Arab J Sci Eng (2013) 38:777–786

DOI 10.1007/s13369-012-0529-2

RESEARCH ARTICLE - CHEMICAL ENGINEERING

Optimum Operating Conditions for Production of Crystalline

Monoammonium Phosphate Form Granulated Diammonium
Phosphate
Yousef Ahmad Mubarak

Received: 26 March 2011 / Accepted: 3 June 2011 / Published online: 18 January 2013
© King Fahd University of Petroleum and Minerals 2013

Abstract A method of obtaining crystallized monoammo-

nium phosphate of good quality using Jordanian granular
diammonium phosphate (18 wt% N and 46 wt% P2 O5 ) and
impure wet process phosphoric acid (about 50 wt% P2 O5 ) is
presented. About 84 % of the total P2 O5 fed to the reactor as
dissolved diammonium phosphate and impure wet process
phosphoric acid is recovered as crystalline monoammonium
phosphate of about 11 wt% N and 62 wt% P2 O5 , the obtained
crystals are quadratic prisms in shape. The main steps of the
production process include dissolution, filtration, reaction,
crystallization, centrifuging, and then drying. It is found that
the best operating conditions to produce monoammonium
phosphate of good quality, quantity, and crystals size are: 1:1
as DAP/water weight ratio, 1:1 H3 PO4 /DAP mole ratio, 3 h
dissolution time, 35 ◦ C reaction temperature, 45 min reaction
time, 15 ◦ C crystallization temperature, 90 min crystalliza-
tion time, and 70 rpm agitation speed in both the reactor and
crystallizer.
1 Introduction
Keywords Diammonium phosphate · Monoammonium
phosphate · Wet process phosphoric acid · Granular · Fertilizers have always played an integral role in the agri-
Nucleation · Crystallization culture industry despite two completely different method-
ologies: organic and inorganic. Among the many types of
inorganic fertilizers, crystalline fertilizers have many advan-
tages over others, such as granulated fertilizers, because of
their higher purity, improved water solubility, and its rapid
release in the soil.
It is desired and preferred to have a fertilizer with highest
content of the macronutrients and lowest content of impuri-
ties, for the purpose of the most efficient supplying nutrients
to plants. Both MAP (monoammonium phosphate) and DAP
(diammonium phosphate) are excellent sources of phospho-
Y. A. Mubarak (B)
rus and nitrogen and have a proven, historical record of yield
Department of Chemical Engineering, Faculty of Engineering
and Technology, University of Jordan, Amman 11942, Jordan increases. Differences in fertilizer placement, cropping sys-
e-mail: ymubarak@ju.edu.jo tems and soil reactions may favor one source over the other in

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specific locations. There are many of reasons to recommend
using MAP as a source of phosphorus rather than DAP. One
of these reasons is when MAP is applied, the soil solution pH
surrounding the granule ranges from an acid pH of 3.5–4.2,
in contrast, the initial pH around the DAP granule is alkaline
with a pH of 7.8–8.2. This high pH, combined with the extra
ammonia found in DAP, can result in zones of free ammo-
nia in the soil. These zones have the potential to cause seed
germination problems and seedling injury and can potentially
interfere with root development. Also, P is taken up from soil
solutions by roots in two forms: H2 PO4 and HPO4 . Research
has shown a trend that plants take up H2 PO4 more rapidly
than HPO4 . This factor is important in the MAP–DAP com-
parison, because the acid soil solution in MAP favors the
formation of H2 PO4 , thus more potential P uptake.
Generally, MAP is manufactured by combining one mole
of ammonia with one mole of phosphoric acid. DAP is pro-
duced by adding 2 mol of ammonia with one mole of phos-
phoric acid. The additional ammonia in DAP adds beneficial
nitrogen, but can create unfavorable chemical reactions in
soil solution. Crystalline MAP and DAP are usually pro-
duced using pure hot furnace phosphoric acid (analytical
grade phosphoric acid) which is expensive, especially to be
used in fertilizers industry, while granulated MAP and DAP
are produced using phosphoric acid produced by wet process
which is cheap, but it contains a lot of impurities which appear
in the final product (the granulated DAP and MAP). During
production processes of MAP or DAP, usually the producers
use fillers to speed up the granulation step, but these fillers
are insoluble in water and make granular MAP and DAP not
suitable for drip irrigation systems as an example [1]. Dif-
ferent compositions of MAP can be produced depending on
phosphoric acid used, whether it is purified or not before pro-
cessing and whether impurities are precipitated and filtered
during production process.
Huge quantities of phosphate rocks are available in
Jordan from which about 105,000 ton wet process phospho-
ric acid is produced annually by the Jordan Phosphate Mines
Company with a P2 O5 content of 50–52 wt%. This produced
acid is mainly used to produce 750,000 ton/year granular
DAP, unfortunately the presence of the solid filler with the
DAP limits its usages as mentioned above. In addition to
that, the present cost of the granular DAP is 450–500 $/ton
compared to 900–1,000 $/ton the cost of crystalline MAP,
this difference in cost makes it crucial to find a suitable and
competitive way in which a crystalline MAP is produced
in Jordan from the available raw materials and without the
need of both the furnace grade phosphoric acid and ammo-
nia which requires special handling and storage facilities. In
the present work, a procedure for the conversion of granu-
lated diammonium phosphate to crystalline monoammonium
phosphate using untreated wet process phosphoric acid is
presented. The most suitable operating parameters were also
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obtained, these parameters include DAP/water ratio, reaction
temperature, reaction time, crystallization temperature, and
crystallization time.
2 Theoretical Background
Monoammonium phosphate is the salt of ammonia and phos-
phoric acid and it has the formula of NH4 H2 PO4 and consists
of ammonium cations and phosphate anion. It is used as an
ingredient in some fertilizers as a high source of elemental
nitrogen, it is also used as a flame retardant in thermoplastic
compositions. The conventional way for MAP production is
done by the reaction of anhydrous ammonia and phosphoric
acid in a batch or continuous reactors and crystallized in con-
ventional crystallizers, since the partial pressure of ammonia
over this acidic solution is low. MAP crystals are filtered or
centrifuged and dried at a temperature below 100 ◦ C in a
rotary dryer, and the mother liquor is recycled to the reactor.
The reaction represented by the following equation:
H3 PO4(aq) + NH3 → NH4 H2 PO4 . (1)
Previous research into mono-ammonium phosphate
(MAP) crystallization dates back to 1967 and 1970 by Mullin
and co-workers [2,3]. Brief descriptions of some processes
used in the production of crystalline MAP are presented here.
Von Semel and Schibilla [4] described a method of obtain-
ing crystalline ammonium phosphate of good quality using
ammonia and technical grade phosphoric acid that was liber-
ated from the major portion of impurities after precipitation
with an organic solvent. Crerar et al. [5] invented a two-stage
process for preparing ammonium phosphates; in the first
stage, ammonia is reacted with phosphoric acid in the liquid
phase to yield an immediate product which is then ammo-
niated further in the second stage under elevated pressure.
A process for the manufacturing of solid MAP with good
granulation properties suitable for use in compound fertilizer
manufacture is presented by Davidson [6]. An improvement
in product quality is obtained when 20–80 % of aqueous
slurry of ammonium phosphate is mixed with a second acid
prior to entry into a moisture disengagement unit. This treat-
ment precipitates some monoammonium phosphate crystals,
which provide nuclei for further crystal growth. Kolmeijer et
al. [7] reacted NH3 , steam, and H3 PO4 to produce a partially
neutralized phosphate which, on continued reaction, yields a
slurry of NH4 H2 PO4 . Further continuation of reaction with
H3 PO4 yields solid NH4 H2 PO4 .
In 1982 Weston et al. [8] described a method of produc-
ing purified mono-ammonium phosphate from wet process
phosphoric acid and ammonia in two stages, the acid being
ammoniated in the first stage to a pH between 1.5 and 2.5.
The mixture is allowed to age and then is ammoniated to a
pH between 4 and 5 in the second stage. According to the
Arab J Sci Eng (2013) 38:777–786
author, most of the impurities will be removed as precipi-
tate formed in both stages. Anastasi et al. [9] reacted ammo-
nia and untreated phosphoric acid at a temperature ranged
from 80 to 95 ◦ C and produced a water-soluble ammonium
phosphates. Under high temperature conditions, the obtained
suspension is filtered into aqueous solution of ammonium
phosphate and an impurity-containing sludge. The aqueous
solution of ammonium phosphate is then crystallized to form
ammonium phosphate crystals. Another process for produc-
ing purified mono-ammonium phosphate directly from wet
process phosphoric acid with a high yield was investigated
by Kajitani et al. [10]. This process comprises reacting wet
process phosphoric acid with NH3 at 50 ◦ C while keeping the
molar ratio of NH3 /H3 PO4 at about 0.9–1.35, separating the
resulting slurry into MAP crystals and an insoluble sludge.
Meng et al. [11] invented a process in which phosphate rock
is reacted with phosphoric acid to produce monobasic cal-
cium phosphate, and then reacted the monobasic calcium
phosphate with ammonium carbonate to produce ammonium
phosphate.
Recently, Utomo et al. [12] utilized a seeded batch cool-
ing crystallizer to produce mono-ammonium phosphate crys-
tals. The effects of different initial saturation, seed size and
seed loading ratio on crystal size distribution were thoroughly
studied to gather more insight into mono-ammonium phos-
phate batch crystallization, its kinetics, and for model vali-
dation purposes. The author reported that seed loading ratio
shows the most significant effect on the crystal size distri-
bution profiles followed by the supersaturation factor and
seed size. It is also reported that the supersaturation level
not only influences the growth rate but the crystal shape as
well. In another study, Utomo et al. [13] used a semi-batch
reactive crystallizer equipped with a cooling jacket, a dual
feed system and a turbine type agitator to understand the
kinetics of MAP crystallization process. Effects of N/P ratio,
seed crystals, feeding system, feed flow rate, initial supersat-
uration, feeding time and mixing intensity to the real-time
supersaturation, crystal yield, crystal shape and final crystal
size distribution were studied. The authors found that in a
non-seeded system, the nucleation process prevails and the
induction time is significantly long, almost one-third (1/3) of
the total batch time. On the other hand, in a seeded system,
supersaturation is mainly used for seed growth and nucle-
ation dominates the process in the initial stage only.
It is very clear that most of the available processes for
crystalline MAP production using wet process phosphoric
acid as the main source of phosphorus have the ammonia-
tion as a crucial step. These available methods are expen-
sive given that they are dependent on the reaction between
ammonia and furnace grade H3 PO4 acid. The present study
reports an alternative route to produce a crystalline MAP
without the ammoniation step. In the proposed method, the
granular DAP will be converted into a crystalline MAP after
779
removing the solid filler used in the granulation step. In addi-
tion to the minimization of the cost, the present method will
also avoid problems and safety precautions associated with
handing liquid or gaseous ammonia which is essential for the
crystalline MAP production process. Initially, DAP granules
will be dissolved in water to free up the solid filler which
will be removed by settling and filtration, after that wet pro-
cess phosphoric acid can be added to react with the dissolved
DAP and produce MAP according to the following reaction:
(NH4 )2 HPO4 + H3 PO4 → 2NH4 H2 PO4 . (2)
To convert DAP to MAP, the ratio of NH4+ :PO3− 4 should
be converted from 2:1 to 1:1, theoretically this means that
the number of moles of phosphoric acid to be added should
be equal to DAP moles fed to the reactor.
3 Experimental
3.1 Materials
Granular diammonium phosphate (18 wt% N and 46 wt%
P2 O5 ) and wet process phosphoric acid (50 wt% P2 O5 ,
70 wt% H3 PO4 ) both produced by Jordan Phosphate Mines
Company were used in the present work. The wet process
phosphoric acid is used without any treatment.
3.2 Procedure
More than 25 experiments were performed, the aim was to
produce, improve the product quality, and yield by chang-
ing the operating conditions of the dissolution, reaction, and
crystallization steps. In all of the performed experiments, dif-
ferent quantities of water and 500 g of granular DAP were
mixed in a batch mixer for a certain period of time, the agi-
tation speed at this step was 200 rpm. Afterwards, the mix-
ture was filtrated and then transferred to a controlled reactor
where the reaction was initiated by the slow addition of wet
process phosphoric acid to the DAP mixture in a batch reac-
tor, 530 g (315 ml) of untreated H3 PO4 is added which makes
the mole ratio of H3 PO4 to DAP 1:1. While the phosphoric
acid was being added, the mixture was being agitated at a
rate of 70 rpm. On completion of the reaction, the mixture
was then transferred to a controlled crystallizer at a fixed
temperature and left for enough time to allow the formation
and growth of MAP crystals. Filtration of the crystals was
then performed in a centrifuge, and dried at room tempera-
ture. Figure 1 shows a schematic flow diagram for the pro-
cedure followed to convert DAP granules into a crystalline
MAP.
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Fig. 1 Schematic flow diagram for conversion of granular diammonium phosphate to crystalline monoammonium phosphate

Table 1 Experimental parameters covered in the present work

DAP/H2 O (g/ml) Reaction Reaction Crystallization Crystallization Yield (%) Observations
temperature time (h) temperature time (h)
(◦ C) (◦ C)

1:1 35 45 15 90 84 Large crystals

1:1.25 58 72 Large crystals
1:1.5 70 49 Large crystals
1:2 135 38 Very large crystals
1:3 180 – No MAP obtained
1:1 25 27 15 90 Powder
30 33 Fine crystals
35 45 Large crystals
40 65 Large crystals
50 75 Fine crystals
60 95 Powder
70 105 Powder
1:1 35 30 15 90 78 Fine crystals
45 84 Large crystals
60 83.5 Large crystals
90 85 Large crystals
1:1 35 45 5 90 90 Powder
10 86.5 Fine crystals
15 84 Large crystals
20 75 Large crystals
1:1 35 45 15 30 45
45 55
60 72
90 84
120 86

3.3 Parameters studied in the present work in an attempt to find the opti-
mum values for these parameters. Only one variable was
There are many parameters affect the production pro- changed for each run, while all other parameters were
cess. Table 1 presents the experimental parameters fixed.

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Fig. 2 Temperature variations of the 1:2 DAP/water (g/ml) mixture as
a function of mixing time
4 Discussion of Results
To achieve a level of confidence in the proposed work, numer-
ous trials were carried out to obtain an optimum set of process
conditions. A summary of the experimental work, trial condi-
tions, the results, and observations regarding the results will
be presented and discussed here.
4.1 DAP/Water Ratio
To get rid of the solid filler particles used in the DAP granula-
tion step, DAP granules should be dissolved and then filtered;
all mixtures were agitated for about 3 h in an insulated beaker
before they filtered. There was a slight increase in the mixture
temperature during the agitation step which indicates that the
dissolution of DAP granules is an exothermic process; Fig. 2
shows the temperature variation of the 1:2 DAP/water (g/ml)
mixture as a function of time.
Decreasing water to DAP ratio will require higher tem-
perature to dissolve the DAP granules; on the other hand,
increasing water to DAP ratio will affect the crystalliza-
tion step, hence an optimum ratio must be investigated. Five
DAP/water (g/ml) ratios were tried in this work. Figure 3
shows the required temperature to dissolve 500 g granular
DAP as a function of volume of added water, and there was
no need for any heating source to dissolve the 500 g of DAP
for DAP/water (g/ml) ratios of >1:2, while to dissolve the
same amount of DAP in 500 ml of water [i.e. DAP/water
(g/ml) ratio 1:1] it was found that the mixture’s temperature
must be raised to 70 ◦ C. A solubility of 106.7 g DAP in
100 ml of water at a temperature of 100 ◦ C is reported in
literatures [14], while only 57.8 g DAP dissolved in 100 ml
of water at 10 ◦ C. It is noticed that about 18 wt% of the DAP
used in the present work was filtered as solid filler and other
insoluble materials, a chemical analysis of the cake showed
that it contains about 9 % of its weight as P2 O5 .
On completion of the filtration process, part of the
DAP/water mixture was left to settle down for a period of
781
Fig. 3 The required temperature to dissolve 500 g granular DAP as a
function of volume of added water
time while the other part of the mixtures was used directly
after filtration. It is noticed that for those settled mixtures,
the turbidity of the mixture still very high after 0.5, 2, 3, and
4 h, especially for DAP/water (g/ml) ratio of 1:1, 1:1.25, and
1:1.5; while the mixtures turned to clear mixtures with a light
green color after 8 h. For those clear mixtures, it is observed
that a layer of soft sludge was precipitated as a bottom layer.
Many attempts were carried out to produce crystalline MAP
from the clear mixtures, but all the attempts were failed, it
seems that settling of the mixtures for a long period of time
(>4 h) decreases the concentration of the clear mixture as a
result of the precipitation of the suspended matters to a point
at which it is not possible to form the MAP crystals at any
condition. The presence of the suspended very fine particles
may work as a nucleating agent or seeds on which MAP crys-
tals grow [15], precipitation of these suspended fine particles
left the DAP mixture without a nucleating agent and hence
it was difficult to form MAP nuclei, this could be the only
reason for the failure of obtaining MAP crystals from the
clear DAP mixtures. A chemical analysis of these clear mix-
tures after settling did not show much variation in the P2 O5
content compared with the unsettled mixtures. Utomo [16]
studied the crystallization of MAP both with and without the
presence of seed crystals and found that the concentration
of the seed crystals plays an effective rule in the nucleation
step.
For filtered DAP/water mixtures without settling or set-
tled for a period time of <4 h, it was possible to crystal-
lize MAP from all DAP/water mixtures prepared except the
ratio of 1:3. Different operating conditions were tried by
changing the reaction temperature, reaction time, crystalli-
zation temperature, crystallization time, and agitation speed
until success was achieved. It is noticed that as the water to
DAP ratio increases longer time is required to nucleate and
grow the MAP crystals, the amount of obtained crystals is
less but they are larger in size and they all have a quadratic
prisms structure. In addition to the chemical analysis, the qua-
dratic prisms structure is another evidence that the obtained
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Fig. 4 Images of the dried
MAP crystals obtained at
different DAP/water (g/ml)
ratios; a 1:2, b 1:1.5, c 1:1.25
and d 1:1
crystals are MAP crystals which is in agreement with what is
reported in the literature [17]. Figure 4 shows images of the
dried MAP crystals obtained at different DAP/water (g/ml)
ratios. A polarized light microscope with a magnification of
160X was used to show the quadratic prisms structure of the
MAP crystals. It is clearly seen that decreasing the water to
DAP ratio, the size of the obtained quadratic prisms crystals
slightly decreased. This reduction in crystals size is expected
since decreasing the amount of water will increase the con-
centration of the suspended fine particles in the mixture, and
hence increase and speed up the nucleation rate. As a result of
the rapid nucleation rate, large number of crystals appears in
the solution in a very short period of time and consumes MAP
from the solution. Consumption of MAP from the solution
by the large number of the formed crystals decreases MAP
concentration and reduces the growth driving force, and this
leads to a reduction in the final size of the crystals. Utomo
et al. [12] reported that increasing the seed loading ratio will
decrease the size the obtained crystals and this is in good
agreement with what is found here.
The presence of water in the reaction mixture is very
important as increasing the fluidity of the reaction mixture
has some advantages over the reaction of reactants without
excess water; some of these advantages are easy agitation,
preventing the buildup of MAP layer on the inside wall of
the reactor and crystallizer which reduces the heat transfer
between the coolant and the mixture, increasing the available
space in which MAP crystals need to grow up and give large
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Arab J Sci Eng (2013) 38:777–786
size, easy pumping of the slurry from one unit to another. The
resulted MAP crystals can be easily separated from the liquor
due to the large amount of liquid, and most of the mineral
impurities accompanying the wet-process acid remain in the
mother liquor. On the other hand, high ratio of water to DAP
has some disadvantages such as the size of the equipments
and the required time for the production process. Larger reac-
tor and crystallizer sizes are required to give a reasonable pro-
duction rate because most of the equipment’s volume will be
occupied by water. In addition to that, longer reaction and
crystallization time are needed to allow the MAP crystals to
nucleate and grow; increasing the water to DAP ratio will
delay the nucleation and slow up the growth of the crystals.
Since MAP nucleation and growth found to be fast enough
and the quantity and quality of the obtained crystals are sat-
isfactory at a DAP/water (g/ml) ratio of 1:1, this ratio will be
used as a best ratio and the subsequent results and discussion
is based on this ratio.
4.2 Reaction Temperature and Time
Seven experiments were carried out at different reaction tem-
peratures (25, 30, 35, 40, 50, 60, and 70 ◦ C) while keeping all
other parameters fixed at: DAP/water ratio = 1 g:1 ml, crys-
tallization temperature = 15 ◦ C, crystallization time = 90 min,
agitation speed of 70 rpm. After the filtration step, the mix-
ture was transferred to the reactor where the required amount
Arab J Sci Eng (2013) 38:777–786 783

of the wet process phosphoric acid is added slowly until the

reaction is completed and the formation of MAP nuclei is
started. The rate of H3 PO4 addition was adjusted according
to the time of the reaction, since the acid was added from the
beginning of the reaction until the very end; division of the
total volume of H3 PO4 by the total reaction time gave better
results over the bulk addition of phosphoric acid. In the first
few trials, the required amount of the acid was added to the
reactor at once, but the results were not satisfactory because
it took very long time to crystallize MAP and the size of
the crystals was very small and the recovered amount was
little. The addition of the 50 wt% P2 O5 wet process phos- Fig. 5 Required time to start the nucleation of the MAP fine crystals
phoric acid (70 wt% H3 PO4 and 30 wt% H2 O) at once to the as a function of the reaction temperature
reaction vessel to react with the DAP mixture will result in
more dilution to the mixture. As a result of this dilution, the
driving force for nucleation of MAP crystals will be reduced,
and the induction period before detection of the first MAP
crystals or solid particles will extend for long period of time.
To overcome this problem, H3 PO4 was added slowly to the
reactor and this made H3 PO4 the limiting reactant in the reac-
tion and kept the mixture’s driving force for crystallization
high enough. Nakamura et al. [18] produced purified mono-
ammonium phosphate from wet-process phosphoric acid by
reacting NH3 with H3 PO4 at a mole ratio of 0.9–1.35 and in
a temperature range from 50 to 80 ◦ C.
Figure 5 shows the required time to start the formation
of the MAP fine crystals as a function of the reaction tem- Fig. 6 Variation of the mixture’s temperature inside the reactor as a
perature. It is clearly seen that the required time increases function of reaction time
as the reaction temperature increases, the required time is
measured visibly as the elapsed time from the point at which
the mixture is transferred to the reactor to the point at which
MAP fine crystals start to appear in the mixture. For reactions
carried out at 25 and 30 ◦ C, the nucleation of MAP crystals
process started immediately and a viscous suspension was
formed within a short period of time but after crystallization
and centrifuging the product looked like a powder which is
not favorable. On the other hand, reactions carried out at tem-
peratures higher than 40 ◦ C took very long time (>65 min)
to start the nucleation of the MAP crystals. As a result of
this part, a reaction temperature of 35 ◦ C is considered as
an optimum value to carry on the reaction. Nucleation of the Fig. 7 Monoammonium phosphate crystals recovery as a function of
MAP crystals starts after 45 min; after crystallization and crystallization temperature
drying, the final MAP crystals were large in size in addition
to a good recovery. Variation of the mixture’s temperature
inside the reactor is shown in Fig. 6; the mixture was fed to H3 PO4 , the slurry is transferred to the crystallizer to allow
the reactor at room temperature (21 ◦ C). further growth of the crystals and increase the recovery of
MAP. In the present study, outputs from the reactor were
cooled at several different temperatures leading to differ-
4.3 Crystallization Temperature and Time ent MAP crystals size; the quadratic prisms crystals grew
to a certain extent in length and width. Figure 7 represents
One of the most widely used methods for achieving the super- the recovery of MAP crystals as a function of crystalliza-
saturation essential for crystallization is cooling of a solution. tion temperature, all other conditions remain fixed. Reaction
On completion of the reaction between the DAP mixture and temperature, reaction time, crystallization time, DAP/water

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Fig. 8 Monoammonium
phosphate crystals size as a
function of crystallization
temperature; a 5 ◦ C, b 10 ◦ C,
c 15 ◦ C and d 20 ◦ C
Fig. 9 Monoammonium phosphate recovery as a function of the crys-
tallization time
ratio, and agitation speed were fixed at 35 ◦ C, 45 min, 90 min,
1 g:1 ml, and 70 rpm, respectively.
The results showed that decreasing the crystallization
temperature will increase MAP crystals recovered but the
obtained quadratic prisms crystals are smaller in size as
shown in Fig. 8. At low temperatures (5 ◦ C), the crystals
were small; they are about 150 µm in length, while cooling
at 20 ◦ C created crystals as great as 300 µm. Cooling temper-
ature is known to influence the rate of growth and size of crys-
tals through its effect on supersaturation [19–21]. In general,
the crystal size decreases at higher levels of supersaturation
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Arab J Sci Eng (2013) 38:777–786
Fig. 10 Variation of the mixture’s temperature inside the crystallizer
as a function of crystallization time
due to increased nucleation rates. Therefore, a larger number
of small crystals can be achieved with low cooling temper-
atures. It is also noticed that only small number of MAP
crystals nucleated in the reactor at a temperature of 35 ◦ C,
these crystals continued to grow in the crystallization step
and resulted in large crystals size but most of the MAP crys-
tals were excessively nucleated in the crystallizer which was
maintained at low temperature. Increasing the temperature
difference between the reactor and the crystallizer, excessive
nucleation will occur in the crystallizer and this result in rel-
atively small size product crystals. The recovery increases
Arab J Sci Eng (2013) 38:777–786
Table 2 Streams properties for the lab scale production of crystalline MAP according to Fig. 1
Stream number S1 S2 S3, S4 S5 S6, S7
Mass (g) 500 500 995 90 900
%P 19.8 – 9.9 9.0 10.1
%P2 O5 45.37 – 22.68 – 23.14
%N 17.53 – 8.7 – 9.6
from 75 to 84 % as the crystallization temperature decreases
from 20 to 15 ◦ C, while the value increases only from 84
to 90 % as the temperature decreases from 15 to 5 ◦ C, as a
result a crystallization temperature of 15 ◦ C is considered as
an optimum value.
As expected, the crystal recovery increased with time [22],
the effect of the crystallization time on the crystalline MAP
recovery is shown in Fig. 9; each point on the curve is a com-
plete experiment with similar operating conditions except
crystallization time which is varying from one experiment to
another. Reaction temperature, reaction time, crystallization
temperature, DAP/water ratio, and agitation speed were all
fixed at 35 ◦ C, 45 min, 15 ◦ C, 1 g:1 ml, and 70 rpm, respec-
tively. It is clearly seen that the recovery increased from 45 %
up to 84 % when the crystallization time increased from 30
to 90 min, while the recovery only increased from 84 % up to
86 % when the time increased from 90 to 120 min. Since the
increment in MAP recovery is very small as the crystalliza-
tion time increased from 60 to 90 min, it is suggested to stop
the crystallization after 90 min. Variation of the mixture’s
temperature inside the crystallizer is shown in Fig. 10; the
mixture was fed to the crystallizer at a temperature of 15 ◦ C.
It is noticed that the smaller the size of the crystals the
more difficult is the separation of the crystals from the mother
liquor. Also the physical appearance of the fine crystals is not
satisfactory as they stick to each other and are not free flow-
ing, and this makes it very hard to dry the obtained MAP
crystals even with a high air temperature and long residence
time inside the dryer (see Fig. 8a). Unlike large size crystals
that are easily separated from the mother liquor and do not
require a long time to dry (see Fig. 8c, d).
4.4 Best Operating Conditions
To verify the obtained results in this study, an experiment was
carried out at the obtained best operating conditions: 1 ml:1 g
as DAP/water ratio, 3 h dissolution time, 35 ◦ C reaction tem-
perature, 45 reaction time, 15 ◦ C crystallization temperature,
90 min crystallization time, 70 rpm agitation speed in both
the reactor and crystallizer. Crystalline MAP from granular
DAP is produced according to the flow sheet presented in
Fig. 1, and Table 2 presents input and output streams to and
from each unit in addition to the analysis of each stream,
785
S8 S9 S10, S11 S12 S13
530 1430 1430 781 645
21.8 14.4 – 4.1 27.0
49.95 33.0 – 9.39 61.8
– 5.9 – 1.6 11.2
the values tabulated here are average values of three trials.
About 84 % of the MAP is recovered from the mixture as
MAP crystals of large size.
Stream number 12 which leaves the centrifuge contains
4.1 % P2 O5 and 1.6 % N, this stream can be recycled to the
dissolution tank or can be used in production of suspension
or fluid fertilizers [23].
5 Conclusions
• According to the present work, conversion of granular
DAP to crystalline MAP can be achieved after dissolution
of DAP granules and removing the solid filler and then
react the DAP mixture with an equimolar of unpurified
H3 PO4 .
• It is advised not to leave DAP/water mixture settle down
for longer period of time (>4 h), longer period of settling
time will result in precipitation of all solids and a clear
green mixture will be obtained which is found to be very
hard to give MAP crystals at any operating conditions.
• According to the suggested procedure, a crystalline mono-
ammonium phosphate can be obtained with the follow-
ing operating conditions: DAP/water (gm/ml) ratio = 1:1,
H3 PO4 /DAP mole ratio = 1:1, dissolution time = 3 h, reac-
tion temperature = 35 ◦ C, reaction time = 45 min, crystal-
lization temperature = 15 ◦ C, crystallization time = 90 min,
agitation speed in both the reactor and crystallizer = 70 rpm.
• A recovery of about 84 % of the total P2 O5 fed to the reac-
tor as dissolved DAP and untreated wet process phospho-
ric acid is achieved as MAP crystals with quadratic prisms
structure. The size of the obtained crystals increases as the
crystallization temperature increases while the recovery
reduces. A recovery value of 90 % can be achieved at 5 ◦ C
crystallization temperature but as a powder form.
References
1. Young, R.D.; Hicks, G.C.; Davis, C.H.: TVA process for produc-
tion of granular diammonium phosphate. J. Agric. Food Chem. 10,
442–447 (1962)
2. Mullin, J.W.; Amatavivadhana, A.: Growth kinetics of ammonium
and potassium dihydrogen phosphate crystals. J. Appl. Chem. 17,
151–156 (1967)
123
786
3. Mullin, J.W.; Amatavivadhana, A.; Chakkraborty, M.: Crystal habit
modification studies with ammonium and potassium dihydrogen
phosphate. J. Appl. Chem. 20 153–158 (1970)
4. Von Semel, G.D.; Schibilla, E.: Process for the Manufacture of
Crystallized Ammonia Phosphates. US patent number 3894143
(1975)
5. Crerar, J.D.; Hemsley, J.D.C.; Hepworth, I.C.: Process for Pro-
ducing Ammonium Phosphate in Two Stages. US patent number
3974263 (1976)
6. Davidson, E.: Manufacture of Solid Ammonium Phosphate. US
patent number 4017588 (1977)
7. Kolmeijer, N.W.; Anderton, P.H.; Windmill Holland, B.V.; Vlaard-
ingen, N.: Powder monoammonium phosphate production at
resources Tunisie SA. Phosphorus Potassium 86, 39–43 (1976)
8. Weston, C.W.; Wen, J.W.: Purified monoammonium phosphate
process. US patent number 4325927 (1982)
9. Anastasi, F.; Anania, G.; Cultrera, V.; Carfi’, G.: Process for the
production of Water Soluble Ammonium Phosphates. US patent
number 4632813 (1986)
10. Kajitani, T.; Fujii, S.; Sato, T.; Yonehara, I.; Fukumura, C.;
Harita, K.: Process for Producing Purified Monoammonium Phos-
phate from Wet Process Phosphoric Acid. US patent number
4610853 (1986)
11. Meng, X.; Tsobanakis, P.; Peacock, A.; Clark, D.; Weyrauch, C.:
Process for Producing High Purity Phosphates. US patent number
7374740 (2008)
12. Utomo, J.; Maynard, N.; Asakuma, Y.; Maeda, K.; Fukui, K.; Tadé,
M.: Experimental kinetics studies of seeded batch crystallization of
mono-ammonium phosphate. Adv. Powder Technol. 21, 392–400
(2010)
13. Utomo, J.; Asakuma, Y.; Maynard, N.; Maeda, K.; Fukui, K.; Tadé,
M.: Semi-batch reactive crystallisation of mono-ammonium phos-
phate: an experimental study. Chem. Eng. J. 156, 594–600 (2010)
123
Arab J Sci Eng (2013) 38:777–786
14. Lide, D.R.: Handbook of Chemistry and Physics, 90th edn. CRC
Press, Boca Raton (2009)
15. Kubota, N.; Doki, N.; Yokota, M.; Jagadesh, D.: Seeding effect
on product crystal size in batch crystallization. J. Chem. Eng. Jpn.
35(11), 1063–1071 (2002)
16. Utomo, J.: Experimental Kinetics Studies and Wavelet-Based Mod-
eling of a Reactive Crystallization System, Thesis (Ph.D.), Curtin
University, Australia (2009)
17. Mullin, J.W.: Crystallization, 4th edn. Butterworth-Heinemann,
Boston (2001)
18. Nakamura, S.; Hayakawa, S.; Shibata, T.; Yamashita, T.: Pro-
cess for producing purified monoammonium phosphate from wet-
process phosphoric acid. Chinese patent number 619908 (1986)
19. Jones, A.G., Mullin, J.W.: Programmed Cooling Crystallization of
Potassium Sulphate Solutions. Chem. Eng. Sci. 29, 105–118 (1974)
20. Myerson, A.S.; Ginde, R.: Crystals, crystal growth and nucleation.
In: Handbook of Industrial Crystallization, pp. 33–63. Butterworth-
Heinemann, Boston (1993)
21. Schüth, F.: Nucleation and crystallization of solids from solutions.
Curr. Opin. Solid State Mater. Sci. 5, 389–395 (2001)
22. Zainal Abidin, S.; Ling, G.K.F.; Abdullah, L.C.; Ahmad, S.; Yunus,
R.; Choong, T.: Effects of temperature and cooling modes on yield,
purity and particle size distribution of dihydroxystearic acid crys-
tals. Eur. J. Sci. Res. 33(3), 471–479 (2009)
23. Wilbanks, J.A.; Faulkner, L.C.: New suspension products and
processes under development by TVA. In: Proceedings of
the 30th Annual Meeting-Fertilizer Industry Round Table,
pp. 130–142 (1980)