + 2HF

4HF + SiO2 SiF4 + 2H2O

3SiF4 + 2H2O SiO2 + 2H2SiF6

Overall reaction

CaF2.3Ca3(PO4)2 + 7H2SO4 + 3H2O 3CaH4(PO4)2.H2O + 2HF + 7CaSO4

The manufacture of superphosphate involves following steps
a) Preparation of phosphate rock
The quality of the product is determined by the grade of phosphate rock.
Fine grinding is demanded due to low reactivity of the rock.
Phosphate rock is finely ground up to the size of less than 100 meshes.
Grinding of phosphate rock to fine powder has following advantages
Increase the rate of reaction
Less sulfuric acid is needed
A higher grade of product in better condition is obtained.
It is difficult to make SSP from igneous apatite.
Up to a point, the presence of aluminum and iron compounds can be
tolerated, though they reduce the solubility of phosphorus in water.
The increase in the ratio of CaO:P2O5 raises the consumption of sulfuric
acid per unit of P2O5 and decreases the grade.
Silica has no adverse effect and higher chloride content in the phosphate
rock is acceptable.
b) Mixing with acid
A finely ground (less than 100 meshes) phosphate rock is mixed with sulfuric
acid in a cone mixer. The commercial concentrated sulfuric acid (77 to 98 %)
is diluted to around 68 to 75 % before reacting with the rock.
c) Curing and drying of the original slurry by completion of the reactions
The fluid material from the cone mixer goes to a den where it solidifies
owing to a continued reaction and crystallization of monocalcium phosphate.
The superphosphate is removed from the den after 0.5 to 4 hours. It is still
at temperature of about 100°C and plastic in nature.
d) Excavation, milling, and bagging of the finished product
The product from the den is sent to storage piles for final curing of 2 to 6
weeks. During curing, the free acid, moisture and the unreacted rock
content decreases, whereas the available water-soluble phosphorus content
increases. As the reaction approaches completion during curing, the
material hardens and cools. The cured product is crushed in a hammer mill
or cage mill to a size of about 6 mesh.
e) Granulation
When granular superphosphate is required, the product is granulated before
or after curing. Granulation before curing is advantageous as it requires less
steam or water. After granulation, the product is dried in a direct contact
drier and screened.
Super phosphate is manufactured by
1. Batch process
2. Continuous process

1. Batch - den process

Rock phosphate and sulfuric acid in correct quantities are added to a pan
mixer of 1 to 2 tons capacity. After mixing for 2 minutes, the fluid slurry is
discharged into a box den which has 10 to 40 ton capacity. When the den is
filled completely after 1 hour, it is moved slowly to a mechanical cutter
which removes thin slices of product to the conveyor. Some plants have two
dens, which are used alternatively. This set up gives a production rate of 40
tons per hour.
Advantages

If only igneous rock is available, batch mixing are preferred due to

precise control of mixing conditions available and den can be made tight
enough to contain the very fluid slurry.
For a small phosphate source in a remote place, batch process can be
built.

Although newer plants use continuous processes, some plants still conduct
these operations stepwise. All plants first pulverize the rock with modern
pulverizing and air-separation equipment, most rock is ground so that 70 to
80% of particles are passed through 200mesh screen.
2. Continuous-den process
Finely ground phosphate rock is fed by a weigh feeder into a double-
conical mixer, where it is thoroughly mixed with metered quantities of
sulfuric acid.
The acid and water are fed into the cone mixer tangentially to provide the
necessary mixing with the phosphate rock.
The sulfuric acid is dilute with water in the cone to the concentration of
51°Be.
The heat of dilution of the sulfuric acid serves to maintain proper reaction
temperature, and excess heat is dissipated by evaporation of extra water
added.
The rate of water addition and acid concentration may be varied to control
product moisture.
The fresh superphosphate is discharged from the cone mixer into a pug
mill, where additional mixing takes place and the reaction starts.
From the pug mill the superphosphate drops onto the den conveyor, which
has a very low travel speed to allow about 1hr for solidifying before reaching
the cutter.
The cutter slices the solid mass of crude product so that it may be
conveyed to pile storage for "currying" or completion of the chemical
reaction, which takes 10-20 day to reach P2O5 availability acceptable for
plant food.
The conveyers den is enclosed so that fumes do not escape into the
working area.
These fumes are scrubbed will water sprays to remove acid and fluoride
before being exhausted to the atmosphere.
Scrubber water is neutralized by passing through the limestone bed.
Nitric and mixed acid acidulation of phosphate rock
First use of nitric and mixed acid acidulation of phosphate rock was
carried out in Europe.
It is desirable, since nitrogen has an essential value as plant food and can
be resold at its purchase price.
Also, this saves sulfur.
Simple acidulation of phosphate rock with nitric acid produces the
hydroscopic superphosphate, since it contains calcium nitrate.
There are various commercial modification in the process is carried out.
In one, the phosphate rock is extracted by mixed nitric and sulfuric acids,
followed by ammonization, drying.
In another method, mixed nitric and phosphoric acidulation followed by
the conventional steps and others use nitric acid alone for acidulation.
These processes, as well as conditioning against moisture absorption as
practiced for ammonium nitrate, have led to an extension of this
acidulation with nitric acid.
Nitrophosphate is also gaining importance particularly in European
countries.
Phosphate rock is decomposed with nitric acid plus small amount of
phosphoric acid.
The resulting slurry is ammoniated and carbonated and, if desired,
combined with potassium salts and spray-dried to yield a uniform palletized
product.
Granulation
Both granulation and drying of the SSP are carried out in the same piece of
equipment.
The powdered superphosphate enters to rotary drum granulator, where it is mixed
and granulated with recycled fines (recycle ratio: > 0.6).
Granulation is controlled by adjusting the water content and temperature of the
product in the 1st part of the rotary drum.
Drying is achieved near the exit from the granulator and involves adding more
sulfuric acid and ground limestone (about 60 kg/ton SSP).
The heat produced by the reaction dries the product and the calcium sulfate formed
encapsulates the product in such a way that caking is avoided during final curing and
storage of the product.
No P2O5 reversion is noticed.
Product is sized using a conventional system of screens and crushers such that 90 %
of the product is between 1 and 4 mm in size.
Final curing of the product occurs during storage for less than two weeks.
Handling and storage
Powder SSP is not free flowing and has the tendency to cake.
Granulated SSP can be easily handled and uniformly distributed in the
field without any problem.
Due to the presence of free acid, single superphosphate is normally
bagged in polyethylene lined HDPE woven bags.
Polypropylene woven bags can also be used.
Cost
The costs of bagging, transportation and storage of SSP are high, because
the mass of SSP required is more than twice that for TSP.
Hence small plants of SSP are economically better suited to serve small
local markets.
Uses

It is the principal carrier of phosphate, the form of phosphorus usable by

plants, and is one of the world's most important fertilizers.
it is low cost source of phosphorous in a wide range of pasture and
cropping situations.
Generally mixed with sulfate of ammonia and muriate of potash, but can
be blended with other fertilizers.
PRODUCTION OF TRIPLE SUPERPHOSPHATE
General Information

Triple superphosphate (TSP) is the more concentrated fertilizer than

ordinary
superphosphate, containing from 44 to 51 % of available P2O5 or nearly three
times the amount in the regular superphosphate.
Owing to the high concentration of phosphorus, TSP is used widely in the
production of high analysis compound fertilizers.
Triple superphosphate, also known as concentrated superphosphate,
contains 45 to 50 % monocalcium or water-soluble phosphate and 17 to 20 %
lime.
Its concentrated form is cheaper to transport, store and apply when
compared with the dilute form.
TSP is manufactured by adding phosphoric acid to rock phosphate,
producing mainly water-soluble monocalcium phosphate with no calcium
sulfate.
In most processes, a large percentage of fluorine remains in the product,
probably as fluorosilicate or calcium fluoride.
When triple superphosphate is used as a fertilizer, the yield from short
season crops like cereals, potato and some vegetables is markedly higher.
This fertilizer lets a weak root system establish itself firmly and
supports the crop to stand during the growing period.
Properties

Molecular formula : Triple superphosphate

Molecular weight : 252.07 gm/mole
Appearance : White or gray granules
Solubility : water soluble
Density : 1.089 gm/ml
pH : 2.5-3.0 (aqueous solution)
P2O5 (water soluble) : 42.5 % minimum
Free phosphoric acid : 3 % by wt. (Max.)
Angle of repose : 450
Bulk density : 800-881 kg/m3
Moisture : 12.0 % by wt. (Max.)
The manufacture of triple super phosphate involves following steps
a) Reaction
b) Denning or Den process step
c) Storage and curing
d) Granulation
a) Reaction
The reaction is carried out in a cone-mixer.
A similar process known as Kuhlman process uses a mixer that has a high-
speed stirrer in a cylindrical vessel.
95 to 98 % of the ground rock phosphate, passed through 100 mesh sieve,
is mixed with phosphoric acid (1 kg rock phosphate of 34 % P2O5 is mixed
with 2.6 kg acid).
The acid is of commercial grade with P2O5 content of 52 %.
b) Den step
The den step, of TSP is faster (10-30min) than that for SSP (30-120min).
The mixture from the reaction vessel goes to the den where it solidifies
owing to continued reaction and crystallization of monocalcium phosphate.
c) Storage and curing step
Product from den step is stored in piles for curing.
Curing requires 3 to 6 weeks, depending on the quality of raw materials.
During curing, the free acid, moisture and unreacted rock contents
decrease and the available phosphorus and the water soluble P2O5 increase.
Fluorine compounds evolved in minor quantities which are scrubbed to
prevent atmospheric pollution.
After storage and curing, TSP is ground to a 6 mesh screen (3.3 mm).
This material is called run off pile TSP or ROP-TSP and is used for making
compound fertilizers by agglomeration granulation.
d) Granulation process
Granulation is preferred due to powder form have dusty nature and caking
quality when moist.
The milled and screened TSP is conveyed to a drum granulator where water
is sprayed and steam is spurge underneath the bed to wet the material.
The wet granules are dried in the rotary drier.
The dried granules are screened, and the oversized and the fines are
returned to the granulator.
The dust and fumes from the drier are scrubbed or removed by the dust
filter.
Raw Materials
Basis: 1000 kg Triple superphosphate
Phosphate rock = 386 kg
Phosphoric acid = 540 kg
Power = 40 kWH
Steam = 20 kg
Labour = 0.3 man-hr
Fuel = 140000 Btu
Sources of raw material
Phosphate rock can be obtained and purified as described in H3PO4
Phosphoric can be manufacture by electric arc furnace, blast furnace
or wet process.
Reaction
CaF2 + 3Ca3(PO4)2 + 14H3PO4 10Ca(H2PO4)2 + 2HF
Manufacturing Process:
Finely ground phosphate rock and 62 % H3PO4 are charged continuously
to the granulator, where reaction and granulation take place.
Fines from the product screen are recycled to the granulator, and the
moisture and temperature required for proper granulation are maintained
by addition of water and/or steam.
The granulator is a cylindrical vessel rotating about a horizontal axis and
has in overflow dam at the discharge end.
The phosphoric acid is fed uniformly under the bed of material through
a perforated pipe.
When wet-process phosphoric acid is used, it is also necessary to
provide an acid pre-heater.
The granules overflow the dam into the rotary cooler, where they are
cooled and dried slightly by counter current flow of air.
The exhaust gases from the cooler pass through the cyclone, where dust is
collected and returned to the granulator as recycle, the cooled product is
screened, the coarse material being milled and returned, along with the fines,
to the granulator.
The product is then conveyed to bulk storage, where the material is cured
for 1 to 2 weeks, during which a further reaction of acid and rock occurs,
which, increases the availability of P2O5 as plant food, the exhaust gases from
the granulator and cooler are scrubbed with water to remove silicofluorides.
The cost per unit of P2O5 is higher as compared to ordinary superphosphate,
because of more capital investment and additional labour and processing.
However, this is balance to the great extent by the ability to use the lower-
grade, cheaper phosphate rock to make the phosphoric acid.
There are also substantial savings on handling, bagging, shipping, and
distributing.
Granulation
The Den process or direct slurry granulation process may prepare triple
superphosphate either in a granular or non-granular form. The granular form
of TSP is preferred for direct application or blending and the non-granular
form for making compound fertilizers.
Advantages of the direct slurry granulation process
Product is available at a lower cost
Generate denser and stronger granules
Use of conventional granulation equipment
Disadvantages
Uses phosphate rocks which have a short reaction time, resulting in a
greater loss of soluble phosphorus (as P2O5) due to an incomplete reaction or
higher ratio of phosphoric acid
Granular triple superphosphate is produced directly rather than from the
powder fertilizer.
Ex-den granulation
In this process, phosphate rock is further ground and the den retention time
is larger (25 to 45 minutes instead of 10 to 30 minutes).
The product from the den directly goes to granulation instead of to curing.
The granulated product is dried to get a product with 4 to 6% moisture.
Further reactions take place during storage.
The product is much easier to granulate than cured TSP because of the
plasticity and heat content.
This requires less recycle, water and steam, resulting in the saving of power
and manpower.
Advantages direct granulation process
Low cost
Dense and strong granules
Interchangeability of granulation equipment with that for other
ammonium phosphates.
Disadvantages of the direct granulation process
Short reaction time makes the un-reactive rocks unsuitable
Greater loss of soluble P2O5 due to incomplete reaction.
Handling and storage
TSP in powder form is not free flowing and has a tendency to cake on
storage.
The granulated product has excellent handling and storage
characteristics, and is free flowing.
The material is packed in polyethylene film lined HDPE bags.
Advantages of TSP

It is a highly concentrated straight phosphate fertilizer.

It has a low-cost source.
Its manufacture requires small capital investment and low-skilled manpower.

Disadvantages of TSP

Its total nutrient content is lower than that of ammonium phosphate.

Its acidic character deteriorates storage bags.
It is not suitable for blending with urea as it causes the latter to deteriorate
PRODUCTION OF AMMONIUM SULFATE
General Information
Ammonium sulfate containing 21% nitrogen is another important
nitrogenous fertilizer.
It occurs naturally as the mineral mascagnite and offers many advantages
as a fertilizer, such as low hygroscopicity, good physical properties, excellent
chemical stability, good agronomic effectiveness and long shelf life.
Ammonical nitrogen is fixed in the soil in an exchangeable form until
nitrated by nitrifying bacteria.
The ammonical nitrogen of ammonium sulfate does not leach out easily.
Ammonium sulfate is an acid forming fertilizer, and hence used in neutral or
alkaline soils.
In its free flowing form, it is directly applied to the soil or blended with
other granular materials.
Ammonium sulfate also supplies sulfur, which is an essential nutrient for
plants.
It is a quick-acting fertilizer.
It is resistant to leaching as it gets adsorbed on the soil colloids, clay and
humus, and replaces calcium.
This adsorbed ammonium salt is converted to nitrate by nitrifying bacteria
for use by growing plants.
It can be obtained as a by-product or may be manufactured synthetically.
Ammonium sulfate is obtained as a byproduct; in the steel industry in
which NH3 (another by-product) from coke ovens is absorbed in sulfuric
acid.
(NH4)2SO4 is also manufactured by reacting synthetic ammonia with
sulfuric acid.
(NH4)2SO4 is obtained from waste streams of chemical and metallurgical
industries e.g. ammonia leaching of ores, production of pigments and
synthetic fibers, manufacture of caprolactam produce by product; solutions
containing ammonium sulfate.
Flue gases are another source of the ammonium sulfate.
The metallurgical smelters and coal burning power plants liberate large
quantities of SO2 that pollute the atmosphere.
SO2 is collected and converted into sulfuric acid, (NH4)2SO4 is then
produced by passing ammonia gas through 60 % sulfuric acid placed in lead
lines vats at about 60°C the crystals of ammonium sulfate separate out on
cooling.

2NH4OH + H2SO4 (NH4)2SO4 + 2H2O

Properties

Molecular formula : (NH4)2SO4

Molecular weight : 132.14 gm/mole
Appearance : Fine white hygroscopic granules or crystals
% of nitrogen : 20-21 %
Bulk density : 720-1040 kg/m3
Melting point : >2800C
Specific gravity : 1.769
Angle of repose : 320
Solubility : Solubility in water and insoluble in alcohol,
ether, acetone
Moisture : 1 % wt. (Max.)
Manufacture
a) As by-product from caprolactam
b) Recovery from cock oven
c) Direct neutralization
d) Gypsum process
Gypsum process
Raw materials
Ammonia
CO2
Gypsum
Sources of raw material
Ammonia can be synthesized by Haber – Bosch or Modern process.
CO2 shall be obtained from any one source as described earlier.
Reaction
2NH3 + H2O + CO2 (NH4)2CO3
(NH4)2CO3 + CaSO4 (NH4)2SO4 + CaCO3
CaCO3 CaO + CO2
Ammonia is manufactured by Haber process and CO2 is manufactured by
heating limestone.
Ammonia is absorbed in water and carbonated at the pressure of about 2.1
kg/cm2 in towers packed with aluminum rings.
The prepared liquor strength corresponds to approximately 170 gms of
ammonia and 225 gms of CO2 per liter.
 In another method jet absorbers are used for preparing ammonia solution
and ammonium carbonate liquor in conjunction with a carbonating tower.
Natural gypsum or anhydrite, when used, is ground so that about 90 % of
the material passes through 120 mesh sieve.
When the byproduct gypsum of phosphoric acid plant is used, the
impurities are removed by repulping the filter cake prior to washing and
dewatering on a drum or disc filter.
Now proper proportion of finely ground gypsum or anhydrite is fed into
the aqueous solution of ammonium carbonate in large tanks, whereby
calcium carbonate is precipitated gradually as a result of double
decomposition.
Reactions of ammonium carbonate and gypsum solutions are carried out
in a series of wooden vessels or mild steel vessels having steam coils and
agitators to give a total retention time of 4 to 6 hours.
CO2 and NH3 are passed until all the gypsum is converted into CaCO3.
The slurry produced is filtered and the calcium carbonate cake washed
and dewatered.
The solution is evaporated and the crystals are centrifuged and dried in a
rotary drier at 1200C.
CaCO3 obtained as by product is used as a raw material for the
manufacture of cement.
Action of (NH4)2SO4 as fertilizer
It reacts with lime present in the soil to for ammonium hydroxide which is
oxidized by air with the help of nitrifying bacteria into nitrous acid.
Later is then converted into nitrites.
The nitrous acid and nitrites also undergo oxidation by means of air in
presence of nitrifying bacteria and form nitric acid and nitrate.
Handling and storage
Crystalline ammonium sulfate is free flowing and does not normally pose
any problem in handling and storage.
However, it generally contains some powdered material which causes
caking, especially under high humidity.
Due to its susceptibility to caking and slight acidity, ammonium sulfate is
normally bagged in polyethylene lined gunny bags or high density
polyethylene (HDPE) woven sacks.
Uses
Most commonly used in fertilizers.
It is often used in combination with other materials, such as urea, to make
dry fertilizers.
It is a good source of nitrogen for cotton, rice, wheat, barley, maize,
sorghum, sugar cane and fiber crops.
It is also used as a general purpose food additive, dough conditioner and
food for yeast.
In medicine, ammonium sulfate plays an important role in the
development of vaccines. The DTaP vaccine, for example, which protects
children from diphtheria, tetanus and whooping cough, uses ammonium
sulfate in the purification process.
Used in rice and jute cultivation.
The Baumé scale is a pair of hydrometer scales developed by French pharmacist Antoine Baumé in 1768 to
measure density of various liquids. The unit of the Baumé scale has been notated variously as degrees
Baumé, B°, Bé° and simply Baumé (the accent is not always present). One scale measures the density of liquids heavier
than water and the other, liquids lighter than water. The Baumé of distilled water is 0. The API gravity scale is based on
errors in early implementations of the Baumé scale.
The relationship between specific gravity (s.g.) (relative density) and degrees Baumé is function of the temperature.
Different versions of the scale may use different reference temperatures. Different conversions formulae can therefore
be found in various handbooks.
As an example, a recent handbook indicates the following conversion rules at a temperature of 60 °F (16 °C):
For liquids more dense than water:

For liquids less dense than water:

An older handbook gives the following formulae (no reference temperature being mentioned):
For liquids more dense than water:

For liquids less dense than water: