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R. M. BEHBAHANI
Research Department, Petroleum University of Technology, Ahwaz, Iran
H. MULLER-STEINHAGEN
Institute for Thermodynamics and Thermal Engineering, University of Stuttgart, Germany; Institute of Technical
Thermodynamics, German Aerospace Centre, Stuttgart, Germany
M. JAMIALAHMADI
Research Department, Petroleum University of Technology, Ahwaz, Iran
Multistage shell and tube evaporators are frequently used in phosphoric acid plants to increase the concentration of dilute
phosphoric acid to 5255 wt% P2 O5. The concentrated phosphoric acid solution is supersaturated with respect to calcium
sulfate. As a result, part of the calcium sulfate in the liquor deposits on the heat exchanger tube walls. Because the thermal
conductivity of these scales is very low, thin deposits can create a significant resistance to heat transfer. Therefore, regular
cleaning of heat exchangers is required, frequently at shorter than biweekly intervals. As the major costs in modern phosphoric
acid plants are the cost of energy, a thorough understanding of the fouling kinetics and of the effects of various operational
parameters on the behavior of calcium sulfate is required to improve operation and design of the shell and tube heat
exchangers, which are extensively used. In this investigation, a large set of heat exchanger data was collected from shell
and tube heat exchangers of the phosphoric acid plant of the Razi Petrochemical Complex in Iran, and the fouling deposits
were analyzed with respect to appearance and composition. The overall heat transfer coefficients and fouling resistances
were evaluated at different times, and a kinetic model for the crystallization fouling was developed. It is shown that the
crystallization rate constant obeys an Arrhenius relationship with an activation energy of 57 kJ/mol. The average absolute
error of 12.4% shows that the predictions of the suggested model are in good agreement with the original plant data.
INTRODUCTION below:
The principal reaction occurring in a phosphoric acid plant CaF2 + H2 SO4 CaSO4 + 2HF (2)
is the reaction between tricalcium phosphate and sulfuric
acid to give soluble phosphoric acid and insoluble calcium 6HF + SiO2 H2 SiF6 + 2H2 O (3)
sulfate:
3SiF4 + 2H2 O 2H2 SiF6 + SiO2 (4)
Ca3 (PO4 )2 + 3H2 SO4 + 6H2 O 2H3 PO4 + 3CaSO4 .2H2 O
CaCO3 + H2 SO4 + H2 O CaSO4 .2H2 O + CO2 (5)
(1)
In addition to this main reaction, there are a number of par- Fe2 O3 (orAl2 O3 ) + 2H3 PO4 2FePO4 (orAlPO4 ) + 3H2 O
allel minor reactions, the most important of which are shown (6)
292
R. M. BEHBAHANI ET AL. 293
Figure 1 Forced circulation evaporator for phosphoric acid concentration. Figure 3 Typical control system for a forced-circulation evaporator.
The inlet and the outlet temperatures (Tin and Tout ) of the acid
in the tubes, the mass flow rate of the shell-side steam ( M st ), and
the steam pressure (Pshell ) and its temperature (Tshell ) were mea-
sured on the plant heat exchangers every four hours. The tubes
were clean at the start. The overall heat transfer coefficient in
the plant, including both film resistances, is therefore calculated Figure 6 Variation of heat transfer coefficient versus time at different surface
by a simple energy balance, assuming that the heat contribu- temperatures.
tions of steam de-superheating and condensate subcooling are terface between deposit and liquor (surface temperature) re-
negligible: mains constant at the value of the clean heat transfer surface.
st hv (Pshell )
M
U= (7) The measured overall heat transfer coefficients for different sur-
Tlm .A
face temperatures are plotted against time in Figure 6 for phos-
with phoric acid solutions at a constant velocity, bulk temperature,
Tout Tin and solution concentration. The initial U values compare favor-
Tlm = Tin
(8)
ln TTststT ably with the design values. The corresponding fouling resis-
out
tances are plotted against time in Figure 7. For all runs depicted
Because no fouling will occur on the steam-side of the heat in Figures 6 and 7, the flow liquor velocity and the bulk tempera-
exchanger, the fouling resistance on the liquor side can be cal- ture were 1.8 m/s and 73 C, respectively. The results show an al-
culated from: most linear increase in fouling resistance with time. The deposit
1 1 formation rate also increases with increasing surface tempera-
Rf = (9) ture and calcium sulfate concentration. Previous investigations
U U0
on scale formation from aqueous solutions of CaSO4 [1, 2] have
where U0 is the overall heat transfer coefficient at the beginning shown comparable trends. For a chemical reaction-controlled
and U is the coefficient some time later, when fouling has taken system, the main effect of wall temperature is via the reaction
place. The physical properties of phosphoric acid are available rate constant. As the temperature of the heat transfer surface is
from standard reference tables. raised, the reaction rate and hence the fouling resistance due to
During plant operation, the steam temperature (i.e., pressure) crystallization increases.
is continuously increased in order to maintain a constant heat
flow rate despite the fouling-related drop in overall heat transfer
coefficient. This leads to a constant heat flux thermal boundary
condition, if the small decrease in internal tube diameter due to
the thin deposits is neglected. The surface temperature is then
calculated using the following simplified procedure:
ERROR ANALYSIS
DEPOSIT ANALYSIS
2 Kw 2
= CCaSO4 CCaSO4 (12)
d frd
where frd is the mass fraction of the calcium sulfate in the deposit,
which was determined to be 0.86 (see above).
Solving Eq. (12) with initial boundary conditions (dd (0) = di )
yields the scaled diameter as a function of time:
2 Kw 2
dd (t) = di CCaSO4 CCaSO4 t (13)
d frd
Substituting Eq. (13) into Eq. (10) gives the time-dependent
fouling resistance for scale:
di di
Rf (t) = ln 2 (14)
2d di 2 Kw CCaSO C
d frd 4 CaSO4 t Figure 11 Comparison of measured and predicted fouling resistances at dif-
ferent surface temperatures.
The surface reaction rate constant Kw is assumed to follow an
Arrhenius relationship: CONCLUSIONS
Eact
Kw = k0 . exp (15) A large number of plant operating data of the heat exchangers
R Ts
Fouling resistance data for all plant measurements were re- of the phosphoric acid evaporation unit at the Razi Petrochemi-
gressed to fit the model given by Eq. (14) with the average ab- cal Complex in Iran were collected every four hours, with each
solute error of 11.5%. The Arrhenius dependency of the surface run lasting about 812 days. Heat transfer coefficients and foul-
reaction rate constant for the selected plant measurements is ing rates were evaluated. A linear increase of fouling resistance
shown in Figure 10. The activation energy evaluated for the sur- with time has been observed, which is strongly affected by the
face reaction of the deposit formation is found to be 57 kJ/mol. surface temperature. A kinetic model for crystallization fouling
This value matches the measured activation energy of 56 kJ/mol was developed. It has been shown that the crystallization rate
obtained by Behbahani [5] from measurements with an ex- constant obeys an Arrhenius relationship with an activation en-
perimental fouling test rig, indicating the validity of the pro- ergy of 57 kJ/mol. The predictions of the suggested model are in
posed model. The frequency factor (k0 ) is determined to be good agreement with the plant operating data; hence the model
43,000 kg/(m2 .min.wt%2 ). The magnitude of the activation en- can be used to determine fouling rates and cleaning cycles for
ergy is also a strong indication that the formation of the fouling modified heat exchanger design and plant operating conditions.
resistance is indeed controlled by surface reaction. The fouling
resistances calculated using the proposed model are compared ACKNOWLEDGMENT
with measured values in Figure 11 for different surface temper-
atures. The average absolute error of 12.4% shows reasonable The support of the presented investigations by Razi Petro-
accuracy of prediction. chemical Complex of Iran is gratefully acknowledged.
heat transfer engineering vol. 28 no. 4 2007
298 R. M. BEHBAHANI ET AL.