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Modelling of a solid dissolution in liquid with chemical reaction:

Application to the attack reaction of phosphate by sulphuric acid

Article  in  The Canadian Journal of Chemical Engineering · October 2014

DOI: 10.1002/cjce.21986

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Modelling of a Solid Dissolution in Liquid With Chemical Reaction:
Application to the Attack Reaction of Phosphate by Sulphuric Acid

Nader Frikha,* Amira Hmercha and Slimane Gabsi

Unit of Research: Environment, Catalysis and Processes Analysis, National Engineering School of Gabes, Gabes University,
Street Omar Ibn ElKhattab 6029, Gabes, Tunisia

This paper aims at the determination of the kinetics and thermodynamics of a liquid–solid reaction: the attack reaction of the phosphate ore by
sulphuric acid. This reaction, which is used industrially for the production of phosphoric acid, has two stages, the first of which consists in the
dissolution of phosphate ore in the diluted phosphoric acid diluted and the second relates to the attack of the dissolved ore by sulphuric acid. The
thermodynamic properties and the kinetic parameters of each reaction are determined using a calorimetric approach. The complete kinetic study of
the step in dissolving the phosphate ore was conducted to develop a kinetic model involving the process of transfer kinetic liquid–solid and the
chemical kinetic processes. This model takes into account the coupling between the mass and heat balance and the multitude particles' sizes of
phosphate and the stirring speed. The study of the attack of monocalcium phosphate by sulphuric acid allows the evaluation of the reaction order and
the values of various parameters that describe the kinetic model of the precipitation reaction. The comparison of different parameters determined with
those reported in the literature shows the reliability and the relevance of the proposed methodology.

Keywords: liquid–solid reaction, reactive dissolution, modelling, thermodynamic, calorimetry

INTRODUCTION and/or sulphuric acid. The attack reaction is exothermic and takes
place in two stages. The first one is the dissolution of the phosphate

T
he dissolution of solid particles in a medium liquid is quite
commonly encountered in the chemical process industry
(precipitation, hydrometallurgy, desalination, etc.). The
determination of kinetic models is of great importance, either for
industrial reactors optimization or for environmental reasons.[1,2]
The modelling of reactive dissolution of solids in liquids is a big
challenge. Actually, the reactional mechanism of this heteroge-
neous reaction can be a very complex one, comprising several
elementary steps. On the other hand, kinetics, mass transfer, and
heat transfer effects are coupled.[3]
The majority of published studies devoted to kinetics and
thermodynamic reactions were developed for the control of
homogeneous reactions, for which, most of the time, the studied
parameters are the initial reactant concentrations and temperature.
Fewer studies have been devoted to heterogeneous reactions in
multiple phases,[4,5] whose implementation is much more delicate.
As opposed to homogeneous reactions, hydrodynamic parameters,
such as the stirring speed, that can modify the multiphase mass
transfer should be taken into account.
Despite the multitude of reactive dissolutions, presently there is
not a systematic method known for determining the kinetic and
thermodynamic properties needed without resorting to expensive
equipment such as commercial calorimeters.
The present paper aims at the use of a calorimetric approach for
the determination of thermodynamic and kinetic parameters of a
solid dissolution with a chemical reaction. It also aims at the
proposition of a model that takes into account the diversity of
particle sizes, the stirring speed and the variation of properties of
reactional medium during the dissolution (particles sizes, temper-
ature, composition, etc.).
KINETIC MECHANISM
The production of phosphoric acid and phosphate fertilizers is
carried out by the attack of the phosphate rock by phosphoric acid
ore in diluted phosphoric acid which leads to the formation of
monocalcium phosphate (CaH2PO4). As for the second stage, it is
the attack of the monocalcium phosphate by sulphuric acid:[6]
Ca10 F2 ðPO4 Þ6 þ 14H3 PO4 ! 10CaðH2 PO4 Þ þ 2HF: ð1Þ
10CaðH2 PO4 Þ þ 10H2 SO4 þ 20H2 O ! 20H3 PO4
ð2Þ
þ 10CaSO4  2H2 O:
Ca10 F2 ðPO4 Þ6 þ 10H2 SO4 þ 20H2 O ! 6H3 PO4
ð3Þ
þ 10CaSO4  2H2 O þ 2HF:
The second reaction is used to concentrate the phosphoric acid and
leads to the precipitation of gypsum.
EXPERIMENTAL STUDY
In this section, the imposed operating conditions, the adopted
operating mode, and the experimental results are presented.
Experimental Setup
The reactor used in this study was a cylindrical stainless steel tank
equipped with a jacket on its side wall. Agitation was ensured by a
Rushton turbine with right blades, whose stirring speed was
controlled between 0 and 3000 rpm.
*Author to whom correspondence may be addressed.
E‐mail address: nader.frikha@enig.rnu.tn
Can. J. Chem. Eng. 92:1829–1838, 2014
© 2014 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.21986
Published online 19 August 2014 in Wiley Online Library
(wileyonlinelibrary.com).

VOLUME 92, OCTOBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1829
 Considering that the aim of the present work is to determine the
reaction kinetics of dissolution and the crystallization, rapid
dissolution is seen as a challenge. To overcome this problem, it is
advantageous to slow down this stage whilst operating with
relatively low temperatures. We chose to work with temperatures
between 20 and 65 8C.
Since the minimal stirring speed for suspending the phosphate
ore particles, as determined using the relation of Zwietering,[7] is
804 rpm, it was decided that the minimal stirring speed should be
1000 rpm.

Study of the Dissolution Reaction

Figure 1. Experimental setup. The first studied reaction is the dissolution of fluoroapatite into
diluted phosphoric acid. An experimental study pertaining to this
reaction was carried out, whose objective was to evaluate the heat
of dissolution and the expression of the diffusion coefficient in
Resistance heating was used to control and regulate the order to lead to a model describing dissolution. With this intention,
temperature in the reactor by circulating the cooling in the jacket. various tests were conducted according to the mode. The jacket
The heating power varied from 0 to 3500 W. The device was also temperature Tw was maintained constant using a cooling liquid.
equipped with a plate heat exchanger which allowed the After introducing the acid solution and once the desired initial
adjustment of the cooling temperature. Several temperature probes temperature was reached, the mass of phosphate ore was rapidly
(Pt100) allowed the tracking of the reactional medium and the added. Immediately after this addition, stirring was started. We
external cooling liquid temperatures. assume that the amount of reactants that react during this time is
The temperature of the cooling liquid, the reactor temperature negligible. This assumption is justified firstly because the time
and the heating power were recorded against time. The acquisition between the addition of the phosphate and the beginning of the
rate was 10 points/s. stirring is low and secondly because the mass transfer rate is
A sketch of the experimental setup is presented in Figure 1. negligible in the absence of stirring and so the reaction rate will be
very low.
Reactants The temperature of the cooling liquid and the reactor tempera-
The phosphate used in this study was characterized by a relatively ture were recorded against time.
low concentration of P2O5 (30 wt. %) and high concentration of We conducted a series of experiments for different values of
CaO (50 wt. %). The observations of phosphate using a microscope jacket temperature. Figure 2 shows an example of the variations of
showed that there was a multitude of particle shape, but the the reactor and wall temperatures.
hypothesis that the shape of phosphate ore particles would be of
spherical shape was adopted. The particle size distribution is a Study of the Reaction of Precipitation
parameter of great importance, which directly affects the surface The second stage of the attack of phosphate ore is the reaction of
reaction and the reaction time. To characterize the particle size of sulphuric acid with the products of dissolution (monocalcium
phosphate, a sifting of a sample was conducted. The results are phosphate). It leads to the precipitation of calcium sulphate and the
summarized in Table 1. formation of phosphoric acid (Equation (3)). The heat generated by
the precipitation reaction is accompanied with the heat of dilution
Operating Conditions of sulphuric acid in the solution of diluted phosphoric acid. To
In all manipulations, a reaction volume equal to 1 L was chosen, identify the exact value of the heat generated by each reaction, we
and a weight concentration of H3PO4 equal to 18 % was imposed. performed the first experimental study which consisted in
The conversion decreased with the increase in the solid–liquid preparing different mixtures containing a solution of phosphoric
ratio. We chose to work with a weak ratio of solid to overcome the acid (without fluoroapatite) which was added to a solution of
limitations due to the saturation phenomenon. Besides, a solid ratio sulphuric acid.
equal to 9 % was adopted for all experiments, which corresponds to The second experimental study relates to the study of the
a mass of 100 g of phosphate. reaction of precipitation. The procedure consisted in dissolving
phosphate grains beforehand in the diluted phosphoric acid, then
adding a mass of H2SO4 (96 %) which corresponds to an equimolar
mixture of reactants. These experiments were carried out under the
Table 1. Particle size distribution of phosphate ore same conditions of the study of dilution (cooling temperature,
concentration of H2SO4, etc.).
Size class (i) dp (mm) Weight fraction (%) Both studies were conducted in isoperibolic mode, and the tests
1 >1.250 2.33 were performed in the same reactor described above.
2 0.800–1.250 1.81 Figure 3 shows an example of the experimental results. In fact,
3 0.630–0.800 1.50 two temperature curves were superimposed; the first of which is
4 0.500–0.630 2.95 relative to the dilution of sulphuric acid in a phosphoric acid
5 0.315–0.500 7.39 solution (continuous line Tdilution) and the second is pertaining to
6 0.160–0.350 41.04 the attack of fluoroapatite dissolved in phosphoric acid by
7 0.080–0.160 36.60 sulphuric acid (dashed line Treactionþdilution).
8 0.063–0.080 4.69 The rise of temperature of the Treactionþdilution curve is found to be
9 <0.063 1.66 more important than Tdilution.

1830 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, OCTOBER 2014
 32
Tr
Mass and Heat Balances
Tw
30 Mass balance
The dissolution of solid particles in liquids involves the dissociation
28 of solute molecules on the solid surface through a surface reaction,
and the subsequent diffusion of the disintegrated solute molecules
T (°C)

26 toward the bulk liquid phase. The dissolution rate depends upon
the rates of these processes. A distinction should be made between
the diffusional regime where mass transfer has the limiting step
24
and the chemical regime that takes place when the chemical
reaction itself imposes its kinetics should be made. Thus the
22 dissolution rate coefficient kd can be expressed as a function of
the rate constants of two basic processes involved in the solid
20 dissolution as
0 500 1000 1500 2000 2500
time (s) 1 1 1
¼ þ ; ð4Þ
Figure 2. Temperatures variations during a dissolution experiment,
kd kr kt
N ¼ 1000 rpm, Tw ¼ 23 8C.
where kr is the rate constant for the dissolution reaction at the solid
surface, and kt the mass transport coefficient of solute from the
surface to the bulk solution.
The authors who have studied the kinetics of the attack of
This is explained by the fact that for Treactionþdilution, the phosphates are in agreement with the fact that the reaction is
temperature rise comes from the heat released by the dilution limited by the diffusional regime.[6,8–10] Thus, the dissolution rate
and the precipitation reaction. coefficient kd was taken equal to the mass transport coefficient kt
(kd ¼ kt).
MODELLING OF THE DISSOLUTION REACTION The dissolution rate can be expressed as follows:
The general principle of the determination of kinetic and dm
thermodynamic parameters consists in exploiting the experimental  ¼ N p Skd ðC eq  CÞ; ð5Þ
dt
profiles of temperatures according to time. The parameters’
identification requires the development of a model that takes with C the weight concentration of fluoroapatite, Ceq the
into account mass and heat balances in the reactor. The model was saturated concentration, m the total mass of the solid, S the
developed according to the following assumptions: surface area of the particle fluoroapatite and Np the number of
‐ The particle shape does not change during the dissolution particles.
process. The saturated concentrations are determined from the research
‐ There is no particle breakage by attrition, nor any growth by work of Elmore and Farr[11] and Farr et al.,[12] who studied the
coalescence among particles. equilibrium for the system CaO–P2O5–H2O and CaO–P2O5–HF–
H2O, which corresponds to the phosphate rock dissolved in a
solution of phosphoric acid.
In our case, the particles have different sizes, taking into account
this parameter. For a class of size given (i), the corresponding mass
in the reactor is equal to

4
mi ¼ N pi V pi rs with V pi ¼ pR3i : ð6Þ
3

The weight concentration of solid in the liquid bulk is given by

the following equation:
Pnc Pnc
m0  mi i¼1 rs N pi ð4=3ÞpðR30;i  R3i Þ
C¼ i¼1
¼ ; ð7Þ
V V

with rs is the density of the phosphate rock, m0 is the initial mass of

solid, R0,i is the initial radius of the particle in class (i), Ri is the
particle radius at time t, Vpi is the volume of fluoroapatite particle
having a radius Ri and V is the liquid volume. nc denotes the
number of size classes of phosphate particles.
For a given size class (i), the mass balance leads to

dmi
Figure 3. Temperatures variations during dilution (Tdilution) and the  ¼ N pi Si kdi ðC eq  CÞ; ð8Þ
reaction of attack (Treactionþdilution), N ¼ 1000 rpm, Tw  31 8C. dt

VOLUME 92, OCTOBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1831
where Spi represents the surface area of fluoroapatite particle with For the studied phosphate ore, we considered that it comprises 9
radius Ri. classes of size: nc ¼ 9 (Table 1), thus we will have a system
comprising of 9 differential equations.
Si ¼ 4pR2i : ð9Þ The combination of Equations (7) and (10) is conducted
with a simplified expression of the concentration in reactional
kdi is the mass transport coefficient for particles with radius Ri. Npi medium:
denotes the number of particles in class (i):
 
m0 X
nc
R3
wi m0 3 wi m0 C¼ wi 1  3i : ð17Þ
N pi ¼ ¼ ; ð10Þ V i¼1 R0i
rs V p0i 4 prs R30i

with wi the fraction of particles with initial radius Ri,0.

The influence of temperature on the mass transfer coefficient Heat balance
(kd) can be determined by the Arrhenius relationship: The heat balance can be expressed as follows:
 
E dT
kdi ¼ kdi;0 exp  : ð11Þ UAðT w  TÞ ¼ ðmreactants C preactants þ mreactor C preactor Þ þ rVDH r :
RT dt
ð18Þ
On the one hand this coefficient depends on the particle size (dp),
the stirring speed (N) and the geometry of the reactor. On the The reaction rate is defined as follows:
other hand, it depends on the effective diffusivity (De) and the
physicochemical properties of the solution (m, r), which in turn d½Fluoroapatite n0 dX
r¼ ¼ ; ð19Þ
depend on the temperature. In this work, since we considered the dt V dt
variation of temperature and particle size during dissolution, we
used an empirical correlation proposed by Elnashaie et al.,[13] with n0, initial number of moles of the fluoroapatite.
expressing the Sherwood number in the event of dissolution of The heat balance is easily rearranged into
phosphate rock:
  dT dX
kd dp 3dp 0:479 0:33 0:359 UAðT w  TÞ ¼ mreactants C preactants w þ n0 DH r : ð20Þ
Sh ¼ ¼ 0:587 Sc Re ; ð12Þ dt dt
De dreac
w is the thermal inertia such as w ¼ 1 þ ððmreactor C preactor Þ=
NrL d2ag m ðmreactants C preactants ÞÞ, w is the ratio of the total heat flow, necessary
Re ¼ ; Sc ¼ ; for the heating of the reactants and the reactor, to the reactants
m rL De
heat flow.
with dreac the reactor diameter and dag the stirrer diameter. DT ad;dis is the adiabatic temperature rise:
For a given temperature, the mass transfer coefficients for two
different sizes (i and j) satisfy the following equation: n0 ðDH r Þ
DT ad;dis ¼ : ð21Þ
mreactants C preactants
 0:521
kdi dp;i
¼ : ð13Þ
kdj dp;j The heat balance (Equation (20)) is easily rearranged into

Thus, if we consider the mass transfer coefficient (kd,ref) for a dT ðT w  TÞ DT ad;dis dX

¼ þ ; ð22Þ
particle radius (Rref), we can write dt tc w w dt

 0:521  0:521 where tc is a characteristic thermal constant:

dp;i Ri
kdi ¼ kd;ref ¼ kd;ref : ð14Þ
dp;ref Rref
mreactants C preactants
tc ¼ : ð23Þ
UA
We finally find
 0:521   The thermal characteristics of the reactor used for the thermody-
kdi ¼ kd;ref;0
Ri
exp 
E
: ð15Þ namic and kinetic determination are first determined using a
Rref RT traditional calorimetric measurement.
The method consists firstly in the introduction of a fluid,
The mass balance (Equation (8)) is easily rearranged into whose physicochemical properties are known, in the reactor.
It consists secondly in making disturbances on the wall tempera-
    ture and in following the reactor temperature in the function of
dRi Ri 0:521 1 E
 ¼ kd;ref;0 exp  ðC eq  CÞ: ð16Þ time.
dt Rref rs RT The resolution of the heat balance in such conditions leads to a
thermal inertia w of 1.25 and an overall heat transfer coefficient UA
The initial condition stipulates that for t ¼ 0 we have Ri ¼ Ri0. of 13.52 W K1.

1832 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, OCTOBER 2014
Identification of Kinetic and Thermodynamic Parameters relative error (Equation (27)) was used as the objective function to
identify the parameters’ values for the performed experiments. The
Determination of the enthalpy of dissolution procedure is to search values of E and kd,ref,0 corresponding to the
The integration of Equation (22) leads to minimum value of the relative error

nj  
Zt 1X T expi  T calci 2
DT ad T  Tw relative error ¼ ; ð27Þ
X ¼ ðT  T 0 Þ þ dt: ð24Þ nj i¼1 T expi
w tc w
0
where nj is the number of experimental and calculated points for
For t ¼ 0 we have X ¼ 0 and T ¼ T0 or t ! 1 we have X ¼ 1 and the experiment j.
T ¼ Tw. The relative error between the calculated and measured
In the experimental study, an initial temperature (T0) equal to temperatures was minimized using the subroutine ‘fminsearch’.
that of wall (Tw) was imposed, leading to the following simplified The values of the parameters identified correspond to the minimum
expression: relative error.
The regression procedure is the one used by the ’fminsearch’
Z1 function. It is based on the simplex method and uses Nelder–Mead
1
DT ad ¼ ðT  T w Þdt: ð25Þ simplex algorithm. Simplex Method is an iterative procedure that
tc
0 allows the improvement of the solution at each step. This
procedure is finished when the improvement of the solution is
Based on the experimental results, the value of adiabatic not possible.
temperature rise can be determined and the reaction enthalpy The optimization was performed on all the performed experi-
can be deduced: ments. Figure 4 presents an example of comparison between the
theoretical and experimental temperatures. From the conducted
DT ad mreactants C preactants experiments, an agreement between both temperatures can be
DH r ¼ : ð26Þ
n0 observed.
From the different values of kd,ref,0 and E determined for each
Several experiments were conducted under different operating experiment, it was possible to determine the average values of
 
conditions. On the one hand these experiments were used to these parameters kd;ref;0 ¼0:135 m s1 and E ¼ 22:7 kJ mol1 .
determine a mean value of the dissolution enthalpy; on the other
Determination of parameters uncertainties
hand to evaluate the experimental reproducibility. Table 2 gives
the determined experimental values. To perform a comprehensive statistical analysis of all experiences,
The results were analyzed using a valid statistical method which we define a function D which corresponds to the sum of squared
is Student’s t analysis with 95 % CL. The uncertainty of the deviations calculated over all the experiments performed:
dissolution enthalpy is estimated at 2.5 %. Thus the determined !
enthalpy value is DHr ¼ 136.81  3.39 kJ mol1. As for the X
N X
nj
2
enthalpy value, it is related to the fluoroapatite mole number. D¼ ðT expi  T calci Þ : ð28Þ
j¼1 i¼1
A brief look at the literature allows us to discover a value given
by Brahim et al.[14] DHr ¼ 172 kJ mol1, which is different from
N and nj are respectively the total number of experiments carried
our value. This can be explained by the fact that the fluoroapatite
out and the number of points corresponding to the experiment j.
studied by these authors is synthetic.
In order to establish the Information Matrix, we first determined
Identification of mass transfer coefficient the matrix of the second partial derivative (@ 2 D=@a2 ).[15,16]
The kinetic identification was finally carried out by coupled
resolution of heat and mass balances for the performed experi-
ments. As the differential equations (Equations (16) and (22)) are
nonlinear, an exact analytical solution cannot be obtained and
numerical techniques are required to deduce the kinetic param-
eters. The set of mass and heat balances was solved using a
Matlab1 explicit Runge–Kutta method ‘ode45’. It is to be noted that
the mass balance (Equation (16)) leads to nine differential
equations since our phosphate has nine size classes.
The established system of differential equations is solved while
searching the values of kinetic and thermodynamic parameters
leading to the best agreement between the experimental and
calculated temperature profiles. The predefined ‘fminsearch’
function was used to identify the parameters (E and kd,ref,0). The

Table 2. Values of the enthalpy of dissolution

Experience 1 2 3 4 5 6
1
Figure 4. Example of the comparison between the experimental and
DHr (kJ mol ) 134.38 135.57 143.08 135.27 137.43 135.14 modelled temperature profiles, N ¼ 1000 rpm, T ¼ 23 8C.

VOLUME 92, OCTOBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1833
 This matrix can be calculated as follows: The uncertainty can be defined by
2 
   3 t a=2;ðnmÞ Sai
@2D @2D s ai ¼   100: ð36Þ
6 7 ai
@2D 6 @k2 k ;E @k@E k ;E 7
¼6
6  2   2  7 ¼ 2FT F:
7 ð29Þ
@a2
4 @ D @ D 5 We can also calculate a correlation coefficient given by the
@k@E k ;E @E2 k ;E following equation:[17]
Pn



i¼1 ðT exp;i T mod;i  T exp T mod Þ
‘a’ denotes the vector of parameters to be determined: a ¼ {kd,ref,0, qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
r¼ P P ; ð37Þ
  n
2 n
2
i¼1 ðT exp;i  T exp Þ i¼1 ðT mod;i  T mod Þ
2 2
E}. k and E are the average values determined of kdref,0 and E.
The terms of the matrices are numerically calculated by taking
the approximation of derivatives by finite differences. For
mod represent the mean value of the experimental

exp and T
where T
example, the derivatives of D with respect to k can be calculated
temperature and calculated by the model.
as follows:
Statistical analysis is realized on the basis of all experiments
 2  performed. The values of covariance, variance and correlation
@ D Dk ð1þeÞ;E þ Dk ð1eÞ;E  2Dk ;E
¼  ; coefficient are Covkd;ref;0 ¼ 2:01  104 , CovE ¼ 7:46  106 ,
@k2 k ;E ðk eÞ2 S2kd;ref;0 ¼ 4:80  103 , S2E ¼ 931, s kd;ref;0 ¼ 5:88 %, s E ¼ 6:75 % and
  ð30Þ
@D Dk ð1þeÞ;E  Dk ð1eÞ;E r ¼ 0.986.
¼  : The proposed model gives a very good description of the
@k k ;E 2k e
performed experiments. The values of the parameter uncertainties
are relatively low and the value of the correlation coefficient is very
For the numerical computation of gradients, a value of e ¼ 103 close to 1. This shows the good agreement between the model and
was taken. the experimental measurements.
By calculating the inverse of the Information Matrix (FTF), The activation energy value determined in this study is E ¼
the covariance matrix of parameters (Cov) can be determined: 22:7  1:53 kJ mol1 (E=R ¼ 2730:9  184:3 K). Besides, for the
reference diameter dp,ref ¼ 4.08  104 m (this diameter corre-
 2 1
1@ D sponds to the average diameter of the 5th class size, see Table 1),
Cov ¼ ðFT FÞ1 ¼ : ð31Þ
2 @a2 the diffusion coefficient is kd;ref;0¼0:135  0:008 m s1 .

   
The diagonal elements of the matrix Cov: Cov1,1 and Cov1,2 dp 0:521 2730:9
correspond respectively to the covariance of parameters kd,ref,0 and kd ¼ 0:135 exp  : ð38Þ
dp;ref T
E. The variance of the identified parameters is given by the
following equations:
The low value of activation energy enables us to ensure that the
chemical regime is not the limiting step and thus the mass transfer
S2kd;ref;0 ¼ Cov1;1 S2y S2E ¼ Cov2;2 S2y : ð32Þ
is the rate‐controlling step. Furthermore, the activation energy
value is in the interval of the values reported in literature, whose
S2y is estimator of the variance of measures: values lie between 15 and 29 kJ mol1.[9,18–20]
For a fixed particle size, the mass transfer coefficient depends
DðkÞ on the temperature and the particle size. Table 3 presents the
S2y ¼ : ð33Þ
nm variation of the values of mass transfer coefficient against
temperature, which correspond to a particle size equal to
n and m are, respectively, the total number of Ppoints of all tests 4.08  104 m.
performed and the number of parameters (n ¼ Nj¼1 nj , m ¼ 2). From the values of kd and using Equation (12), we can estimate
The confidence interval of the parameter ‘ai’ is given by the values of effective diffusion coefficient De.
  The values of diffusion coefficient are of the same order of
ai  t a=2;ðnmÞ Sai < ai < ai þ t a=2;ðnmÞ Sai : ð34Þ magnitude as the value provided by Elnashaie et al.[13] which is

equal to 9.7  1010 m2 s1 for a particle size of 3.61  104 m, a
Thus ai ¼ ai  t a=2;ðnmÞ Sai : ð35Þ temperature 70 8C and speed stirring 800 rpm. It is worthwhile
to mention that the comparison cannot be meaningful and
With t a=2;ðnmÞ is the value of Student, a confidence level of 95 % rational, given the difference of operating conditions (nature of
(a ¼ 0.05) was taken. phosphate).

Table 3. Values of mass transfer coefficient and effective diffusivity against temperature, N ¼ 1000 rpm, dp ¼ 4.08  104 m

T (8C) 25 35 45 55 65

kd (m s1) 1.41  105 1.92  105 2.44  105 3.33  105 4.15  105
De (m2 s1) 2.25  1010 3.57  1010 5.11  1010 8.13  1010 11.3  1010

1834 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, OCTOBER 2014
SIMULATION AND PARAMETRIC STUDY
The model established allows the study of the effect of different
parameters on the reaction of dissolution of the fluoroapatite.
Among the multitude of factors that can be studied, the initial
radius of particles and the stirring speed are selected in the present
study.

Influence of initial radius of particles

The variation of the size of a particle with time can be obtained by
the proposed model. Figure 5 illustrates a simulation example
describing the effect of the initial particle radius. Since a mass of
particles lower than the maximum mass that can dissolve
(m < CeqV) was chosen in this study, all the rays decrease until
they reach zero. In the opposite case (m > CeqV), the radius tends to
a non‐zero limit. Moreover, the bigger the size of the particle is, the
slower the dissolution reaction will be. Indeed, the time required to
dissolve a particle varies from 220 s for diameter particles of Figure 6. Influence of stirring speed, m ¼ 50 g, dp0 ¼ 0:4 mm, T ¼ 30 8C.
250 mm to 530 s for diameter particles of 400 mm.

Influence of stirring speed

While in the study of the dilution reaction, the reactor contains
The stirring speed is a very significant parameter in the dissolution
phosphoric and sulphuric acids, in the study of the precipitation
process, which conditions the hydrodynamics of the system and
reaction, the reactor comprises the phosphate in addition to the two
affects the diffusion coefficient. Figure 6 shows a simulation
acid solutions (found in the study of the dilution reaction). As
describing the effect of the particle radius. It is significant to note
phosphate has low heat capacity and is added in small proportions,
that the radius evolves in the same way regardless of the stirring
the difference between the heat capacities of the two charges can be
speed, and only the dissolution time is extended when the agitation
neglected. This can be written as follows:
is less strong. With respect to the limiting case which reaches a null
stirring speed, reducing the ray, it is much slower and the time
mC p ¼ mreactants C preactants þ mreactor C preactor : ð39Þ
required to dissolve a particle becomes much larger.

MODELLING OF THE PRECIPITATION REACTION Dilution reaction

The reaction rate is expressed by the following equation:
Mass and Heat Balances
The second stage of the attack of phosphate ore is the reaction of d½H2 SO4  dX 1
sulphuric acid with the dissolution product (monocalcium r dilution ¼  ¼ ½H2 SO4 0 ; ð40Þ
dt dt
phosphate). What should be born in mind at this level is that for
the same jacket temperature imposed (Tw), we conducted two with X1 the conversion of the dilution reaction.
types of experiments the first of which is the dilution of the The heat balance of the dilution reaction, implemented in batch
sulphuric acid in phosphoric acid and the second is the reaction of mode, leads to
attack.
dX 1 dT 1
UAðT w  T 1 Þ ¼ ½H2 SO4 0 VDH dilution þ mC p : ð41Þ
dt dt

The heat balance is easily rearranged into

dT 1 ðT w  T 1 Þ DT ad;dilution dX 1
¼ þ ; ð42Þ
dt tc w w dt

which can finally be integrated as

Zt
DT ad;dilution T1  Tw
X 1 ¼ ðT 1  T 0 Þ þ dt; ð43Þ
w tc w
0

with DT ad;dilution the adiabatic temperature rise due to dilution.

V½H2 SO4 0 ðDH dilution Þ

DT ad;dilution ¼ : ð44Þ
mC p

Figure 5. Influence of initial particles size, m ¼ 50 g, N ¼ 1000 rpm, The exploitation of all tests was carried out with the same
Tw ¼ 30 8C. previously described manner (Determination of the Enthalpy of

VOLUME 92, OCTOBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1835
Dissolution section). This exploitation makes it possible to Identification of Kinetic and Thermodynamic Parameters
determine the rise in adiabatic temperature and to deduce the Based on the equations provided by the heat and mass balance, a
dilution enthalpy: DH dilution ¼ 12:86  0:69 kJ mol1 . The un- program using Matlab has been developed. This program can not
certainty was calculated by means of Student confidence interval only handle the experimental evolution of the temperatures against
based on 6 measurements with a confidence level of 95 %. The time, but also allows the determination of the reaction enthalpy
enthalpy value is related to the sulphuric acid mole number. (DH reaction ) and the identification of kinetic parameters (k, a)
Attack reaction always using a methodology similar to that presented above.
The reaction rate is expressed by the following equation: Determination of the enthalpy of the precipitation reaction
From the heat balance (Equation (49)), the following relationship
d½CaðH2 PO4 Þ can be written:
r¼ : ð45Þ
dt
dT 2 ðT w  T 2 Þ DT ad;dilution dX 1 DT ad;reaction dX 2
On the other hand, the kinetic expression of the reaction can be ¼ þ þ : ð53Þ
dt tc w w dt w dt
expressed as follows:
This equation is easily rearranged into
r ¼ k½CaðH2 PO4 Þn ½H2 SO4 m ; ð46Þ
Zt
with k as the rate constant, n and m are the reaction orders DT ad;dilution DT ad;reaction ðT 2  T w Þ
X1 þ X 2 ¼ ðT 2  T 0 Þþ : ð54Þ
pertaining to monocalcium phosphate and sulphuric acid, w w tc w
respectively. 0

[Ca(H2PO4)2]0: Initial concentration of monocalcium phosphate

(mol m3). With the following conditions:
[H2SO4]0: Initial concentration of sulphuric acid (mol m3). for t ¼ 0 we have X1 ¼ X2 ¼ 0 and T2 ¼ T0,
Defining X2 as the conversion of monocalcium phosphate, we for t ! 1 we have X1 ¼ X2 ¼ 1 and T2 ¼ Tw.
can easily rearrange Equations (45) and (46): For T0 ¼ Tw, Equation (43) leads to the following simplified
 m expression:
dX 2 ½H2 SO4 0
¼ k½CaðH2 PO4 Þnþm1 ð1  X 2 Þn X 2 : ð47Þ
dt 0
½CaðH2 PO4 Þ2 0 Z1
1
DT ad;dilution þ DT ad;reaction ¼ ðT 2  T w Þ: ð55Þ
In what follows, work will be with equimolar reactants and the tc
0
overall reaction order (a ¼ n þ m) will be defined.
The mass balance (Equation (47)) can then be simplified into The reaction enthalpy has been determined using the adiabatic
temperature rise DT ad;dilution . From the different values of DH reaction
dX 2
¼ k½H2 SO4 a1 a
0 ð1  X 2 Þ : ð48Þ determined for each experiment and using a Student t test with a
dt confidence level of 95 %, it was possible to determine the average
value and the corresponding uncertainty. For all the experiments
The heat balance must take into account the heat release associated performed, it was found that: DH reaction ¼ 228:7  8:04 kJ mol1 .
with the attack reaction and the dilution reaction. Heat balance in The enthalpy value is related to the fluoroapatite mole number.
batch isoperibolic mode leads to the following equation: This value is close to that reported in the literature by Antar
et al.[20]: DHreaction ¼ 224.5 kJ mol1.
dX 2
UAðT w  T 2 Þ ¼ ½H2 SO4 0 VDH reaction þ ½H2 SO4 0
dt Determination of kinetic parameters
ð49Þ
dX 1 dT 2 The elaborated program consists in solving the system of
VDH dilution þ mC p :
dt dt differential equations from mass and heat balances (Equations (48)
and (52)). In fact, this program treats the signal DT ¼ T2  T1 ¼
After the rearrangement of the two heat balance equations Treactionþdilution  Tdilution, and identifies the kinetic parameters of
(Equations (41) and (49)), the following equation is obtained: the precipitation reaction (k and a), so as to find the best
coincidence between experimental profiles and those provided by
dX 2 dDT the model.
UADT ¼ ½H2 SO4 0 VDH reaction þ mC p : ð50Þ
dt dt The regression procedure used for the identification of kd,ref,0 and
E is the same. The ‘fminsearch’ function was also used to identify
DT is the difference between the attack reaction temperature (T2) the parameter (k and a). The objective function is a relative error
and that obtained during dilution alone (T1): based on the temperature differences DT.
DT ¼ T 2  T 1 ; ð51Þ   !1=2
1 P DT exp  DT calc 2
relative error ¼ : ð56Þ
After reorganization, Equation (50) gives n n DT exp

dDT DT DT ad;reaction dX 2 Figure 7 shows an example, from which the accordance between
¼ þ : ð52Þ
dt tc w w dt experimental and theoretical curves was found to be satisfactory.

1836 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, OCTOBER 2014
 dissolution time of a particle as a function of its size and of the
stirring speed. Furthermore, the developed kinetic model of
dissolution takes into account the effect of the variation of the
reactor temperature and that of the concentration on the
dissolution kinetics.
This reaction studied can be further used as a model reaction for
the study of thermal stability or thermal runaways of heteroge-
neous reactors. The methodology developed for the identification
of kinetic parameters and heat can be applied to other heteroge-
neous reactions.

NOMENCLATURE
A heat transfer area (m2)
C concentration (mol m3)
Cp specific heat capacity (J kg1 K1)
d diameter (m)
Figure 7. Identification of the kinetics of precipitation reaction, Tp ¼ 31 8C, De effective diffusivity (m2 s1)
N ¼ 1000 rpm.
E activation energy (J mol)
i class of size
k rate constant (mol1 m3 s1)
After treating a series of experiments, an average value and k0 frequency factor (mol1 m3 s1)
the uncertainty of the rate constant was determined and follows kd rate dissolution coefficient (m s1)
the same procedure described in Identification of Mass Transfer kr rate constant for the dissolution reaction (m s1)
Coefficient section: k ¼ ð5:46  0:203Þ  105 m3 s mol1 and ks mass transport coefficient (m s1)
a ¼ 2.05  0.097. m mass (kg)
The statistical analysis allowed us to determine the values of m reaction order as regards H2SO4
covariance, variance and correlation coefficient: Covk ¼ 2:72 N particle number
1011 , Cova ¼ 2:28  102 , S2k ¼ 2:03  106 , S2a ¼ 5:87  102 nj mole of component j (mol)
and r ¼ 0.974. n reaction order regarding Ca(H2PO4)2
The uncertainties of parameters are 6.11 % for k and 4.71 % for R particle ray (m)
a. The value of the correlation coefficient shows good agreement r reaction rate (mol m3 s1)
between the model and experiment. Sp particle surface area (m2)
These results show that the precipitation of calcium sulphate in T temperature (K)
phosphoric acid solutions is of a second order (a  2). Such a value t time (s)
is close to those found previously by several authors in their studies U overall heat transfer coefficient (W m2 K1)
on crystal growth of gypsum.[21–23] V volume (m3)
X conversion

CONCLUSION
The present work undertakes the study of the dissolution reaction Greek Symbols
of phosphate in phosphoric acid solution as a model reaction of a reaction order
liquid–solid reactions. A methodology has been developed for the DHr adiabatic temperature rise (J mol1)
identification of kinetic and thermal parameters of the reaction F thermal inertia
based on simple temperature measurements within the reactor. m viscosity (kg m1 s1)
The calorimetric approach used does not appeal to large, expensive r density (kg m3)
equipment. While calorimetry is very often used for the s relative standard deviation
determination of thermodynamics parameters alone, the resolu- tc thermal constant (s)
tion of the coupled heat and mass balances also allowed the
determination of kinetics parameters.
With the help of this methodology, the dissolution of fluoroa- Superscripts
patite in a solution of diluted phosphoric acid along with the 0 initial
precipitation reaction have been studied. 1 dilution
Two kinetic models based on the resolution of heat and mass 2 attack reaction
balances and associating the solid liquid mass transfer with ag stirrer
chemical kinetic processes as well as describing these reactions cal calculated
were carried out. It is through the agreement with the results eq equilibrium
found by other authors that the proposed methodology proved exp experimental
to be trustworthy. It appears that the kinetic model of dissolution l liquid
is capable of simulating the behaviour of the phosphate p particle
particle dissolution. Besides, the model predicts the variation of s solid
particle size as a function of time and the variation of the w wall

VOLUME 92, OCTOBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1837
REFERENCES
[1] A. Bhattacharya, Chem. Eng. Process. 2007, 46, 573.
[2] H. Markusa, S. Fugleberg, D. Valtakaria, T. Salmi, D. Y.
Murzin, M. Lahtinen, Chem. Eng. Sci. 2004, 59, 919.
[3] T. Salmi, H. Grenman, H. Bernas, J. Warna, D. Y. Murzin,
Chem. Eng. Sci. 2010, 65, 4460.
[4] P. O. Mchedlov‐Petrossyan, W. B. Zimmerman, G. A.
Khomenko, Chem. Eng. Sci. 2003, 58, 2691.
[5] P. L. Mills, R. V. Chaudhari, Catal. Today 1997, 37, 367.
[6] P. Becker, Phosphate and Phosphoric Acid, Fertilizer Science
and Technology Series, Marcel Dekker, New York 1983.
[7] T. N. Zwietering, Chem. Eng. Sci. 1958, 8, 244.
[8] F. Gioia, G. Mura, A. Viola, Ind. Eng. Chem. Process Des. Dev.
1977, 16, 390.
[9] S. V. Sluis, Y. Meszaros, W. G. J. Marchee, H. A. Wesselingh,
G. M. V. Rosmalen, Ind. Eng. Chem. Res. 1987, 26, 2501.
[10] K. Shakourzadeh, R. Bloise, F. Baratin, “Modeling of a Wet‐
Process Phosphoric Acid Reactor: Influence of Phosphate
Rock Impurities”, Proceedings of the Second International
Congress on Phosphorus Compounds, Boston 1980, p. 443.
[11] K. L. Elmore, T. D. Farr, Ind. Eng. Chem. 1940, 32, 580.
[12] T. D. Farr, G. Tarbutton, H. T. Lewis, J. Phys. Chem. 1962, 66,
318.
[13] S. Elnashaie, T. Al‐Fariss, S. Abdel Razik, H. Ibrahim, Ind.
Eng. Chem. Res. 1990, 29, 2389.
[14] K. Brahim, I. Khattech, J. P. Dubes, M. Jemal, Thermochim.
Acta 2005, 436, 43.
[15] J. P. Corriou, Commande des procédés, Lavoisier Technique &
Documentation, Paris 2012.
[16] J. P. Corriou, Process Control—Theory and Applications,
Springer‐Verlag, London 2004.
[17] E. B. Manoukian, Guide de statistique appliquée, Hermann,
Paris 1986.
[18] F. Sevim, H. Saraç, M. M. Kocakerim, A. Yartasi, Ind. Eng.
Chem. Res. 2003, 42, 2052.
[19] A. Yarstri, M. M. Kocakerim, S. Yappici, C. Ozmetin, Ind. Eng.
Chem. Res. 1994, 33, 2220.
[20] K. Antar, K. Brahim, M. Jemal, Thermochim. Acta 2006, 449,
35.
[21] E. Cetin, I. Eroglu, S. Ozkar, J. Cryst. Growth 2001, 231, 559.
[22] J. S. Gill, G. H. Nancollas, J. Cryst. Growth 1980, 48, 34.
[23] B. R. Smith, F. Sweett, J. Coll. Interface Sci. 1971, 37, 612.

Manuscript received April 28, 2013; revised manuscript received

October 20, 2013; accepted for publication November 2, 2013.

1838 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, OCTOBER 2014

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