NITROGENOUS FERTILIZERS

AMMONIA [NH3] UREA [(NH2)2.CO] AMMONIUM NITRATE [NH4NO3] AMMONIUM SULPHATE [(NH4)2SO4] AMMONIUM CHLORIDE [NH4Cl]

MIXED NITROGEN CONTAINING PRODUCTS MAP [ NH4.H2PO4] DAP [(NH4)2HPO4] POTASSIUM NITRATE [KNO3]

UREA

Amongst richest sources of Nitrogen, most popular Fertilizer grade : as prills, coated with lime stone/phosphate rock [Elsewhere as Liquor : Urea, NH3 solutions] Other uses Animal Feed Resins [ Urea Formaldehyde] Melamine Adhesives

PRODUCTION [India] ; 106t 2005-06 06-07 07-08 20.09 20.27 19.84 IMPORTS 2.06

08-09 19.92

09-10 21.12

4.72

6.93

5.67

5.12

SUBSIDY [US$109] 2.64 3.54

5.12

6.78

4.00

PROJECTED USAGE [106t] 2010-11 27.56 SHORTAGE 6.31 Plants needed (2250tpd) 100% capacity utilization 8 7.03 10 8.00 11 8.71 12 11-12 28.28 12-13 29.25 13-14 29.96

Where are the plants? - Gestation period

CONTD..
(g) (g) (s/melt)

SIDE REACTION

RAW MATERIALS Ammonia Carbon dioxide

Process Flow Sheet

CRITICAL PARAMETERS

Temperature Pressure NH3/CO2 mol ratio Operating pressure > dissociation pr. of carbamate Dissociation pr with temperature

CHALLENGES Corrosion MOC Bouret formation Management of excess reactant

 Reference to Flowsheet [Dryden] Principal Reactions Ammonium Carbamate formation ; Ammonium Carbamate decomposition + (s/melt) (s) (l) Side reaction (biuret formation) (g) (s/melt)

Features Separate compression of ammonia and Carbon dioxide [why?] Carbamate formation non catalytic temperatures for reasonable rates 1800C Dissociation pr. Of Carbamate 1800C is >100 atm. Rate increases with increase in pressure. Increase in temperature increases biuret formation Use of excess ammonia provides a slight advantage [compression costs?] Typical Reactor (Autoclave) conditions - Temperatures 1700C - 1900C - Pressures 100-200 atm. - Feed NH3/CO2 mol ratio:2.0 plus - Av. residence time (continuous reactor !!) 1.5 2.0 h. - 45-50% Conversion [single pass] Reactor operation conditions: - compromise/optimization between thermo, kinetics and corrosion.

Major variations in commercial processes

o

Management of unconverted gases - Once through : excess NH3 converted to by products - partial recycle : recycle + byproducts - total recycle : preferred option [See Dryden for commercial processes]

Materials of Construction
o

Severe corrosion conditions

- Autoclave : Silver/Tantalum/Zirconium lined - other parts : Titanium/Hastelloy C/SS 321

Carbamate Decomposition
o -

In stages Stage 1 : Flash to 27 atm; 1400C

steam heating prior to flashing/in flash chamber Water cooling to condense flashed gases Gases + condensate recycle Melt to steam heater

Stage 2 : Flash to 1 atm.

Gases to recycle melt to steam heater & vacuum evaporator

Evaporation, Finishing - evaporator product 99% urea melt - prilling: cooling/drying in : counter current spray tower - prills/granules:small 2-3 mm spherical particles - coat: if necessary

Other features - high cooling water consumption - modest steam consumption - rarely stand alone; adjucnt to NH3 plants Why is urea the most preferred Nitrogenous Fertilizer vis--vis Other Nitrogen rich Fertilizers?