AMMONIUM NITRATE

N. W a t c h o r n
I m p e r i a l C h e m i c a l Industries Ltd.
B i l l i n g h a m , Durham, E n g l a n d

At ICI, our range of compound f e r t i l i z e r s i s e r t i e s of s u c h f e r t i l i z e r s approach those of p u r e a m -

b a s e d on ammonium n i t r a t e and, t h e r e f o r e , in r e c e n t monium n i t r a t e . In g e n e r a l the wide range of N-P-K
y e a r s we have been doing r e s e a r c h work on the t h e r m a l f e r t i l i z e r s a r e not susceptible to this type of hazard,
stability of compound f e r t i l i z e r s based on ammonium but i t i s n e c e s s a r y to t e s t for this type of instability
n i t r a t e a s well a s the safety p r o b l e m s that a r i s e during b e f o r e a p r o j e c t to m a r k e t a new ammonium n i t r a t e
the manufacture and distribution of s t r a i g h t ammonium based fertilizer has progressed very f a r .
n i t r a t e f e r t i l i z e r i t s e l f . F o r the discussion to be useful
I think i t i s e s s e n t i a l to c l e a r l y differentiate between
the t h e r m a l instability p r o b l e m s a s s o c i a t e d with c o m - F u s e - t y p e reactions
pound f e r t i l i z e r s that contain ammonium n i t r a t e and the
s a f e t y a s p e c t s that a r i s e during the manufacture, s t o r - In r e c e n t y e a r s , i n the United States, Germany,
age, and distribution of f e r t i l i z e r ammonium n i t r a t e . and Holland, h a z a r d o u s incidents have o c c u r r e d in
The a r t i c l e by A. P a r k e r and myself (1) is which s e v e r a l thousand tons of compound f e r t i l i z e r
mainly concerned with the t h e r m a l instability of c o m - based on ammonium n i t r a t e have decomposed resulting
pound f e r t i l i z e r s . This i s a subject which h a s not r e - i n l a r g e clouds of toxic g a s e s sweeping a c r o s s the
ceived a g r e a t d e a l of attention in r e s e a r c h w o r k . In countryside and causing considerable c o n c e r n to the
r e c e n t y e a r s , the safety a s p e c t s of compound f e r t i l i z e r s local population. Even m o r e recently, a s you m a y r e -
based on ammonium n i t r a t e has caused a s much con- call, the S.S. Sophocles c a r r y i n g 6,000 ton of compound
c e r n to the international f e r t i l i z e r i n d u s t r y a s any of f e r t i l i z e r sank i n the Atlantic. We consider that these
the incidents involving f e r t i l i z e r ammonium n i t r a t e incidents w e r e due to what we t e r m fuse-type o r " c i g a r -
itself. burning" r e a c t i o n s which have not been p r o p e r l y under-
stood, to date, by the f e r t i l i z e r i n d u s t r y . A fuse-type
r e a c t i o n i s a specific f o r m of exothermic decomposi-
Aspects of t h e r m a l instability tion, which can self-propagate throughout a m a s s of
m a t e r i a l , and r e q u i r e s the p r e s e n c e of an oxidizing
T h e r e a r e five a s p e c t s of t h e r m a l instability of c h e m i c a l and a reducing o r catalytic agent. In c o m -
compound f e r t i l i z e r s which should be considered s e p a - pound f e r t i l i z e r s ammonium n i t r a t e a c t s a s the oxidiz-
r a t e l y since a formulation which shows one f o r m of i n - ing agent and potassium chloride, which i s p r e s e n t i n
stability m a y o r m a y not be i n e r t in other r e s p e c t s . f e r t i l i z e r s , provides the chloride ion which c a t a l y z e s
The f i r s t one, Type A, i s fuse-type r e a c t i o n s . the ammonium n i t r a t e decomposition.
This will be d i s c u s s e d in detail l a t e r . F i g u r e s 1 and 2 indicate what we mean by c i g a r -
Type B i s spontaneous decomposition a t high burning of f e r t i l i z e r s . F i g u r e 1 shows two compound
t e m p e r a t u r e s . This o c c u r s in a l l f e r t i l i z e r s b a s e d on
ammonium n i t r a t e and chloride if the whole m a s s of
f e r t i l i z e r i s r a i s e d to a high t e m p e r a t u r e . This type
of decomposition r e s u l t s f r o m the acidity that devel-
ops when these f e r t i l i z e r s a r e held above about 115°C
and i s c h a r a c t e r i z e d by an induction period whose d u r a -
tion depends on the t e m p e r a t u r e and p r e s e n c e o r ab-
sence of components which buffer the s y s t e m and p r e -
vent acidity f r o m developing. If inorganic f e r t i l i z e r s
a r e kept below' 115°C this type of decomposition i s
avoided.
Type C i s self-heating and mainly c o n c e r n s f e r -
t i l i z e r s which can become acidic and contain organic
i m p u r i t i e s . F r e e acidity m a y develop f r o m superphos-
phate in f e r t i l i z e r s and the subsequent oxidation of any
organic m a t t e r can cause a self-heating p r o b l e m . Sev-
e r a l p a p e r s in the p a s t have indicated how these prob-
l e m s can b e o v e r c o m e , in p a r t i c u l a r the mixing of o r -
ganic m a t t e r with any f e r t i l i z e r containing ammonium
n i t r a t e should be avoided.
Type D and E instability, i.e., explosibility and
oxidizing ability only become important a t l e v e l s of Figure 1. Cigar burning on a laboratory scale; initiation
about 8 0 % ammonium nitrate and above, when the p r o p - stage.
Figure 2 . Cigar burning of N - P - K fertilizer containing water
insoluble phosphate (left-hand tray) and nonburning formula-
tion (right-hand tray).

f e r t i l i z e r s being h e a t e d . In a c t u a l fact, the left-hand

one contains about 3570 while the right-hand s i d e one
contains about 50% a m m o n i u m n i t r a t e . While h e a t i s Figure 3. Standard test vessel for cigar burning ability and
applied both f e r t i l i z e r s d e c o m p o s e . F i g u r e 2 shows front velocity.
that when the s o u r c e of h e a t i s r e m o v e d the f e r t i l i z e r
on the right-hand s i d e , d e s p i t e i t s high a m m o n i u m n i -
t r a t e content, s t o p s decomposing. The one on the l e f t
s i d e though, once initiated continues to b u r n like a f u s e
d e s p i t e the f a c t t h a t t h e s o u r c e of h e a t h a s b e e n r e -
m o v e d . You c a n s e e that f e r t i l i z e r s s u c h a s t h i s p r e -
s e n t a p r o b l e m to the i n d u s t r y s i n c e if a c c i d e n t a l i n i t i -
ation o c c u r s due to a n y s o u r c e of h e a t , f o r e x a m p l e hot
m e t a l f r o m a welding o p e r a t i o n , the decomposition will
not b e r e s t r i c t e d to the l o c a l a r e a of initiation b u t could
r e s u l t i n the whole s t o r e of f e r t i l i z e r d e c o m p o s i n g . It
i s t h i s kind of t h e r m a l i n s t a b i l i t y that c a u s e d the i n c i -
d e n t s i n the United S t a t e s , G e r m a n y , and Holland p r e v i -
ously r e f e r r e d t o .

Test procedure
We d e s c r i b e d a t e s t p r o c e d u r e ( 1 ) f o r showing
whether any f e r t i l i z e r i s , o r i s not, a c i g a r - b u r n e r .
Using t h i s p r o c e d u r e a m a n u f a c t u r e r c a n go through
the m a t e r i a l s he p r o d u c e s and s e e if a n y a r e s u s c e p t i -
b l e to this type of h a z a r d . F i g u r e 3 shows the p r i n c i -
ple of the t e s t method. Decomposition i s initiated b y
b u r i e d e l e c t r i c light bulbs o r hot m e t a l b a l l - b e a r i n g s .
P u t t i n g t h e r m o c o u p l e s in d i f f e r e n t p o s i t i o n s i n the
velocity zone allows the r a t e of burning of the f e r t i -
l i z e r to b e d e t e r m i n e d . In o t h e r t e s t s we have a l s o
m e a s u r e d the r a t e of decomposition in the v e r t i c a l d i -
r e c t i o n w h e r e the hot decomposition g a s e s c a u s e
channelling and a f a s t e r r e a c t i o n .
F i g u r e 4 shows 'the a c t u a l a p p a r a t u s employed
a t ICI. I should point out that we think i t i s always
n e c e s s a r y to w o r k behind a sandbag b a r r i c a d e when
v e r y hot m e t a l i s being added to f e r t i l i z e r s containing
ammonium nitrate.

Figure 4 . Test procedure: initiation rig in charging position.

Liability to fuse-type reactions
F i g u r e 5 shows the r e s u l t s we have obtained i n
a study of f e r t i l i z e r s b a s e d on a m m o n i u m n i t r a t e , p o -
t a s s i u m c h l o r i d e , and a m m o n i u m phosphate. The zone
of f e r t i l i z e r c o m p o s i t i o n s that a r e l i a b l e to c i g a r - b u r n
i s shown b y the shaded a r e a . This shows that l i a b i l i t y
t o c i g a r - b u r n i n g i s not s i m p l y p r o p o r t i o n a l to a m m o -
nium n i t r a t e content, but the s u s c e p t i b l e f o r m u l a t i o n s
a r e r e s t r i c t e d to a well-defined a r e a bounded on one
s i d e b y the a m m o n i u m n i t r a t e - p o t a s s i u m c h l o r i d e edge
of the g r a p h . You c a n s e e t h a t if sufficient a m m o n i u m
phosphate i s p r e s e n t you g e t r i g h t out of the cigar-
burning r a n g e and get r i d of t h i s p a r t i c u l a r h a z a r d .
 &looPOTASSIUM
F i g u r e 5. C i g a r burning ability of N - P - K f e r t i l i z e r s b a s e d on a m m o n i u m n i t r a t e , p o t a s s i u m c h l o r i d e , and a m m o n i u m p h o s p h a t e .
We have also c a r r i e d out some work on other
formulations including some containing ammonium
sulphate and some in which the ammonium phosphate
i s replaced by calcium phosphates. Some details of
this work a r e given in our paper (1). -
P o r o u s structure
Basically what we have shown i s that for cigar-
burning to occur an ammonium nitrate content i s nec-
e s s a r y , a chloride content i s necessary and, thirdly,
the fertilizer must possess a rigid porous structure
a t the temperatures (200 to 500°C) involved in cigar-
burning. Not all fertilizer formulations containing a m -
DISCUSSION
GRAHAM- Tennessee Valley Authority. I r e a d your
excellent paper very recently and noted that you said
that it was very difficult if not impossible to put this
out with a jet of water.
WATCHORN: Yes, i f you t r y to penetrate a bulk s t o r e
of compound fertilizer, particularly one that i s decom-
posing, with water, what generally happens i s that a
c r u s t forms on the top and the water does not get down
to the r e s t of the material. Now cigar-burning i s a
chloride catalyzed decomposition of ammonium nitrate
and does not require a i r o r oxygen for i t s propagation
so it will continue below the surface and will not be put
out very easily. Remember, this i s not like normal
monium nitrate and a chloride have a suitable s t r u c -
ture and, therefore, not all of them a r e subject to
cigar-burning . As shown in Figure 5, the presence of
water soluble phosphates only r e s u l t s in a small range
of N - P - K formulations capable of cigar-burning.
Addition of ammonium sulphate o r water insoluble phos
phates r e s u l t s i n more rapid rates of burning and a
wider a r e a capable of cigar-burning.
LITERATURE CITED
1. P a r k e r , A. B., and N. Watchorn, "Self-Propagating
Decomposition in Inorganic Fertilizer Containing
Ammonium Nitrate," J . Sci. Food Agriculture (June,
1965).
burning, oxygen i s not required, there a r e no flames,
the main hazard a r i s e s from the toxic gases evolved
from the chloride catalysed decomposition.
In our paper we recommend that if you have a
fertilizer that i s a cigar-burner, you t r y and change
the m a t e r i a l s used so that you take the formulation out-
side the cigar-burning zone. If this cannot be done and
you have to manufacture a cigar-burner, we recom-
mend that it not be stored i n bulk but in bags with gaps
left between stacks of bags. In this way a cigar-burning
incident can be restricted to the small tonnage in each
stack. Since no flames a r e involved, this fuse type of
reaction cannot jump a c r o s s even a small a i r gap and
this i s a practical way of limiting the effect of any ac-
cidental local initiation of a cigar -burning formulation.
Anonymous: I s t h i s a s e l f - a c c e l e r a t i n g p r o c e s s ? Does
the r e a c t i o n a c c e l e r a t e a s t i m e goes o n ?
WATCHORN: T h i s i s not e a s y to a n s w e r f o r a l l f o r m u -
l a t i o n s , however, i n f e r t i l i z e r s b a s e d on a m m o n i u m
phosphate we did not find any tendency to a c c e l e r a t e .
At one s t a g e we w e r e w o r r i e d about t h i s . We wondered
w h e t h e r , a t the p r e s s u r e s that could b e envisaged in a
l a r g e bulk s t o r e , s o m e a c c e l e r a t i o n of the r e a c t i o n
might o c c u r . In o u r p a p e r we mention that we did do
burning t e s t s i n vented b o m b s w h e r e the e s c a p e of the
d e c o m p o s i t i o n g a s e s w a s r e s t r i c t e d . T h i s w o r k did
not s u g g e s t t h a t a n y a c c e l e r a t e d r e a c t i o n s would o c c u r
under the low p r e s s u r e conditions l i k e l y to o c c u r i n
n o r m a l land s t o r a g e n o r did i t s u g g e s t that a t t h e s e
r e l a t i v e l y low p r e s s u r e s a n o n - b u r n e r would b e c o m e
capable of s u s t a i n e d b u r n i n g .
SWAN-Sohio Chemical: Is t h i s type of behavior p o s s i -
b l e i n t r u e compound f e r t i l i z e r s o r blended f e r t i l i z e r s ?
A r e d r y blended f e r t i l i z e r s made f r o m t h r e e s e p a r a t e
components s u b j e c t to t h i s type of t h e r m a l i n s t a b i l i t y ?
WATCHORN: Both t r u e compound f e r t i l i z e r s and
blended f e r t i l i z e r s a r e s u b j e c t t o c i g a r - b u r n i n g and, i n
g e n e r a l , the a r e a of c o m p o s i t i o n s which a r e capable of
undergoing t h i s s e l f - s u s t a i n i n g d e c o m p o s i t i o n a r e s i m i -
l a r . I n the m a r g i n a l r e g i o n s however, on the b o r d e r of
the c i g a r - b u r n i n g a r e a , s o m e d i f f e r e n c e s will o c c u r .
B e c a u s e a blend obviously h a s a d i f f e r e n t s t r u c t u r e to a
compound f e r t i l i z e r of the s a m e a n a l y s i s s o m e d i f f e r -
e n c e c a n b e e x p e c t e d . In a blend the c h l o r i d e and a m -
m o n i u m n i t r a t e a r e i n l e s s i n t i m a t e contact, t h e r e f o r e ,
i n the c a s e of m a r g i n a l b u r n e r s , t h e r e will b e o c c a s i o n s
i n which the blend will not c i g a r - b u r n but the equivalent
compound f e r t i l i z e r would.