Straight ammonium nitrate fertilizer

stabilization:theoritical possibilities

 1. Physicochemical properties of pure ammonium nitrate.

 2. Definition of thermocycling and thermal stability.

 3. Legal requirements in Europe.

 4.The impact of thermocycling on AN based straight N fertilisers

quality.

 5. Ways to improve the thermal stability.

 6. Pro’s and con’s in selecting the optimal stabiliser.

1. Physicochemical properties of pure ammonium nitrate.

Solubility-critical relative humidity

high water solubility
exceptionally high temperature coefficient of solubility
Hygroscopic---> low critical relative humidity
Salt DeltaS/deltaT (20- Solubility (20°C) Critical relative
30°C) humidity (20°C)
gr per 100gr water gr per 100 ml %
solution
NH4NO3 4.9 66.0 66.9
NH4Cl 0.4 27.1 79.3
(NH4)2SO4 0.3 42.8 81.0
KNO3 1.4 24.0 92.3

solubility decreases with pressure-->caking during storage

atmospheric conditions cause moistening or drying

Mollier diagram including moistening and drying zone of AN

55

50
RH=40%
drying zone
45

RH=60%
40
te m pe ra ture in °c

RH=80%

35
RH=100%

30

25

moistening zone
20

15

10
0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04
gr H2O /kg dry air
Thermal conductivity

Low thermal conductivity

--> low thermal transfer during cooling in granules / prills

--> high temperature gradient in granules / prills
--> difference of temperature linked with change of volume causes
mechanical stress

Material Rate of travel of heat through material

Cal/(sec).(cm2.).(°C/cm)
Iron 0.161
Soft glass 0.0025
AN33.5 Kemira Tertre (0.35%H2O- 0.000208
density 0.965)
Fire brick 0.00028
Crystal forms:density, specific heat, heat of transition
Stable transitions.
AN is polymorphic and assumes 5 crystalline forms with different densities and
enthalpies
Every form, designed by a roman number, is stable over a certain temperature
range
During normal cooling, AN passes successively through the crystalline form I to V
The stable ofrm at ambiant temperature is the form IV
The change of crystal form occurs with a change of volume and heat of transition
Crystalline form Stable region Transition Transition Heat of
temperature transition
°C °C kcal/kg
Liquid 169.6
I Cubic 169.6-125.2 169.6 MeltI 18.3
II Tetragonal 125.2-84.2 125.2 III 13.2
III Orthorhombic 84.2-32.2 84.2 IIIII 4.0
IV Orthorombic 32.3- -16.9 32.3 IIIIV 5.1
V Tetragonal <-16.9- -16.9 IVV 1.4

Metastable transitions.

Form II shows a considerable delay during cooling to form III--->if cooling

proceeds too quickly, form II transforms immediately to form IV, by-passing form
III.
This transition occurs at 51°C and is explained by the close structure of forms II and
IV, form III being different from the others.
Heat of transition is lower : 5.56 kcal/kg instead of 9.11 needed for the successive
transitions II-->III-->IV but specific heat is higher in the metastable region to
respect the thermodynamic law
Crystalline Temperature range Specific Heat of Specific heat
form in which crystalline volume transition
form is stable
°C cm3/gr kcal/kg kcal/kg°K
II 84.2-51 0.603-0.598 0.441-0.431
IIIV 51 5.56
IV 51- -16.9 0.585-0.572 0.442-0.374
 Variation of specific volume for different crystalline forms of
ammonium nitrate according to temperature

0.72
m elt
0.71

0.7

0.69
specific volume cm3/gr

0.68

0.67

0.66

0.65
I
0.64

0.63

0.62
III
0.61 II

0.6
V II metastable
0.59
IV
0.58
IV metastable
0.57
-50 0 50 100 150 200

temperature °C

Specific heat of ammonium nitrate

0.5

I
0.48

0.46
specific heat kcal/(kg.°K)

II metastable II

IV metastable
0.44

IV 125.2°C

0.42

0.4

0.38
III
84.2°C
0.36
32.2°C

0.34
20 40 60 80 100 120 140

temperature in °C
The type of transition II-->III-->IV or II-->IV can influence the profile of
temperature of an AN fertilizer in a cooler

Influence of type of transition:stable (IV-->III-->II) and metastable (IV-->II) on the enthalpy

variation of ammonium nitrate with temperature

70
enthalpy variation in kcal/kg (hyp.: enthalpy=0 at 20°C form

60

50

II

40

metastable II
IV)

30

III
20

10

IV

metastable IV
0
20 40 60 80 100 120 140

temperature in °c

The choice of additive that increases or lowers the transition

temperature will also affect the temperature profile in a cooler
 Kinetics of transition : influencing parameters

 Transformations show delays by undercooling or superheating AN far away from its

transition temperature. This is done by entering quickly in the stability field of a
neighbouring crystalline form or when the amount of water is very low. The delay is
very much less when both phases are initially present.

The influencing parameters are:

the number of seeds
the humidity
the temperature gradient

The number of seeds:

The transition starts at points made of crystals that for any

reason haven’t changed during the previous transition in the
opposite direction. The number of pre-existing points depends
upon the temperature and duration at which the crystal was kept
before.
 The humidity:
The transition kinetic is increased by humidity:
the III-IV transition is realised through the intermediate of the solution:
dissolution-recrystallisation route.
Kinetic of transition III-->IV at 31.1°C

100.0
% o f tr a n s fo r m a tio n

90.0

wet AN
80.0

70.0

60.0

50.0

dry AN
40.0

30.0

20.0

10.0

0.0
0 50 100 150 200 250 300 350 400 450 500

time in minutes

The undercooling of dry AN is larger compared to wet AN : the AN cools

down before the kinetic of transition has got the opportunity to be in a
measurable magnitude
Influence of humidity on undercooling of ammonium nitrate transition
III-->IV

35

30 gr of AN dried at 150°C during 1h

34

s am ple poured 1-7 and 19 days in H2SO4 des s icator

te m p e r a tu r e in ° c

33
1 day heating at 45°c followed by s low cooling

32

31

30
7 days

29

28

27
19 days

26

25
0 20 40 60 80 100 120 140

time in minutes
The temperature:
The kinetic of transition increases with a broader difference of temperature
between the surrounding media and the crystal.

Influence of temperature on IV-->III transition kinetic on standard AN

450

35°c
g r a d u a t i o n o f d i la t o m e t e r

400

34.5°c

350

34°c

300

250

200

33.5°c

150

100

50 33°c

0
0 20 40 60 80 100 120 140 160 180 200

time in minutes

The curve obtained by the dilatometric method on granules represent a

combination of the kinetic of transition but also of the thermal transfer
from the granule to the external media.
Influence of temperature-humidity on the transformation speed at 32.1°C

250

Form IV Form III

m ax.wet AN

200
tr a n s fo r m a tio n s p e e d in % /h o u r

m in. wet AN

150

100

m in. dry AN

m ax. dry AN
50

0
26 27 28 29 30 31 32 33 34 35 36 37
temperature in °C
2. Definition of thermocycling and thermal stability.
Thermocycling = raising and lowering the temperature of discrete particles through the
phase transition temperature, of which the 32°C transition is the most significant in
practice related to conservation properties.
Thermal stability = preventing the deformation and cracking of the particles at phase
transition temperature such as 32°C.

Purpose of thermal stability = modify the handling and storage properties so that the
product may be safely stored for extended periods of time without development of dust,
caking or low density which increases the susceptibility to detonation.

Equipment: a climate chamber equiped with the following devices : cooling and
heating coils thermostatically controlled, a fan, a heating-cooling timer and a multi-point
temperature recorder.
A sample sealed in a container can be thermo cycled around 32°C or 84 °C several times
in a certain period of time. The example in the graph shows a 15-50°C cycle made in 6
hours.
Example of one thermocycling in a climate chamber:15-50°c during 6 hours

50

45

oven temperature phas e III

40
te m p e r a tu r e ,° c

AN temperature

35

30

phase IV
25

20

15
0 1 2 3 4 5 6

time inhours

Measures.

-The sample can then be further checked for caking, friability, hardness,
porosity, swelling, density…..
One can measure the percentage of unbroken granules/prills after each cycle.
Related tests and index.

 One can measure stability using the following parameters :

• stability limit for safety: maximum number of cycles

accepted by the granules before the density is reduced so
much that the product becomes detonable.

• stability limit for quality: maximum number of cycles

which reduce the initial hardness of granules at a hardness
too low for handling.

• inertia : number of cycles supported by the granules without

any modification of hardness.
 3. Legal requirements in Europe.
 Why is there a legislation on straight AN with more than 80% AN?

 AN has some tendancy to detonate which becomes apparent when it is

mixed with some form of carbon containing organic material.

 Several explosions have lead to a poor reputation for ammonium nitrate.

 Ammonium nitrate decomposes with an onset-temperature at about

200°C which may be lowered by certain sensitizing agents, such as
chloride ions, acidity, copper salts.

 The tendancy to detonate is favored by the porosity.

 The porosity is increased by cracking of the crystals during the crystal

transitions.

 This may lead to detonable material which would not have been
detonable before cycling.

 The EEC considers that it is necessary, especially to test ammonium

nitrate under the conditions in which it is being practically handled.

 Therefore, a detonation test is done not on the product as such but after
5 thermocycles.

 Regulations have been given fixing limits for porosity, pH, carbon,
chloride and heavy metals.
The EEC directive 80/876/EEC updated successively by the
87/94/EEC and 88126/EEC directives requests the straight
ammonium nitrate based fertilizer containing more than 28% N to
fulfill limits and characteristics of annex I-II in order to have the
EEC label.
These characteristics including thermal stability garantees the
safety of the fertilizer.

 Annex 1 :

 1. The porosity (oil retention) of a sample submitted to 2 TC from 25 to

50°C can not exceed 4% in weight
 2. The percentage of combustible material, measured in a carbon form,
can not exceed 0.2% for fertilizer >=31.5% N and 0.4% for fertilizers <
31.5% and >=28%.
 3. The pH of 10gr of fertilizer in 100ml H2O must be equal or above 4.5
 4. The fraction below 0.5 and 1mm can not exceed respectively 3 and
5% in weight
 5. Chloride is maximum 0.02% in weight
 6. Copper can not exceed 10ppm

 Annex 2 :

 The product can not be detonable after 5 thermocycles

 Method 1 : method to apply thermocycles

 cycle of 4  hours: 25 to 50°C

 4.The impact of thermocycling on AN based
straight N fertilizers quality.
 It is not only the risk of explosion or the decomposition that are important but also the problems
of degradation and caking due to hygroscopicity, low thermal conductivity and crystal forms.

 Impact of change of volume during cooling of a product showing increased density by

cooling.

When cooling is stopped --> temp.

equalisation starts --> increase
of temp. of the outside layers Thermal gradient is a
Temp. function of thermal
conductivity and
cooling rate

The external layer

core shrinks more rapidly than
the core--> tension in the
crust
crust

As further cooling of the core

proceeds, tension is gradually
relieved
 The II to III transition (84°C).
 This transition produces a volume expansion

The tension resulting

from the contraction The crust already
of the crust and below 84°C cools
expansion of the core Temp. down and contracts
is relieved by 90°C more rapidy than
formation of micro- 84°C underlaying layers
cracks and porosity
generating fines

core
Transition II-III

crust The sheet under transition

expands by 1.3% inducing
mechanical stress in the
crust

The III to IV transition (32°C).

This transition produces a volume contraction
of 3.6%-->less porosity is created
Impact on cooling processes:
 Fluidised bed: back-mixing of granules up and down
expose their oulet layer to varying temperature: no
damaging effect if it doesn ’t cycle through the 32°C
transition point
 drum cooler: advantage as product progress is
countercurrent to the cooling air in such a way that it
makes transition only once
 drum granulator: severe degradation occurs if
product leaving the granulator is below 84°C and is
reheated above 84°C in the drier
Product leaving the plant:
*During cooling, the saturated solution recystallizes on the
surface of the particles. This fixes them together by a solid bond.
Ex:1ton of AN 0.5% H2O at 40°C holds 14 kg AN in solution on
which 3.5 kg recrystallises on cooling to 25°C
*The fact that AN/CAN enters in the storage below 32°C doesn ’t
guarantee that the transition is complete. Due to poor thermal
transfer, the release of heat (5kcal/kg-->12°C) is used to increase
the temperature of the mass. The subsequent dissolution-
recrystallisation will promote caking.
5.Ways to improve the thermal stability.
As the change of volume causes breakage, many
experiments have been conducted to avoid transition in
the temperature range occuring during storage, handling
and use of the product.

This can be done by:

Increasing the transition temperature

minimizing the free water content
by deep drying
by addition of internal dessicants
additives binding crystal water
double salt formation
Suppression of transition III to IV
H3BO3-(NH4)2HPO4-(NH4)2SO4
Lowering the transition temperature
addition of cations that replace NH4+
 5.1 Increasing the transition temperature
5.1.1 Minimizing the free water content
by deep drying

As transition III-IV takes place by dissolution-recrystallisation,

the transition of dry AN at 32°C is replaced by a transition at
about 50-55°C.
It is conceded that it is the metastable transition II-IV
From 0.00 to 0.04% H20, transition increases from 32 to 50°C

Influence of water on the IV-->III transition temperature of pure

ammonium nitrate

52
te m p e ra tu re °c

47

42

37

32
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
water in %WT
 by addition of internal dessicants:
additives binding crystal water
clays
Stability obtained by additives taking up moisture from the surrounding
ammonium nitrate
Some inorganic additives bind reversively crystal water: aluminium sulphate
contains 18-16-10 or 6 moles of water depending of temperature.
m o le c u le s o f c ris ta l w a te r, n u m b e r

Al2(SO4)3.18H2O dehydratation

20

18

16

14

12

10

0
0 50 100 150 200 250

temperature,°C

Al2(SO4)3.17H2O

added in the AN melt as Al2(SO4)3.17H2O

amount of zeolithic water is function of AN melt temperature:165°C-->2-3
molecules of H2O
formation of white colloidal precipitate that reduces pH
aluminium additive starts to agglomerate above pH 6
formula most probable:Al2(SO4)3(NH4)2(OH)2(H2O)6-10
example:2% AlS binding 4 more molecules of H2O consumes 0.4% free H2O
 Mg(NO3)2.xH2O (x=4-6)

most popular inorganic salt

increases progressively the IV-III transition from 32 to 55°C and
the III to II transition from 84 to 90°C.
added in the AN melt in the form of MgO or MgO+HNO3
formula probable:(NH4)3Mg(NO3)5

Phase diagram for the anhydrous system NH4NO3-

Mg(NO3)2

160

140

120 NH4NO3 II
temperature °c

NH4NO3 II
100
(NH4)3Mg(NO3)5

80
NH4NO3 III

(NH4)3Mg(NO3)5
60

40
NH4NO3 IV

(NH4)3Mg(NO3)5
20
0 1 2 3 4 5 6 7 8 9 10

Mg(NO3)2 %wt
After the granulation, Mg(NO3)2 takes remaining water in the AN bulk
2% Mg(NO3)2 can take 1.09% H2O corresponding to 4.5 molecules of H2O
bound to Mg(NO3)2
when the capacity is exceeded, the transition temperature decreases rapidly
normally applied in excess to have an internal drying capacity
disadvantage:hygroscopic:CRH below 10%
p h a s e tr a n s itio n te m p e ra tu re °c

Phase transition temperature IV-->III;II as a function of the water

content for magnesium-ammonium nitrate (2%) prills

52

AN prills + 2% Mg(NO3)2

48

44

AN prills

40

36
0.01 0.1 1 10

water content %

Clays.

0.5 to 3% of porous inorganic substance with a particle size <100um

like alumina gel, silica gel, bentonite, attapulgite, zeolithes,
montmorillonite.

the effect is variable depending of the characteristic of the clay.

Blanco Attapulgite
Origin A Origin B Origin C
AN kg/t 771 771 771 771
Dolomite kg/t 229 214 214 214
Clay kg/t 15 15 15
Hardness N 52 100 62 67
After 10TC N 12 72 36 48
After 20TC N 4 50 9 17
After 30TC N 2 44 4 10
5.1.2 Double salt formation
Ammonium sulphate

Ammonium sulphate forms double salts: 3NH4NO3.1(NH4)2SO4

and 2NH4NO3.1(NH4)2SO4

3 cases considered in the phase diagram:

AS>5% molar
3<AS<5% molar
AS<3% molar melting point :169 to 176°C
transition I to II + 3AN.1AS:124 to 107°C
between 0-3% AS, transition III-IV:32 to 51°C

phase diagram pf NH4NO3-(NH4)2SO4 system

200
liquid + AS
liquid
180
te m p e ra tu re in ° c

160
I

140
I + 3AN.1AS

120

100

80
II + III + 3AN.1AS II + 3AN.1AS

60

III + IV + 3AN.1AS

40
IV + 3AN.1AS

20
0 1 2 3 4 5 6 7 8 9 10

NH4NO3 (NH4)2SO4 mole %

 5.1.3. H3BO3 0.2%-(NH4)2HPO4 0.2%-
(NH4)2SO4 0.01%
Patents granted in the sixties

5.2 Lowering the transition temperature

5.2.1 Addition of cations that replace NH4+
Solid solution of AN by substitution of NH4+
NH4+ radius = 1.43A°; substitute by ions having same radius:K,Rb,Tl,Ca
The influence of these ions is linked to their radius value:
IV--III and III-II transitions facilitated, and their temperature lowered if ion is
smaller than ammonium (K) and more difficult, and their temperature higher when
the ion is bigger (Ca,Tl)
KNO3:
K radius = 1.33A°
lowers the transition IV-III about 6°C for each percent
possible to render form III the stable form throughout the range of normal
temperature:amount needed 5-10%--> reduce the cooling needed

Phase diagram of NH4NO3-KNO3 system

180

liquid

160
te m p e ra tu re in °c

I
140

120

II
100

80

III

60

40

IV

20
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

NH4NO3 KNO3 mole %

 6. Pro’s and con’s in selecting the optimal stabilizer
 The selected additive should fit the best with the following requirements  :

 -prevent thermal shock and cracking at phase transition temperature during the process
and storage.

 -be efficient at low amounts.

 .important in concentrated 34.5%N grade where there is no place for a filler.
 .additives working in combination can reduce the total amount :AS +AlS
 .additives containing N add value : magnesium nitrate, ammonium sulphate…..

 -incorporated in the molten ammonium nitrate prior to solidification. Advantage is that it

is better distributed in the mass.

 -inexpensive : clays are inexpensive if sources are close to the plant ; the same for AS if a
waste material is available (needs to be pure enough).

 -readily available at production sites. This is especially the case when it is part of the used
materials or by-products at fertilizer complexes like silicofluorides, phophatic shales…

 -safe : Aluminium sulphate is suspected to promote Alzheimer’s disease.

 -simple to apply 

 -improve the physical properties of the particles : increase the density, the hardness ;
acting as a binding agent during the granulation.
 doesnt ’t bring disadvantages : Some additives increase the hygroscopicity of AN so
much that they are inappropriate in case of bulk storage in a humid atmosphere.
 Summary of pro ’s and con ’s of some additive.

Usual amounts Thermal Physical Hygroscopicity

stability quality
Al sulphate 1-2% ++ Improve
hardness,
granulating
agent
Mg nitrate 2% +++ No caking, -- inappropriate to
improve bulk storage
hardness without special
coating
Boric 0.4% +++ More resistant Slightly less
acid+phosphate to caking, hygroscopic
s+AS lower friability,
improve
hardness,
reduce
sensitivity to
humidity
KNO3 5% +++
AS 5% ++ Improve +
hardness
K2SO4 5% +++ No effect on
hardness
Ammonium Little
phosphates practical
experience
Clays 0.5-3% ++ depending Improve
on clay hardness, acts
characteristic as granulating
s agent
Summery of pro ’s and con ’s of some additive.
Particuliar effect Saf ety Impact on N Cost
content
Al sulphate -bound water -sensitive to Reduce the N +
depending of high content
AN melt pH :agglomerate
temperature above pH 6,
-lowers the pH
of AN melt
-Alhzeimer
Mg nitrate NO3-N value Less costly if
from
MgO,MgCO3
Boric Increased -Low amount of
acid+phosphates porosity additives
+AS needed.
-doesn’t affect
the N content
KNO3 Reduce the NO3-N value +++ loss of K
cooling needed
by stabilising
form III instead
of IV
AS NH3-N + S Low if waste
value from
caprolactam,
cokery…industr
ies available
K2SO4 ++, loss of K
Ammonium NH3-N value ++, loss of P
phosphates
Clays Contains often Variable
carbonates
acting as pH
buffer