You are on page 1of 22

8/20/15

LECTURE19:
AMMONIUM NITRATE
AMMONIUM PHOSPHATE
AMMONIUM SULFATE
1

CHEMICAL TECHNOLOGY (CH-206)


Department of Chemical Engineering

AMMONIUM NITRATE
8/20/15

It is produced in solid form as pellets, crystals or


flakes by reacting nitric acid and ammonia in
different proportions.
It is widely used either as fertilizer or explosive or for
the production of chemicals.

AMMONIUM NITRATE: PROPERTIES


Chemical formula :

NH4NO3

8/20/15

Molecular weight : 80.05


M.P. :
170oC
B.P.
: Decomposes at 200 oC or higher
Solubility
: Soluble in water, alcohol, and NH3

Grades : C.P.: White hygroscopic crystals or


granules
Fertilizer93-95% containing 33% N
Explosive when mixed with combustible materials or
exposed to high temperatures

AMMONIUM NITRATE: PRODUCTION


Chemical reaction
NH3 + HNO3 NH4NO3;

8/20/15

H = 20.6 Kcal

Raw materials
57

60% HNO3 from oxidation absorption tower


Liquid NH3
Clay such as diatomaceous earth, kieselguhr for coating on endproduct to
avoid explosions

Quantitative requirements:
Basis:

1 ton of ammonium nitrate (98% yield)

Ammonia (NH3)
0.22 ton
60% HNO
1.38 ton
3

Plant

capacity 100500 tons/day

AMMONIUM NITRATE : PROCESSES


8/20/15

Prilling process
Crystalization process
Stangel process
Nitrolime process

AMMONIUM NITRATE : PROCESS


H2O to
waste

Moist air Steam heated conveyor dryer


Scree
n
8/20/15

AMMONIUM NITRATE: PRILLING


PROCESS

The ammonia vapor is reacted with aq. HNO3 in a stainless


steel reaction vessel with agitation.
The heat of reaction causes water to boil off and the final salt
solution is 75% and 140 oC when pumped to a vacuum
evaporator to concentrate further to 95% solids.
The hot liquor is sprayed from the top of a prilling tower
countercurrent to conditioned air flow.
The solidified spherical pellets or prills are about 1.5 mm in
diameter and must be screened and dried before coating with
clay.
Fines and oversized materials are redissolved and sent to the
neutralizing reactor for recycle.
The process is further modified using an oil quenching unit for
prill production to replace the large and uneconomical prilling
tower.

8/20/15

AMMONIUM NITRATE: CRYSTALLIZATION


PROCESS
8/20/15

Upto the point of spraying the process is similar to


the prilling process.
The liquor from the vacuum evaporator contains
8085% solids and is fed to a vacuum crystallizer
where crystal growth is controlled at about 40 oC to
yield a large grain required for fertilizer use.
The crystal slurry with about 40% (wt.) crystals is
centrifuged; the mother liquor is returned to the
evaporator and the crystals are dried in a through
conveyor or a rotary dryer at about 15 oC.
Dusting with clay (24%) is used where explosion
hazards in bulk storage are prevalent and free
flowing non hygroscopic material is specified.

AMMONIUM NITRATE: STENGEL


PROCESS
8/20/15

Preheated HNO3
Preheated
NH3

Reactor and
separator

AMMONIUM NITRATE: STENGEL


PROCESS

The Molten NH4NO3 and water vapors at 200 OC are passed


through the tangential entry of a cyclone separator where air
aids in removal of steam from the molten salt.
The latter is removed at the bottom and solidified on a water
cooled steel belt.
The solids are crushed, ground to flake size and screened.
Oversized are reground and fines are dissolved and returned to
HNO3 preheater stream.

8/20/15

Ammonia vapors are preheated to 140150 OC in an single


stage heat exchanger.
60% HNO3 is preheated first to 95 OC in a stainless steel unit
and then to 160 OC in a tantalum unit to avoid high
temperature HNO3 corrosion.

The product flakes are coated, and bagged or bulk shipped.

10

AMMONIUM NITRATE: NITROLIME


PROCESS

Screen classifying separates 2 4 mm particles which


move on to a coating drum, where fine limestone dust is
added to yield a free flowing product.
Oversize material (> 4mm) is recycled.
Undersize material (< 2mm) is returned to the pug mill
for size buildup.

8/20/15

The 95% melt from evaporator is passed to a pug mill,


which is a screw mixer consisting of a two sets of mixing
blades rotating in opposite directions.
Pulverized lime (325 mesh) is admixed here with some
heat of reaction evolved.
The product flows to a rotary drum granulator, then to a
cocurrent direct heated flue gas dryer where product
moisture is reduced to 0.50.6 % H2O.

11

AMMONIUM NITRATE : PROCESS


H2O to
waste

Moist air Steam heated conveyor dryer


Scree
n
8/20/15

12

AMMONIUM NITRATE:
Major Engineering problems:
Corrosion:

8/20/15

Carbon steel can only be used in the NH3 storage and feed
system.
Type 304, extra low carbon (ELC) stainless steel is used
throughout most of the remainder of an ammonium nitrate
plant.
In the Stengel process, expensive tantulum metal is used in
the heat exchanger.

Crystallization:

Typically the proper size and shape, and distribution of


crystals is not obtained.
An OsloKrystal classifier is used to have adequate growth
of seed crystals to the proper size, shape and strength in a
continuous manner.

13

AMMONIUM NITRATE:
MAJOR ENGINEERING PROBLEMS
Major Engineering problems:
Safety:

8/20/15

Safety precautions are required, since NH4NO3 is extremely


reactive with combustible and it is also sensitive to
explosive decomposition.
Air used in the drying must be free of oil and other
combustibles.
Stangel process has the greatest inherent safety, since it is
designed for short residence times and low holdups.

Air

conditioned requirement

Both NH4NO3 and nitrolime are hygroscopic.

14

AMMONIUM PHOSPHATE
Monoammonium Phosphate (NH4H2PO4)
Mol.

115
M.P.
Decomposes
Density
1.80 gm/cc
Solubility in water
32 gm/100cc at 15 OC

wt.

8/20/15

Diammonium Phosphate ((NH4)2HPO4)


Mol.

wt.

132
M.P.
Decomposes
Density
1.62 gm/cc
Solubility in water
131 gm/100cc at 15 OC

Mostly used as a fertilizer

15

AMMONIUM PHOSPHATE
Chemical Reaction:
NH3 + H3PO4 NH4H2PO4

8/20/15

NH3 + NH4H2PO4 (NH4)2HPO4


NH3 + H2SO4 NH4HSO4
NH3 + NH4HSO4 (NH4)2PO4

16

AMMONIUM PHOSPHATE
Process: Neutralization and granulation
8/20/15

17

AMMONIUM PHOSPHATE
8/20/15

In the first step, neutralization, the phosphoric and


sulfuric acids are added to the first of three continuous
sttirred tank reactors.
Anhydrous liquid ammonia is added beneath the slurry
level in the first neutralizer in an amount equivalent to
80% neutralization.
Further NH3 is added in the 2nd and 3rd reactor to obtain
conversion to the diammonium salt if a higher N fertilizer
is needed.
The exothermic reaction heats the slurry nearly to the
boiling point (130 OC).
Unreacted and excess NH3 vapors are collected from the
top of the each tank and recharge below the liquid level.
It cuts the NH3 losses to less than 3%.

18

AMMONIUM PHOSPHATE
8/20/15

Slurry from third neutralizer is mixed with KCl and


absorbed in a bed of dry recycle fertilizer moving through
a rotating drum granulator.
It provides a tumbling action to coat recycle material
with a slurry film.
A rotary adiabatic dryer reduces the moisture to less
than 1%, with a 10 min contact time with air initially at
150OC.
Dried product is separated into three fractions on a
double deck screen.
A portion of the product from the deck of the lower screen
( 6 +12) is sent to bagging operations.
The balance, together with pulverized oversize and fines,
is returned to the granulator.

19

AMMONIUM PHOSPHATE
Major Engineering Problems:
NH3

losses

8/20/15

Corrosion

- Type 316 SS is used for hot acid and


fume ducts; carbon steel for granulation, drying and
scrrening

20

AMMONIUM SULFATE
8/20/15

Originally it was made using sulfuric acid to


scrub byproduct ammonia from coke oven gas.
Nowadays the ammonium sulfate is
manufactured by reacting synthetic ammonia
with sulfuric acid.
At Sindri, India the ammonium sulfate is
produced by the following reaction:
(NH4)2CO3(aq) + CaSO4.2H2O(s)
CaCo3(s) + 2H2O + (NH4)2SO4(aq)

21

ACKNOWLEDGEMENT
Slides are developed from the following references:
Austin

G. T., "Shreves Chemical Process Industries",


Fifth edition, Tata McGraw Hill, NY.
Kent J.A., "Riegel's Handbook of Industrial
Chemistry, CBS Publishers.
Gopala Rao M. & Marshall Sittig, "Drydens Outlines of
Chemical Technology for the 21st Century", Affiliated
East West Press, New Delhi.
Mall I. D., "Petrochemical Process Technology",
Macmillan India Ltd., New Delhi.
http://nptel.ac.in/courses/103106108/Lecture%207.pdf
(Acetylene)
http://nptel.ac.in/courses/103106108/24

8/20/15

22