Tertre Granulation Plant:: NH3 Acidic Purge of Scrubbing Section Sprayers

Confined space decomposition test of
ammonium nitrate fertilizers in

KEMIRA Tertre lab in Belgium.
• Tertre granulation plant :
• Kemira Tertre granulation plant is equiped with a spherodizer :
the feed to the granulator is a melt of ammonium nitrate (AN) +
a filler. The particles of solid raw materials like dolomite,
calcium sulphate, magnesium sulphate, limestone….are mixed
with a concentrated AN solution in a mixing tank so that the
water content is around 4-9%. The slurry kept around 120-145°c
for 10-20 minutes is then pumped through a manifold and
sprayed onto an existing bed of solid material such that it forms
a skin around the particles.
• The purge of the acidic scrubbing section is recycled in the
mixing tank. Ammonia is fed to neutralize any free acidity and
to keep an alkaline pH in the mixing tank.
NH3
Acidic purge of sprayers
scrubbing section
AN solution +
filler manifold
120-145°c
4-9%H2O
• History :
• In 1993 a decomposition occured in the manifold

between the pump and the spraying nozzles on a
magnesium ammonium nitrate grade : 20N +11MgO
magnesium sulphate based containing 20 kg/T MAP and
7.5 kg/t aluminium sulphate as additives.
• The manifold exploded and pieces were projected out of
the building during it’s cleaning with steam at 185°C.
• Some cracks were found in the manifold filled with
material containing chloride.
• The chloride was brought by the magnesium sulphate
(1.5% max. expressed in CaCl2,MgCl2)
• After investigation, the process was adapted to avoid
any decomposition in the future.
• Bomb test.
• A test to accurately reproduce the decomposition of the

20+11MgO slurry was launched to explain the incident
and measure the influencing parameters. It is inspired
from the ISMA-IFA booklet : Selected tests concerning
the safety aspects of fertilizers. We call it the bomb test
in confined space.
• Procedure :
• 250gr of dry material is added in a closed

2.58liter vessel. Water is added so that the
slurry will contain around 15% water.
• Gaseous and liquid phases are present.
• The vessel is partly immersed in a silicon bath
maintained at 180°c during 8 hours.
• Due to water evaporation, the pressure rises
progressively and stabilises around 1-4 bars
depending of the grade.
• When a decomposition occurs, a gradual
increase in pressure occurs.
• The induction time is recorded when the
pressure reachs 5 bars and the test is stopped.
• If nothing happens, the test is stopped after 8
hours and the recipe is declared to be safe.
• ph 10% + organic content of the slurry are
measured after the test.
Conclusion of the
decomposition of the
20+11MgO grade.
Various bomb tests were made on the 20+11MgO
grade with and without MAP, aluminium sulphate
and dolomite at different pH ’s.
As shown in table + graph underneath, the bomb test
confirms the possibility of 20+11MgO slurry to
decompose at 180°c.
Before Trial After trial Temp.

MgSO4 MAP Al.sulp Dolomite HNO3 NH3 COD Ph10 COD Ph10
. % %
Origin Kg/t Kg/t Kg/t Ppm Ppm °c
Industrial 20 7.5 + 4.64 2.14 180

Industrial 20 7.5 1427 5.02 602 1.86 180
Industrial 20 7.5 + 1329 5.86 637 4.50 170
Industrial 20 7.5 + 1216 5.70 228 1.63 180
Industrial 20 7.5 + 1619 5.82 819 3.49 190
Analytica 20 7.5 1115 4.86 906 4.67 180
l grade
Industrial 7.5 + 977 4.78 1064 5.90 180
Industrial 7.5 50 + 941 6.25 1045 6.80 180
Industrial 20 50 + 1562 5.77 1906 6.65 180
It was observed that :
-The recipe containing MAP+AlS with a pH 10%

of 5.02 decomposes in less than 1 hour at 180°c
-Addition of HNO3 or NH3 to get a pH of
respectively 4.64 and 5.70 leads to a decomposition
in 40 or 140 min.
-The recipe without MAP doesn’t decompose.
-Pure magnesium sulphate (without chloride)
doesn’t show any tendancy to decompose even
when MAP is added.
-Addition of dolomite acting as a pH buffer avoids
any decomposition even when MAP and AlS are
present.
The conclusion made at that time to avoid any

future decomposition in the 20+11MgO grade
was to add dolomite acting as a pH buffer and
remove the MAP.
Confined space decomposition test of 20+11MgO
16
15 MAP+HNO3
MAP
14
13
MAP +NH3
12
pressure in bars
11 MAP+NH3 190°c
10
9
8
7
6
MAP+NH3+dolomite
5
MAP+NH3 170°c
4
MAP+analytical kieserite
3
NH3
2
1 NH3+dolomite
0
0 20 40 60 80 100 120 140 160 180
Application of the bomb test.
Having shown it’s ability to reproduce a decomposition

encountered in the plant, the test is nowadays used whenever
a modification is made in a recipe : new raw material or
additive, new grade….
Experience upto now :
Except the 20+11MgO grade without dolomite and a

CAN27% acidified so that all dolomite is digested with
HNO3, we have never been able to show a decomposition on
other grades such as :ANAS, 27+5MgO ; 24+16SO3 ;
AN33.5 ; 10.0.0+2%Cu or 5%Mn doped with Cl and pH10%
adjusted at 2.
These grades contain all limestone or dolomite as a pH
buffer.
Contaminants Ph
AN 145ppm 2.0
Ba(NO3)2+50ppmCl
AN 170 ppm Ba(SO4)2
AN 30kg/T AS with 3000ppm
COD
AN 20000ppm MnO 3.0
27+5MgO 2.0
AN 33.5 2.0
ANAS Pernis 2.0
ANAS Pernis 10000ppm cl
29+9SO3 2.0
29+9SO3 500ppm Cl
10.0.0 +2%Cu 5000ppm Cl 55mlHNO337%
10.0.0+5Mn
24+15SO3 5000ppm Cl 3.0
24+15SO3 5000ppm Cl +100ppm cu
24+15SO3 5000ppm Cl +100ppm Mn
12.6.24 1500 ppm CuSO4 2aq 5.1
• There was some doubt as to whether the test was sensitive
enough to foresee any decomposition in the plant and
because pure AN with a pH 10% of 2 is not decomposing
at 180°C with the current test. The decomposition of pure
ammonium nitrate at higher temperature was measured.
• Contaminants like acidity, metals and chloride have been
added.
• The purpose was also to link the test with the literature
available on the decomposition of AN.
• AN 85% decomposition : influence of temperature +

contaminants (HNO3, Cl, Cu and Cr) :
• The test is applied on AN 85% in the temperature range

200-245°c
• Ph tested : 5.4-3.0 and 2.0
• Chloride : 0-500 ppm in the form of NaCl
• Cu++ : 500 ppm in the form of CuSO4.5H2O
• Cr+++ :500 ppm in the form of Cr2O3
Table below confirms that the 20+11MgO
grade containing MAP and AlS was dangerous
as it decomposes at 180°c pH 4.6 even faster
than a pure AN acidified at ph 2.0 and heated at
245°c.
pH10% 5.4 3.0 2.0
Temperature °C 200 225 245 200 225 245 200 225 245
ONSET TIME Minutes
AN - - 161’ - 955’ 147’ - - 100’
AN+25 ppm Cl 373’
AN+50 ppm Cl 310’
AN+200ppm Cl 173’
AN+500ppm Cl 269’ 151’ 55’ 213’ 142’ 42’ 147’ 87’ 28’
AN+500ppm - - 145’ - - 134’ - - 103’
Cu++
AN+500ppm - 155’ - 123’ - - 110’
Cr+++
PH after 8 hours
AN 2.84 2.92 2.50 2.85 2.94 2.48 1.96 1.94 1.84
AN+25 ppm Cl 2.80
AN+50 ppm Cl 2.58
AN+200ppm Cl 2.17
AN+500ppm Cl 0.82 1.40 1.20 1.49 1.92 1.52 1.54 1.56 1.53
AN+500ppm 3.01 2.93 2.62 2.98 2.90 2.54 1.98 2.00 1.82
Cu++
AN+500ppm 2.87 2.50 2.91 2.41 1.96 1.97 1.88
Cr+++
The graph below shows that :
-chloride from 0 to 200 ppm reduces

quickly the onset-time of AN at pH=3 and
225°c.
-500 ppm of chloride has same effect than
increasing the temperature by 20°c (from
225 to 245°c)
Influence of chloride on the onset-time of AN at 225°C-pH=3
1000
900
800
700
onset-time in minute
600
500
400
300
200°C
+
200
+
100
245°C +
245°C
0
0 100 200 300 400 500 600
chloride in ppm
Chloride is a stronger catalyst
than copper or chromium
Influence of pH and contaminants on the onset-time of AN at 245°C
300
250
200
AN
AN + 500ppm Cu++
150
ebefore5barsisreached
AN + 500ppm Cr+++
100
tim
50
AN + 500ppm Cl
0
2 2.5 3 3.5 4 4.5 5 5.5
pH 10%
Influence of temperature-pH and chloride on the onset-time of AN
300
250 AN + 500ppm Cl 200°c
200
AN 245°c
time before 5bars is reached
150
AN + 500ppmCl 225°c
100
50
AN + 500ppm Cl 245°c
0
2 2.5 3 3.5 4 4.5 5 5.5
pH 10%
Modification of the bomb test.
The pressure above the slurries is below the one

foreseen.
This is due to the fact that the bomb is not completely
submerged in the heating bath.
The results obtained up to now can not be used for
calculation as the confined space in equilibrium with
the slurry is not the one that we should have.
All the onset-time for decomposition are most probably
overestimated.
A new bomb apparatus will be used in the future.

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Confined space decomposition test of

ammonium nitrate fertilizers in

• In 1993 a decomposition occured in the manifold

• A test to accurately reproduce the decomposition of the

• 250gr of dry material is added in a closed

Before Trial After trial Temp.

Industrial 20 7.5 + 4.64 2.14 180

-The recipe containing MAP+AlS with a pH 10%

The conclusion made at that time to avoid any

Having shown it’s ability to reproduce a decomposition

Experience upto now :

Except the 20+11MgO grade without dolomite and a

• AN 85% decomposition : influence of temperature +

• The test is applied on AN 85% in the temperature range

-chloride from 0 to 200 ppm reduces

Influence of pH and contaminants on the onset-time of AN at 245°C

250 AN + 500ppm Cl 200°c

Modification of the bomb test.

The pressure above the slurries is below the one

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