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Liquid Phase Relationships in

Fertilizer Granulation by a Layering Process

P . 1. SHERRINGTON

Imperial Chemical Industries Limited, Agricultural Division, Billingham, U.K.

In certain variants of the fertilizer granulation process Dans eertaines variations du proc6d6 de granulation des
granulation occurs by deposition of a layer of raw material engrais, celle-ci se fait en dCposant une couche de la
onto a previously formed nucleus. An expression for the matiere premiere sur un noyau form6 prhalablement. On
liquid phase required for layering as a function of the a mis au point une expression mathimatique pour la phase
proportion of nuclei present has been derived from a liquide requise pour deposer la dite couche, laquelle est
simple model of the layered granule and tested against fonction de la proportion des noyaux presents et provient
laboratory simulation experiments on glass beads and sand. d’un modele simple d’nn granule enduit; on en a fait
The expression is applied to fertilizer granulation to define l’dpreuve dans des experiences semblables qu’on a faites
the range of conditions over which layering is possible and au laboratoire sur des grains de verre et du sable. On
the recycle ratios required as a function of fertilizer applique l’expression B la granulation des engrais pour
solubility and the water entering the granulator. Layering indiquer les limites dcs conditions auxquelles on peut
requires a higher recycle ratio than the corresponding dkposer une couche de la matiere premiere et les t a w de
agglomeration process, but in general gives product with reeyelage requis d’apres la solubilite de l’engrais et I’eau
better storage properties and shorter drying time. The qui entre dans le granulateur. La deposition d’une couche
economics of the process depend on the saving in drying sur le noyau exige un taux de recyclage plus ileve que danu
costs compared to the cost of extra conveying equipment. le cas du procedc5 d’agglomkration correspondant, mais elle
Modifications to the basic process to improve its economics permet gendralement I’obtention d’un procedk qu’on peut
are considered briefly. entreposer d’une maniere plus satisfaisante et qui seehe
plus vite. L’Bconomique du proekde depend de 1’8pargne
qu’on peut realiser dans le coat de sechage en comparaison
F ertilizer granules can be formed by one of two mechanisms.
In one of thc;e, agglomeration, the granules are composed
of random aggregates or agglomerates of raw materials and
du coat de l’outillage additionnel de transport. On consi-
dere briivement des modifications au proekde de base pour
le rendre plus bconomique.
recycle particles. In the other mechanism the granules grow
by depxition of one or more layers of the raw materials onto
LIQUOR
a previously formed nuclcus, usually a recycled particle. This
second mechanism is known as layering or onion skinning. SLURRY

Both processes can occur simultaneously in a granulation system


with some of the granules growing by each mechanism but, in
I - 1 I
-- I

general, one or other of the mechanisms will predominate.


In commercial fertilizer production the agglomerative mechanism
usually predominates, but in certain instances layering becomes
IIRECYCLE
the more important, as for example in the production of diam-
moniuni phosphatc as described by Magnati et al.(’) and the
Dorr process(”. -
SCREENS
In the course of rcscarch and development work on a range
of fertilizer formulations it was found that under certain con-
ditions somc formulations showed a marked tendency to enter ,I

the layering regime. ,4s the properties of the granules produced PRODUCI GRADE
--
and the running conditions required for stable plant operation
were appreciably different from the corresponding agglomerative 4
PRODUCI
regime, it was decided to investigate in more detail the con-
Figure 1-Outline of the granulation loop.
ditions tinder which layering could become the predominant
mechanism. A simplified diagram of the Branulation loop is
prescntcd in Figure 1 . Of particular interest rom the vicwpoints
of plant design and process economics is the ratio of recycle to
Model for the Layered Granule
product (recycle ratio) required for stable plant operation. W c In our granulation process there is no provision for drying
had already obtained a reasonable understanding of the relation- in the granulator and each nuclcus takes up only one layer of
ship bctween liquid phase and granule size which governs the raw material per pass through the granulator. ,4 simple model
recycle ratio required for agglomeration. This result has been of such a granule is shown in Figure 2. T h e nucleus is a spherical
presented previously(3). In this paper similar reasoning is applied particle round which is packed a layer of smaller solid particles
to the layering case. of raw material (grains) which adhere to each other and to the

308 The Canadian Journal of Chemical Enlineering, Vol. 47, June, 1969
Figure 2-Model for a layered granule.

nucleus by means of the capillary forces set up in the liquid phase


contained in the pores between the grains. Let us assume that
the pores between the grains are saturated with the liquid phase Figure 3 -Layered granules made from glass beads and
derived from the liquor and/or slurry fed to the granulator. sand.
This condition can be shown to lead to maximum strength(".
Because the nucleus is porous there is opportunity for the liquid
to penetrate into the nucleus to some extent as indicated by the
shading in Figure 2. where x is the fraction of the available pores in the nucleus which
Suppose that we start with a weight W and a number N is filled by the liquid phase, i.e. the degree of ingress of liquid
of nuclei which are granulated together with a weight W / L of into the nucleus. Substituting for V and V' and putting k =
X/u and k' = X'/u' gives
grains to give N layered granules. Let the grains in the layer
pack so that the volume fraction of voids in the layer is 1 and
the volume fraction of solids is u. Similarly let the volume Y =
p'k + Lpxk' . . . . . . . . . . . . . . . . .
fractions of voids and solid in the nucleus be A' and 0'. If the P' + LP
nuclei have a diameter d and the granules a diameter D then the Equations (5) and (7) give expressions for the average granule
volume V ' of a single nucleus is given by size and average liquid phase content in a layering granulation
system. If the nucleus is not porous Equations (5) and (7)
become

where p' is the density of the material comprising the nucleus.


D = d (1 4- &)".
The volume V of the layer is and
y = - p , P'k L p . .
+ ......... , (9)
.(2)
The Size of Nuclei
where p is the density of the grains. T h e feed to a granulator consists of a continuous range of
The total granule volume is particle sizes. With increasing size there will be an increased
tendency for particles to act as nuclei rather than enter into the
V'+ v = 7rD
- = - -+-
6
3

E(u!p' L:p)
. . . , . . . . .( 3 ) layer surrounding another particle or agglomerate together.
The classification into layering material and nuclei, albeit
useful, is inevitably arbitrary. T h e tendency for particles to
The ratio of the final granule volume to the volume of the nucleus adhere will depend on the relationship between the strength of
is the surface tension forces binding them together and the inertial
forces in the granulator tending to separate them. Although
expressions have been derived for the strength of wet granulesc4*6,
there is so far no treatment of the inertial forces in a granulator.
and thc h a 1 granule diameter is In order to determine the size above which a particle will
act as a nucleus it is helpful first to calculate the grain size at
which a granule will collapse under its own weight. Consider
a spherical granule of radius nr composed of uniform spheres of
radius r. Newitt and Conway-Jone~(~) obtain for the load B
The ratio of the liquid volume to the total solid volume, y, is required to break the granule
given by*
xv 4- X X ' V . . . . . . . . . . . . . . . . .( 6 )
y = uv+u'V
For the granule to collapse under its own weight
*The reduction in liquid phase due to withdrawal of the liquid phase into
the interstices between the outermost layer of grains which is important B = 47rn3r3p"g/3, . . . . . . . . . . . . . . . . ( 1 1 )
in agglomeration is neglected here. It is approximate!y balanced by the
decreased packing density of the grains in the layer in contact with the
surface of the nucleus. where p" is the density of the granule and

The Canadian Journal of Chemical Engineering, Vol. 47, June, 1969 309
100 I- 100 -
90

80

70 -
-
- I
II

I
2
p/,
I/
90 -

80

70
-

a
Y

60-
V
5 50-
b

*:Li
L 40
0 "-024
0 0.26 ~
I
a y -027 I
0 7 -. 0-28
I
20
I0 0 9-013 I
I
0 "-021 I
I I + r-023 I
I I + I I
01 I I I I 1 1 1 1 1 I 1 I ! I I I I I I J I I I I I I l l 1 I I - - . L U
01 0.2 0.3 D4 0.5 W 08 1.0 2 3 4 5 6 8 1 0 01 02 03 04 0506 09 10 2 3 4 5 6 8 10
mm rnm

Figure &-Size grading curves for the granulation of sand. Figure 5-Size grading curves for granulation of 70% sand
Starting material X +
30% glass beads.
Liquid phase Starting material X
Volume ratio
Solid phase Liquid phase
Volume ratio
Solid phase

An approximate idea of the size of sphere at which formation of between 3 mm. diameter beads were insufficient to retain thc
a granule becomes impossible may be obtained by solving liquid phase within the tumbling mass of beads.
Equation (12) for the case n = 1, substituting typical values of Experience of layering fertilizers on the pilot plant scale
T = 80 dynes/cm., k = 0.35 and p = 2 g/ml., to give a value indicates that the lower limit for size of nucleus is about 0.7.-
of r = 0.6 cm. From this we deduce that particles of radius 1 mni. It is common knowledge among fertilizer plant operativcs
greater than approximately 0.6 cm. will always act as nuclei that pin-head granules in this sizc range arc extremely difficult
rather than agglomerate with each other. In practice, granules to granulate by agglomeration.
will have to withstand considerably higher forces than those
due to their own weight and it will therefore be difficult if not Laboratory Experimental Work
impossible to form stable granules from spheres more than a
few millimeters in diameter. T o test the predictions of the model in the laboratory a series
This conclusion appears to be borne out in practice. Capes(6) of simulation experiments using glass beads as nuclei and sand
finds that at low liquid contents (the condition of interest in as the layering material were performed. Grade 3 glass ballotini
fertilizer granulation) the limiting size to which granules of supplied by the English Glass Co. Ltd. were used as nuclei.
fine sand will grow by agglomeration is of the order of 1 to These had diameters in the range 1.2 - 1 . 5 mrn. and readily
2 mm. after which the mechanism switches to growth by layered to give granules in the desired product size range of
1 . 5 - 3 . 5 mm. Sand from a local sand pit from which all particles
layering. At high liquid phases the limit is increased to about
5 to 6 nim. but in this case the granules are more plastic and larger than 18 B.S.S. had been sieved out was used. The sand
granule deformation is a contributory factor. In the course of grading is given in Table 1. The sand was thoroughly washed
this work an attempt was made to locate the maximum size of before use.
glass sphere which would form granules in a laboratory drum Charges of 500 g. of mixed beads and sand were granulated
granulator. Various grades of ballotini were investigated ranging for 4 minutes in a drum granulator at room temperature using
from 0.5 mm. to 3 mm. diameter. No well defined spherical saturated ammonium nitrate solution as the liquid phase. Thc
granules could be formed with any of the beads. However drum was 6-ins. in diameter and 9-ins. long and rotated at 5 5
some evidence of aggregation to form lumps was shown by the rpm. T o increase wall friction and ensure a proper cascading
snialler grades of bead. This had almost ceased by the time action the drum was lined with 100 B.S.S. stainless steel mesh.
the beads were 1.2 - 1 . 5 mm. in diameter. The capillary forces The granules were dried in an oven and graded on a set ot
British Standard sieves. Afterwards the ammonium nitrate was
washed out of the granules, the beads were separated, dried
and re-used. T h e gap between the top end of the sand sizc
TARLE1 grading (0.85 mm.) and the beads facilitated separation by
SIZEGKADING
SAND sieving. Figure 3 shows a magnified photograph of some granules
with a portion of the sand layer scraped away to show the layered
British Standard Sieve w t % less than grade structure.
Experiments were done on sand/bead mixtures in ratios:
100:0, 70:30, 60:40, 50:50, 40:60, 30:70 and 1S:HS. Size
18 100.0
25 96.1 grading curves for the experiments with 100:0, 70:30, and
36 85.9 40:60 mixtures are shown in Figures 4, 5 and 6.
52 63.8 There is a marked difference between the grading curves
72 40.6
100 20.4 after granulation with and without the glass beads present.
150 5.0 The curves in Figure 4 for sand alone show the typical behaviour
200 1.9 of granulation by agglomeration. A steadily increasing amount
I
of oversize is formed with increasing liquid phase content.

310 The Canadian Journal of Chemical Engineering, Vol. 47, June, 1969
--O- LAYERING CURVE CALCUUTED F R W EQN.19)

MEASURED MEAN GRANULE DIAM.


GSANULE DIAM. FROM EON.

5
3 0.20-

I
y 0.18 -
Y

E 0.96
0
9 0.16 - o,94 1.03
- 0
01 02 03 04
' '
0506
1 '
08
"
10
I ,
2 3
I
4 5 6
I
8 1 0
e
mrn
0.93 m
Figure &Size grading curves for granulation of 40% sand
+
60% glass beads. mm&
Starting material X
Liquid phase
Volume ratio
Solid phase

O ' I
0.02

With the beads present oversize production is very small at I I I 1


first and the principal effect of adding increasing amounts of 1 2 3 4 5 6
L WEIGHT RATIO OF NUCLEI 1 0 GRAINS
liquid phase is to stick more sand to the nuclei. When the
amount of liquid phase required to stick on all the sand is Figure 7-Test of Equation (9).
exceeded there is a rapid increase in oversize production.
Adding the beads increases the maximum proportion of product
grade granules which can be made from 42% to ca. 80%. The In some experiments the number of nuclei per granule in
maximum proportion of product grade and the liquid phase granules of different sizes was determined. The granulated
required to achieve it, calculated by interpolation, are shown in material was separated into several size ranges and the granules
Table 2. Maximum yield is not greatly affected by the pro- in each size range were broken down by dissolving out the
portion of beads present. The liquid phase content at which the nitrate. After drying, the sand and beads were separated, and
maximum yield is obtained, however, decreases steadily with the average number of nuclei per granule in the various size
increasing proportion of beads. ranges calculated. The results for two mixtures are shown in
The principal factors governing the maximum yield are Table 3 . With 60% of beads there is a tendency for some of the
the efficiency with which the layer adheres to the nucleus and the larger granules to contain more than one nucleus even at low
quality of the mixing in the granulator. Visual observation and
the shapes of the grading curves indicate that adhesion of the
sand to the beads was incomplete. Investigation of the size
grading of the sand left out of the layers showed that it was TABLE
3
appreciably coarser than the starting material. Adhesion could
probably have been improved by using material of finer size AVERAGENUMBER OF BEADSPER GRANULE
I N VARIOUSSIZERANGES
grading to fomi the layers. Capes(?) has recently pointed out
the need for perfect mixing to ensure uniform layer thickness on
the nuclei. Granule Size Range
Y

I I

TABLE2
YIELD
MAXIMUM GRADE
60% beads + 40% sand
C O N U l T l o N S FOR OF PRODUCT
- 1 .o 1 .'I 1.1 -

1 1 1 1 1
~-
0.087
___-
I I 0.109 1 .o 1 .o 1.4

~ ~ ~ ~ ~ + 'Lo' ~ t::~ , ~ :
Vol. ratio of
Maxim um 0.152
0'13' 6il 1u.6
hlixtiire liquid phase for
maximum yield granules 30% beads 70% sand

lOOy, sand
70% sand + 3OLj; beads
0.265
0.21
42
79
0.148
n. 169
I 0.9
0.7 I :::I IT0 1 1 1 -
-

60% sand + 4O%, beads 0.175 78


50% sand + SOY, beads 0.15 80
40% sand + 60% beads 0.11 81

The Canadian Journal of Chemical Engineering, Vol. 47, June, 1969 311 *:
0 4

0 A $.

1.005
6

SATURATED NUCLEUS x.1 2 0 I 2 3 4 5 6 7 8 9 10


8 02 Q R - RECYCLE RATIO
Q
3
I . 3

0.1

NON.PORMS NUCL
I I
0 1 2 3 4 5 6 7 8 9 10 0 2 4 6 8 10 I2 14 I6 I8 20
L-WT. RATIO OF NUCLEI TO GRAINS -
R RECYCLE RATIO

Figure 8-The effect of penetration of the liquid phase into Figure 1 0 4 r n p h i c a l solution of the layering equation.
the nucleus on the amount of liquid phase required for
layering.

Y O
-
E
j
3 0.1
$
0
z
m
5 0.2
I
I
8 ALL RAW MATERIALS
IN LIQUID PHASE
603 0001
t 0 2 4 6 E 10 I2 14 16 I0 7L
RECYCLE RATIO

04 Figure 11-Thickness of the layer at various recycle ratios.


Figure 9-The dependence of the recycle ratio required for
layering on fertilizer solubility and the water entering with
the raw materials. Extrapolation of the data for 100% sand in accordance with the
equation
y = k ( l - 3 L p ) . . . . . . . . . . . . . . . . . .(13)

liquid phase contents. Once a critical liquid phase content is derived previously(3)for granulation by agglomeration gives k =
exceeded oversize granules are formed by agglomeration and 0.31 and u = 0.76. The measured densities were p = 2.65
contain several glass beads. When the proportion of beads is
lower at 30%, under certain conditions some of the smaller
g/ml. for the sand and ,I'
= 2.97 g/ml. for the beads. Thc
results indicate that the curve givcn by Equation (9) is a good
granules are formed by agglomeration of sand. When the critical description of the liquid phase required for layering.
solution phase is exceeded the oversize granules still only contain
one nucleus. Application to Fertilizer Granulation
For an ideal layering system the size distribution of the In fertilizer granulation the nucleus is porous and this has an
granules can in principle be calculated from an assumed law important effect on the liquid phase required for layering. To
governing the deposition of the layer, e.g. that each granule estimate the extent of penetration into the nucleus we fitted
picks up a layer of equal thickness. However, failure of the results for a formulation which had shown pronounced laycring
layering material to adhere completely and the simultaneous behavior in the pilot plant to the modcl outlined previously.
occurrence of some agglomeration complicate the calculation The value of k', the porosity of the nucleus, was estimated from
considerably and no expression for the distribution of sizes has mercury density measurements on the granules. The result
been derived. obtained was x = 0.26 which, assuming uniform distribution of
In order to assess the extent to which layering was achieved porosity within the nucleus and a nucleus diameter of 2 nirii.,
at any given liquid phase content, the measured average granule implies that the liquid phase penetrates to a depth of 0.1 mni.
size was compared with that calculated from Equation (8). from the surface. One would expect the value of x to depend
D measured on the residence time in the granulator. We have found that the
In Figure 7 we have plotted the ratio as a function value of 0.26 can be successfully used to predict the recycle
D calculated ratio required for layering other formulations on the same pilot
of y and L. A value greater than unity indicates agglomeration; plant. The effect of the value of x on the relationship betwecn
less than unity indicates that not all of the sand has adhered to y and L for layering is shown in Figure 8 where curves are
the nuclei. The solid curve is calculated from Equation (9). plotted for x = 0, x = 0.26 and x = 1.

312 The Canadian Journal of Chemical Engineering, Vol. 47, June, 1969
x20 x20
Layered Agglomerated
Figure 12-Layered and agglomerated layered granules pro-
duced on a full scale plant. Figure 13-Agglomerated and layered
granules produced on the pilot plant.

The nuclci for layering in general come from the recycled If in addition x = 0 one obtains
particlcs. If the proccss is truly layering, crushed oversize will
be only a minor constituent; most of the recycle will consist of k z (1
=--
+ s ) P/
................
returned undersize, and, as we shall see later, returned product I - 2s ps
grade matcrial. If the recycle contains an appreciable proportion
of material less than approximately 0.7 mm. diameter this should Equation (18) expresses the result that provided the watcr
be allocated to the layer, but in what follows we shall neglect entering with the raw materials is so adjusted with respect to the
this possihility. Unless coarse or granular raw materials are fertilizer solubility that a paste can be formed from the raw
used, the raw materials will contribute only to the layer. The materials such that the pores between closely packed solid
raw materials will be divided betwcen the grains and the liquid particles are just saturated by the liquid phase, then this paste
phase in a proportion decided by the solubility of the fertilizer can be spread over any convenient number of non-absorbent
at the granulation temperature and thc amount of water entering nuclei. However, in practice it is rare that this desirable state
with the raw matcrials. (It is assumed that part of the raw of affairs is achieved and it is useful to bc able to use the nuclei
materials enter the granulator as a solution or slurry and no to absorb excess liquid phase. This restricts the recycle ratio
further water is added for granulation). I f the weight ratio of which can be used to that describcd by Equation ( 1 7 ) .
fertilizer to water in a solution of the fertilizer at the granulation To explore the implications of Equation ( 1 7 ) we have sub-
temperature is s, and the weight ratio of water to fertilizer in the stituted some typical values for the various parameters. These
incoming raw materials is z, at a ratio of recycle to dry raw values are listed in Table 4. T h e variation of recycle ratio with
materials of R, we have fertilizer solubility and water entering with the raw materials
is shown in Figure 9. Some limits to the range of application of
L=- R .................... (14) the equation are found. The limit for Equation ( 7 ) is y = k
1- 2s
when L = 0. This implies that if the water entering with the
The liquid phasc ratio in the granulator is given by raw materials is insufficient to create enough liquid phase to
fill the voids between the solid particles granulation cannot
VJ ( 1 + s ) P/
................. occur. However, previous work on agglomeration(3) shows
y=--- that because of surface dryness effects, neglected in the deriva-
( 1.- ws) PI
tion of Equation ( 7 ) , granulation by agglomeration can occur
wherc -LT is the weight ratio of water to fertilizer in the granu- at liquid phase contents below this. Equation (13) describes
lator, pf is the density of the fertilizer and ps the density of the the liquid phase required for agglomeration. Assuming an
fertilizer solution. .4 mass balace across the granulator gives average particle size of 0.5 tnm. for the raw materials and a
desired average granule size of 2.5 mm., Equation (13) gives
VJ=- R +e .............. y = 0.26 as the limit for granulation by agzlomeration. Below
this there is insufficient liquid phasc for any granulation to
It is assunicd that the water present in the recycle has no effect
occur. In order that layering should be able to predominate
on the layering system. This will be so provided that the over agglomeration a certain minimum proportion of nuclei
must be present. No attempt was made to locate this minimum
recycle is suficicntly dry that thc water already present in the
nuclci has no cffect on thc limited ingress of liquid phase into since it is unlikely to be well defined and, although it is of
the nucleus. l,'.quations (l4), ( I 5) and ( 1 6) can be combined considerable interest from the viewpoint of granulation thcory,
it is of little practical importance. In the siniularion expcriments
with Ilquarion ( 7 ) to give a relationship betwecn the recycle
described earlier the lowest proportion of bcads used was 30%
ratio rcquircd for layering, thc solubility of the fertilizer, and
the watcr entering with the raw niatcrials. For the casc that corresponding to I, = 0.43. I t is probable that one cannot go
much lowcr than this and still achieve layering. \Ve have taken
p' = p, which is generally true for fcrtilizer granulation, the
this as the lower limit for layering in Figure 9 . The hatched
result is
area between y = 0.26 and L = 0.43 we have de.;ignated the
2 PI k
R = -- - (1s~) -, - -,
x k ps
+kzs
xk xk
agglomeration region. I t should be eniphasised, however, that
whilst layering cannot occur inside the agglomeration region,

The Canadian Journal of Chemical Engineering, Vol. 47, June, 1969 313
agglomeration can occur outside this region. However, under
suitable conditions outside this region layering can be made to
be the dominant mechanism. The final limit is reached when in 50 I
Equation (14) zs = 1, i.e. the water entering with the raw
materials is sufficient to retain all of them in solution at the granu-
lation temperature. Beyond this the model must change to one
in terms of the stable thickness of a liquid film on the surface of
a sphere; its validity becomes doubtful before its limit is
reached.
q
40

z 30
Y I
I x /
Within the layering region the recycle ratio required rapidly
increases with increasing fertilizer solubility and increasing
water entering with the raw materials. Recycle ratios in excess
of 10: 1 are rapidly required. When the fertilizer is very soluble
the recycle contours come closer together and it is probable
that accurate control of the water entering would be required
for stable plant control.
'4lthough the equations can be solved to give the required
lot
O
0
U
01
/ /'
02 03 04
I
0 5
I
06
1
07
I
08
I
09
I
10
recycle ratio directly, it is also instructive to solve them graphi- MOISTURE CONTENT OF GRANULES (WT 2 )
cally. Vquations ( 7 ) and (14) are combined to give the solution
phase required for layering as a function of recycle ratio - the Figure ILLaboratory caking tests on layered and agglo-
layering curve. Combining Equations ( I S ) and (1 6) gives the merated granules manufactured on the pilot plant.
solution phase in the granulator as a function of the recycle
ratio - the operating curve - for a given water input with the
raw materials. (For completeness the heat balance across the
granulator at various recycles should be included in the operating the same starting materials. The two are compared in several
curve to allow for thc effect of changing granulator temperature cases in Table 5. The recycle ratio for agglomeration has bccii
on fertilizer solubility. This, however, has been omitted from calculated by combining Equations (1 5) and (1 6) with l:xquation
these generalised calculations). The point of intersection of the ( 1 3 ) . Values of parameters required in Kquation ( 1 3 ) arc
two curves gives recycle ratio required for layering. Examples listed in Table 4.
of this approach for two different sets of conditions are given in
Figure 10. It can be seen from these that the operating and Plant Operation in the Layering Regime
layering curves approach quite closely before the point of In the previous section we have shown the need for high
intersection is reached. Because of this it is possible to operate recycle ratios in order to satisfy the water balance requirenicnts
a process at recycle ratios one or two units lower than given by for fertilizer granulation by layering. Also, layering gives a
Equation (17), which is mainly layering but with a limited
high proportion of granules in the product size range. It is
amount of agglomeration also occurring. therefore necessary, if plant opcration is to be atable, to have
The layer thickness as a function of the recycle ratio is some device for limiting the rate of product leaving the plant
illustrated in Figure 11. Equation ( 5 ) has been solved on the to balance the raw materials input. Excess product-size granulcz
assumption that the average final granule diameter D is 2.5 mm. are recycled to the granulator together with the fines stream.
using the parameters listed in Table 4. The layer thickness The recycled product grade granules make excellent nuclei.
decreases very rapidly with increasing recycle ratio. Solids
Furthermore, as Equation (5) implies, the granule is not
deposited from a solution or slurry can form very thin layers much larger than the nucleus. Because of this the bottom screeti
but solid raw materials, unless they are very finely ground will mesh has a controlling influence on the final granule size which
obtrude from the surface of the layer and as the recycle ratio is slightly larger than the mesh size. To get an average granule
increases will become increasingly difficult to stick onto the size comparable to that obtained by agglomeration it is necessary
nucleus. As the layer becomes very thin the approximation of to increase the bottom screen mesh aperture. As therc is a very
regarding the grains in the layer as having a constant porosity high proportion of product grade material, reducing the product
equal to that obtaining during agglomeration becoines question- size range in this way does not affect output. The larger sizc
able. At high recycle ratios it is likely that the layers will not recycle particles act more efficiently as nuclei.
be uniformly deposited over all of the nuclei. The model
described above is probably only valid up to recycle ratios of
CU. 10: 1 but will give useful indications above this.

Finally, it is instructive to compare the recycle ratios re-


quired for layering with those required for agglomeration using
TABLE
5
COMPARISON BETWEEN THE IIECVCIL RATIOSREQUIRED f. O K
LAYISRING
A N D AGGLOMERATION
__ -____
TABLE4 I I I
VALUESOF GRANULATION
TVPICAL PARAMETEKS Recycle
~

ratio for
k = 0.35 materials agglomeration
u = 0.14
k' = 0.18
U' = 0.85
0.05
0.05
I 5
I
3.3
7.1
2.2
3.0
x = 0.26 0.10 I 3 6.6 3.0
p = p' = pj = 1 . 8 g/ml. 13.9 4.5
21.4 6.0
p, = 1 . 3 g/rnl. 5.8 2.9
p = 0.5 19.2 5.9

-
t = 0.3 0.30
l 1 12.5 4.3

31 4 The Canadian Journal of Chemical Engineering, Vol. 47, June, 1969


In our pilot plant work it was found that a transition from the Layered granules of one formulation took slightly lon er to
agglomerative to the layering regime could be achieved by
reducing the circulating burden, changing the fines screen from
dry than their agglomerated equivalent. T h e reasons or theB
variable drying behavior are obscure. Variations in internal
2 mm. to 2.5 mm., and agglomerating the burden with the product structure and granule porosity, formation of a tightly compacted
offtake shut until the recycle rate required for layering was layer on the outside of the granule which seals in the moisture,
achieved when product offtake was started. During the period and migration of moisture into the granule interior during the
of complete product recycle the average size of the recycled early stages of drying are possible contributory factors.
material increased until a suitable nucleus size was reached.
The removal of product involves removal of nuclci from the Economics of the Layering Process
system and these must be replaced by suitably sized crushed
oversize particles or some agglomeration of fines proceeding Unless the improved granulation or storage properties of the
simultaneously with the layering. Although one might expect formulation decide the issue, the decision whether to produce a
difficulties to arise in obtaining a balance between the supply given formulation by an agglomerative or layering process must
and depletion of nuclei, in practice this has not been a problem. be made on economic grounds. The layering process requires a
higher recycle ratio and hence larger granulator, screens and
The pilot plant ran steadily for long periods in the layering
regime. When operating in this mode every conveyor band conveying equipment. However, because the drier is the most
expensive item in the fertilizer plant, the saving on the drier
appears to be carrying only product grade granules.
can outweigh the extra costs involved in the other equipment.
Layering plays an important role in the production of only Improved storage properties of the product can be exploited as
one of our commercial fertilizer formulations. Analysis of plant an economy in the amount or quality of anti-caking treatment or
performance in terms of the model described here indicated as a saving on the drier by increasing the final granule moisture
that the process was mainly layering but with an important content to the maximum which is consistent with satisfactory
proportion of agglomeration also occurring. Microradiographs storage properties. Because of the variable drying behavior of
of a layered granule and an agglomerate of two layered granules layered granules no generalised treatment of the economics of
are shown in Figure 12. Calculations indicated that an increase layering can be given. Each case must be treated individually
in recycle ratio from less than 3 : I to ca. 5 : 1 would give complete on the basis of measured drying data.
layering at the expense of reduced plant output. This was
The extent to which any potential savings from a layering
confirmed by experiment. Unfortunately the alternative experi-
ment to determine whether layering at less than 3 : 1 recycle process can be realised in practice depends on how tightly the
drier can be designed. Use of computer methods(ll) improves
ratio is feasible on the commercial scale by reducing the water
the mechanics of drier design, but the accuracy of the design
entering with the raw materials would have involved injusti-
depends on the accuracy with which the drying rates as a function
fiably expensive plant modifications.
of fertilizer moisture content can be measured. If the measure-
The plant and pilot plant granulators were both of the paddle ments are done on material made on the pilot plant or smaller
mixer type, indicating that a pronounced rolling action is not scale, the effect of scale-up must be thoroughly understood.
essential for layering to occur. T h e occurrence of layering is
The difficulty of establishing a clear economic case is a
governed by correct control of rccycle size grading and recycle
barrier to the wider adoption of the layering technique. -4
ratio.
better understanding of the drying mechanism of both layered
Operating in the layering regime resulted in improved granule and agglomerated granules is required to improve the position.
shape and better storage properties. A comparative photograph Where, however, a plant designed for layering includes too
of granules produced on the pilot plant by agglomeration and large a drier, under favourable marketing conditions there is
layering is shown in Figure 1 3 . It should be emphasised that a clear case for increasing output above flowsheet by decreasing
granules made on a full scale plant are more spherical than the recyclc ratio and increasing the proportion of agglomeration
those made on the pilot plant. Laboratory caking tests on the to the maximum consistent with adequate drying.
materials illustrated in Figure 1 3 gave the curves shown in The economics of the layering process can be improved by
Figure 14 for caking (measured in terms of an arbitrary caking decreasing the recycle ratio required. This can be done to a
index) as a function of granule moisture content when both types limited extent by the use of granular raw materials. Larger
of granule were given equivalent anti-caking treatment. effects can be achieved by carrying out simultaneous layering
Some formulations which are difficult to granulate by agglo- and drying. T h e simplest way of achieving this is to spray the
meration have been granulated by a layering in raw materials as a slurry into what is effectively the inlet end
which layering is initiated by using one of the raw materials in of a drier as in the spherodiser process(l*). Alternatively the
granular form. Use of granular raw materials can, however, liquid raw materials can be divided between a conventional
result in a marked dependence of analysis on granule size(Lo). granulator and the drier(13). In the T.V.A. process the heat of
Also, where several different fertilizer formulations are made neutralization of acids by ammonia is used for drying. Magnati
on the same plant, the proportion of nuclei present is governed et al.(I) describe the production of granular dianinionium phosphate
by the fertilizer formulation instead of the needs of the granu- by a layering process in which part of the heat of ammoniation
lation system. Ideally, both fine and granular grades of raw of phosphoric acid is used to prepare a concentrated slurry in a
materials should be mixed in the required proportions. Inducing pre-neutralizer and the remainder for drying the granules in the
layering by correct control of the recycle size grading would granulating drum. When the pre-neutralization stage is omitted,
avoid these complications. the water entering with the raw materials is so large that a
Drying very high recycle ratio is required for layering. To overcome
this problem S.A.1.(14)have designed a double drum in which a
In a layered granule the moisture content is limited to the very high internal recirculation rate can be achieved without
outer laycr of the granule and on a diffusion model of the drying the need for high capacity external conveying equipment.
process one would expect a substantial decrease in the time
required to dry a layered granule as compared to its agglo-
merated equivalent. However, our pilot plant experience
Conclusions
indicates that the expected reduction in drying time is sometimes Geometrical considerations based on a simple model of the
not achieved. The best result obtained was a reduction in drying granule in terms of closely packed particles in the layer yields
time from 27 minutes for agglomerated material made at 3 : 1 a useful relationship for determining the recycle ratios required
recycle ratio to 19.5 minutes for layered material made at 5 : 1 for layering processes for different fertilizer formulations.
recycle ratio. For several formulations, however, drying times Knowledge of the recycle ratio is a basic requirement for plant
for layered and agglomerated materials were very similar. design and process economics. T h e concepts used are similar to

The Canadian Journal of Chemical Engineering, Vol. 47, June, 1969 315 ~1
those used previously(3)to describe thc alternative agglomeration x = fraction of the available pores in the nucleus which is
lilled by the Ii uid phase
process. T h e packing parameters required tiiust be detcrrnined y = volume ratio o? liquid to solid phase in a granulator
by experiment, but data suitable for dcsign purposes can readily z = weight ratio of water to fertilizer in the raw materials
bc accumulated by suitable treatment of plant and pilot plant entering a granulator
results. /3 = ratio of average feed size to average granule size in granu-
Lition by agglomeration
Although a much higher recycle ratio is requircd for a X = fraction of voids i n the parked grains i n the layer oi il
layering process than for the corresponding agglomeration layered granule
process, layering generally gives improved g m u l c appearance, A’ = fraction of voids i n the nucleus of a I;tyered granule
better stora c properties and shorter drying times. The eco- p = density of the solid i l l thc layer of a layered granule
B
nomic case or a layering systcm depends on the saving in drying
costs compared with the cost of extra conveying equipinent.
p’ =
p” =
density of the solid in the riucleus of a layered graniile
density of an agglomerated granule composed of uniforin
spheres
More work on the drying mechanism of both laycrcd and agglo- p/ = density of fertilizer solids
meratcd granules is requircd to define the position more clearly. pr = density of a solution of the fertilizer
u = frartion of solids in the packed grains in the layer of’ i i
layered gran tile
Acknowledgments u’ = fraction of solids i n the nucleus of a layered granule
The author wishes to thank all those of his collegaues who carried out
the laboratory and plant work described in this paper and Imperial Chem- References
ical Industries Limited for permission to publish.
( I ) Magnati, 0.. Buriani, L., lnnamorati, I., Maresca, A., Monaldi, R .
and Viteilaro, A., “Granulation Methods for Straight and Compound
Nomenclature Fertilizers”. PaDer presented to lnternational Superphosphate Manu-
facturers Assoiiati6n Conference, Stresa. Septemiber 1967.
B = load required to break an agglomerated granule composed ( 2 ) Brit. Pat. No. 789,747.
of uniform spheres ( 3 ) Sherrington P. J. Chem. Engr. (London) 46 No. 220, CE 201 (1968).
(4) Newitt, D.’M. aAd Conway-Jones, J. MY, Trans. Inst. Chem. Engrs.
d = diameter of the nucleus of a layered granule (London), 36, 422 (1958).
u = diameter of a layered granule ( 5 ) Rumpf, H., “Agglomeration”, (Ed. Knepper, W. A,), Interscience,
6 = acceleration due to gravity 1962, p. 379.
k = X/u, the ratio of volunle of voids to volume of solid i n the (6) Capes, C. E., lnd. Eng. Chem., Process Design Develop., 6, No. 3,
390 (1967).
packed grains in the layer of a layered granule (7) Capes, C. E., Chem. Engr. (London), 45, No. 207, CE 78 (1967).
k’ = X‘/u’, the ratio of volume of voids to volume of solid i n ( 8 ) Phillips, A. B., Hicks, G. C., Jordan, J. E. and Hignett, T. P., J.
the nucleus of a layered granule Agr. ,Food Chem., 6, 449 (1958).
( 9 ) Harris, F. J., “The Incorporation of Ammonium Phosphates into
L = weight ratio of nuclei to grains Granular NPK Fertilizers”, paper presented to International Super-
n = ratio of granule radius to radius of spheres in an agglo- phosphate Manufacturers Association Conference, Stockholm, Sep-
merated granule composed of uniform spheres tember 1959.
N = number of nuclei ( l o ) Olive, B. M. and Hardesty, J. 0..J. Agr. Food Chem., 12, 492
(1964).
r = radius of sphere in a granule composed of uniform spheres ( I I ) Sharples, K., Glikin, P. E. and Wame, R., Trans. Inst. Chem. Enyra.
R = recycle ratio (London) 42, T275 (1964).
s = fertilizer solubility (wt. of fertilizer per unit wt. of water) (12) u.3. Pat.’ No. 239269079.
t = withdrawal parameter i n Equation (1.3) which describes
the depth t o which liquid is withdr?wn.into the interstices
{;:; !: k:;Es,9;ig:i7
~
and 950,775.

between the outermost layer of grains i n iin agglomerated


granule Manuscript received October 23, 1968; accepted January 31. 1969.
T = surface tension Based on a paper presented to the 1968 Tripartite Chemical Engineering
v = volume of the layer in a layered granule
I.” = volume of the nucleus i n a layered granule
Conference, Montreal, Que., September 22-25, 1968.

w = weight ratio of water to fertilizer in a granulator


w = weight of nuclei * * *

31 6 The Canadian Journal of Cheniical Engineering+ Vol. 47, June, 1969

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