Heat Transfer Engineering

ISSN: 0145-7632 (Print) 1521-0537 (Online) Journal homepage: http://www.tandfonline.com/loi/uhte20

Heat Exchanger Fouling in Phosphoric Acid

Evaporators

R. M. Behbahani , H. Mller-Steinhagen & M. Jamialahmadi

To cite this article: R. M. Behbahani , H. Mller-Steinhagen & M. Jamialahmadi (2007) Heat

Exchanger Fouling in Phosphoric Acid Evaporators, Heat Transfer Engineering, 28:4, 292-298,
DOI: 10.1080/01457630601122468

To link to this article: http://dx.doi.org/10.1080/01457630601122468

Published online: 06 Mar 2007.

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Heat Transfer Engineering, 28(4):292298, 2007
Copyright 
C Taylor and Francis Group, LLC
ISSN: 0145-7632 print / 1521-0537 online
DOI: 10.1080/01457630601122468

Heat Exchanger Fouling in Phosphoric

Acid Evaporators

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)

Address correspondence to Dr. Hans Muller-Steinhagen, Institute of Tech-

Essentially, all iron and aluminum present in the phosphate rock
nical Thermodynamics, German Aerospace Center, Pfaffenwaldring 38-40, D- is dissolved in the form of iron and aluminum phosphates. Most
70569, Stuttgart, Germany. E-mail: Hans.Mueller-Steinhagen@dlr.de solutions in the phosphoric acid plant are saturated with respect

292
 R. M. BEHBAHANI ET AL. 293

to calcium sulfate. The key to success in the phosphoric acid

plant is in the control and operation of the reaction system. The
objectives of the reaction system are to obtain maximum extrac-
tion of P2 O5 and produce easily filterable and washable gypsum
so that there will be a minimum loss of soluble P2 O5 in the waste
product.
The resulting phosphoric acid is separated from the solid
products of the reaction by filtration. The product, called filter
acid, is usually relatively low in concentration, about 30% P2 O5 .
This acid is concentrated to either about 40 or 54% P2 O5 , de-
pending on the process in which it is to be used. If the acid is to
be shipped rather than used in a nearby ammonium phosphate
plant, it is concentrated to 54% P2 O5 , and a clarification step is
employed to remove suspended solids that would settle during
shipping.
Figure 2 Phosphoric acid evaporator plant in Razi Petrochemical Complex,
Multistage forced circulation evaporators are frequently used Iran.
in phosphoric acid plants to increase the concentration of di-
lute phosphoric acid to 5255 wt% P2 O5 . A forced circulation
evaporator is essentially an evaporation circuit comprising the efficiencies, each stage of the evaporation should be controlled
following integral components: heat exchanger, flash chamber, separately.
acid circulation pump, condenser, vacuum pump, and associated After some time of operation, the internal surfaces of equip-
connecting piping, as shown in Figure 1. A picture of the actual ment in contact with the process acid become covered with a de-
evaporator unit in the Razi Petrochemical Complex in Iran is posit of scale, which can be removed by washing out with water
shown in Figure 2. at high velocity. This de-scaling action is partly by dissolution
Evaporator controls can be either simple or highly automatic, and partly by abrasion. The flash chamber, heat exchangers, and
depending on the situation. Control of product strength is ob- acid piping are the main items that require washing at regular
tained indirectly, usually by controlling the absolute pressure intervals. The problems of scaling are primarily economic. As
and the liquid temperature together. In a typical system (see
Figure 3), the operator will set the acid feed rate, absolute pres-
sure, and re-circulating acid temperature. Controls will hold the
feed rate and absolute pressure constant. The acid temperature
controller will operate the steam control valve to the heat ex-
changer. If the acid strength drops, the boiling point of the acid
will drop, reducing the acid temperature. The temperature con-
troller will then open the steam valve to evaporate more water
to bring the acid back to strength. If the acid exceeds the de-
sired strength, the reverse will take place. Automatic cut off
may be used to guard against the possibility of overheating the
acid leaving the heater. To maintain the best production rates and

Figure 1 Forced circulation evaporator for phosphoric acid concentration. Figure 3 Typical control system for a forced-circulation evaporator.

heat transfer engineering vol. 28 no. 4 2007

294 R. M. BEHBAHANI ET AL.
Figure 4 Fouled graphite heat exchanger in phosphoric acid evaporator plant.
scaling becomes more severe, maintenance costs and downtime
are increased. Downtime can be the most costly of these, partic-
ularly when it is unscheduled.
The scaling of the heat exchanger surfaces has been of most
concern because of reduced heat transfer rates and breakage of
the fragile impregnated-graphite tubes. Figure 4 shows the heat
exchanger of a phosphoric acid evaporation plant, taken out of
service due to excessive plugging and damage to the tubes.
PROCESS DESCRIPTION
The Prayon wet process phosphoric acid plant in the Razi
Petrochemical Complex in Iran has a nominal capacity of 1000
metric tons of P2 O5 per day. The basic raw materials for the
phosphoric acid plant are ground phosphate rock and 98% sul-
furic acid. The process consists of digesting phosphate rock with
sulfuric acid at a temperature where calcium sulfate produced by
the reaction crystallizes in the form of CaSO4 .2H2 O (gypsum).
Phosphoric acid is produced at a strength of about 30% P2 O5
and is separated from the gypsum on a Bird Prayon filter. This
acid is concentrated to either about 40 or 54% P2 O5 , depending
on the process in which it is to be used. The flow diagram of the
phosphoric acid plant is shown in Figure 5.
Reaction
The ground phosphate rock is fed to the compartment 1 (see
Figure 5), where it is wetted and well dispersed by mixing with
a portion of the return slurry from the flash cooler and most of
the recycled acid from the filter. The phosphate rock is reacted
in compartments 2 and 3. The major portion of the reaction
is completed in compartment 4, and crystallization continues
through compartments 59, where the slurry is well degasified
and in a condition of stability so that it may be easily pumped
to the flash cooler. The attack tank temperature is controlled by
heat transfer engineering
Figure 5 The simplified flow diagram of wet-process phosphoric acid plant.
recycling a large quantity of slurry, cooled by approximately
45 C in a flash cooler, to compartments 1 and 3. Feed acid for
the flash cooler is obtained from compartment 7.
Filtration
Slurry is pumped to the filter from compartment 10. A flow
control valve along with a stand-pipe arrangement in the return
line to the attack tank assures that the feed rate is held constant.
The feed rate is adjusted as required to keep a constant level in
the attack tank. A constant slurry feed to the filter is essential for
efficient operation and for maintaining good washing conditions
and characteristics of the weak phosphoric acid recycle to the at-
tack tank. Frequent checks for cake thickness, number of flooded
pans, holes in cloth, and pan cleanliness are necessary for good
operation. Wash water requirements are set by the washing ef-
ficiency of the three sequential filter washes. The effectiveness
of the cake washing is determined each shift by the laboratory
analysis of the discharge cake P2 O5 and moisture content.
Evaporation
Product acid (29% P2 O5 ) from the filter section is settled and
stored. From storage, it is fed continuously to three two-stage
evaporators. The acid is concentrated from 2942% in Stage
I and then up to 54% in Stage II. Product acid (54% P2 O5 )
is pumped from the Stage II units to the clarification unit. The
evaporator system has a total capacity to concentrate 1000 metric
tons per day from 29% to 54%. Each evaporator unit (consisting
of Stage I and Stage II evaporators) will concentrate one-third
of the feed. Low-pressure steam is used on the heaters, medium-
pressure steam on the ejectors, and sea water on the barometric
condensers. Condensate from the heaters is saved and used for
washing of the filter. Warm sea water overflows from hotwells
(seal tanks) into trenches and is run by gravity to battery limits.
When the heaters are new and the tubes are clean, it will be found
vol. 28 no. 4 2007
 R. M. BEHBAHANI ET AL. 295

that the pressure on the shell-side of the heaters is very low,

possibly down to 5 psig vacuum. As the units build up scale, the
pressure will rise to a normal value of 58 psig. The operating
pressure should never exceed 12 psig. When this pressure is
reached, a boil-out will be necessary. The pressure safety valve
is usually set to 20 psig.

EVALUATION OF FIELD DATA

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:

1. The initial (clean) temperature at the interface between tube

wall and process liquid is calculated using the calculated heat
transfer resistances on the condensation side and of the tube
wall.
2. The temperature on the tube inside surface is not constant
with time, because the steam temperature is increased to
maintain a constant heat flow rate. For constant heat flow
rate and with the usual assumption that deposition-related
changes in flow velocity and surface roughness can be ne-
glected, it may be assumed that the temperature at the in- Figure 7 Effect of surface temperature on the fouling resistance.

heat transfer engineering vol. 28 no. 4 2007

296 R. M. BEHBAHANI ET AL.

ERROR ANALYSIS

The experimental error for the measured heat transfer coeffi-

cients may be due to the errors of the measurement of steam mass
flow rate, inlet temperature, outlet temperature, and shell pres-
sure. An error of approximately 3% was due to the measure-
ments of steam mass flow rate. The inlet and outlet temperatures
were measured with K-type thermocouples. These thermocou-
ples were initially checked against a quartz thermometer with an
accuracy of about 0.02 K.The inaccuracy in temperature mea-
surements is due to the calibration of the thermocouples, which
leads to a deviation of approximately 0.2 K. The operating
shell pressure was measured with strain-gauge sensors having a
factory calibrated accuracy of about 0.6% of the operating range,
which was adequate for heat transfer measurements.
The maximum error in the heat transfer coefficient measure-
ments was hence determined to be 9% by taking into account
the steam mass flow rate, temperatures, and pressure measure-
ment errors.

DEPOSIT ANALYSIS

The elemental composition of deposits was obtained with

an S-3200n SEM energy-dispersive X-ray spectrometer system.
Samples of the deposits were mounted in the desired orienta-
tion (upper or lower surface or cross-section) and placed under
a vacuum in the scanning electron microscope. The EDAX sys-
tem is able to distinguish between different elements present in
a sample by analyzing the energy of the X-rays given off. The
technique is atomic weight-sensitive; therefore, errors are more
pronounced for the low atomic weight elements. The EDAX sys-
tem is able to detect all the elements down to sodium. Results
for atomic weights below sodium are not reliable. The major
elements identified are calcium, sulfur, and oxygen. The analy-
sis indicated that the deposits contain mainly calcium sulfate. A
typical elemental analysis of the deposits is shown along with
its respective scanning electron micrograph in Figure 8. On av-
erage, it was found that the analyzed deposits consisted of about
86% CaSO4 . The density of the scale had an average value of
d = 2500 kg/m3 .
The value of thermal conductivity of the deposits was deter-
mined by measurements using a thermal conductivity apparatus
in the Bandar Imam Petrochemical Complex (BIPC) laboratory
and found to be d = 0.73 W/m.K. This is a comparatively low
value [3], indicating that only a small deposit thickness is re-
quired to affect the measured substantial reductions in overall
heat transfer coefficient.
MODELING OF THE PLANT FOULING DATA
The linear relationship between fouling resistance and time,
as described in the previous section, is generally characteristic of
tough, hard, and adherent deposits [4]. In such cases, the erosion
of the deposits by wall shear stress impacted by the flowing
heat transfer engineering
Figure 8 Typical elemental analysis of the deposits along with its respective
scanning electron micrograph.
liquid is negligible. Furthermore, previous investigations [1, 2]
showed that for flow velocities above 0.5 m/s, CaSO4 deposition
is controlled by the chemical reaction at the solid-fluid interface
and that the mass transfer-related effect of flow velocity on the
deposition rate can be neglected under these circumstances.
Taking these observations into consideration, a simple model
has been developed based on the field fouling data to allow for
the quantitative prediction of the effect of the main operating
parameters on the deposition rates.
A segment of heat exchanger tube is shown in Figure 9. It
can be analyzed as a cylindrical one-dimensional system with
negligible temperature gradients in an axial direction. For quasi-
steady state conditions with no internal heat generation, the ther-
mal resistance for heat conduction through a cylindrical layer
of deposit, which is identical to the scale resistance in this case,
can be written as:
 
ri ln(ri /rd ) di ln dddi
Rf = = (10)
d 2d
The thickness of the deposited scale layer can be predicted
for reaction-controlled deposition from the following calcium
vol. 28 no. 4 2007
 R. M. BEHBAHANI ET AL. 297

Figure 9 A segment of heat exchanger tube.

sulfate mass balance for an incremental cross-sectional volume
of the heated section:
d   2
mCaSO4 ,w = Ad Kw CCaSO4 CCaSO4 (11)
dt
The rate of change of scaled diameter with time is described by
the following equation:
  Figure 10 Arrhenius dependence of surface reaction rate constant (Kw ).
d 2 d 
(dd ) = . mCaSO4 ,w
dt Ad d frd dt

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.

NOMENCLATURE partment of Chemical and Process Engineering, University of

Surrey, UK, 1996.
A tube outside area, m2 [2] Helalizadeh, A., Mixed Salt Crystallization Fouling, Ph.D. Thesis,
C concentration, kg/m3 Department of Chemical and Process Engineering, University of
Surrey, UK, 2002.
d diameter, m
[3] Muller-Steinhagen, H., Heat Transfer FoulingMitigation and
Eact activation energy, J/mol Control Technologies, Publico Publications, Germany, 2000.
fr mass fraction [4] Bott, T. R., Fouling of Heat Exchangers, Elsevier, Amsterdam,
Kw surface scaling reaction rate constant, m4 /kg.s Netherlands, 1995.
k0 frequency factor, kg/(m2 .min.wt%2 ) [5] Behbahani, R., Heat Transfer and Heat Transfer Fouling in Phos-
L length, m phoric Acid Evaporators, Ph.D. Thesis, Department of Chemical
m mass, kg and Process Engineering, University of Surrey, UK, 2003.
M mass flow rate, kg/s
P pressure, Pa
Reza M. Behbahani is an academic staff member
r radius, m
in the Department of Chemical and Petroleum En-
R universal gas constant, J/mol.K gineering, Petroleum University of Technology,
Rf fouling resistance, m2 .K/W Ahwaz, Iran. He received his Ph.D. in 2003 from
T temperature, C or K University of Surrey, Guildford, UK. His main re-
t time, s search interests are boiling and non-boiling heat
transfer, fouling in heat exchangers, thermody-
U overall heat transfer coefficient, W/m2 .K namics, and process simulation. He has published
v flow velocity, m/s 16 articles in national and international confer-
hv latent heat of evaporation, J/kg ence proceedings and scientific journals. Cur-
T temperature difference, K rently, he is the head of Gas Engineering Department in the Petroleum University
of Technology, Iran.

Greek Symbols Hans Muller-Steinhagen

is the director of the
Institute for Technical Thermodynamics of the
German Aerospace Centre (DLR) and the director
thermal conductivity, W/mK of the Institute for Thermodynamics and Thermal
density, kg/m3 Engineering of the University of Stuttgart. Before
taking up his present positions in April 2000, he
held appointments as research fellow in the Uni-
Subscripts versity of Karlsruhe (19801984), DFG-funded
research associate in the University of British
Columbia (19841985), associate professor in the
b bulk University of Auckland (19861993), and professor and head of school in the
CaSO4 calcium sulfate University of Surrey (19932000). His research work covers a wide range of
d deposit topics related to heat and mass transfer, multi-phase flow, process thermody-
i inside namics, fuel cells, and solar thermal technology. The results of his studies have
in inlet been published in three books and more than 450 papers, and have received
numerous international awards and honors. He is a fellow of the Institution of
lm log mean Chemical Engineers and of the Royal Academy of Engineering and an associate
out outlet editor of Heat Transfer Engineering.
s surface
shell on the shell side Mohammad Jamialahmadi is a professor at
st steam the Petroleum University of Technology, Ah-
w wall waz, Iran. He received his post-graduate diploma
(1978), M.Sc (1980), and Ph.D. (1982) in chem-
0 initial
ical engineering from Aston University in Birm-
ingham, UK. For 10 years, he was the dean of the
University of Petroleum Industry Research Center
Superscript (UPIRC). His research work covers topics related
to heat and mass transfer, multiphase flow, and
saturation heat transfer in porous media, oil field formation
damage, gas injection, and neural networks. He has published more than 300
papers in international journals and proceeding conferences. His work has been
honored with several international and national awards, including the 1992 and
1993 TMS Bauxite Processing Awards (USA), the 1994 Light Metals Award
REFERENCES
(USA), the UK Heat Transfer Society Mike Akrill Trophy, the Best Paper 2000
in Canadian Journal of Chemical Engineering, and the International Iranian
[1] Najibi, H., Heat Transfer and Heat Transfer Fouling during Sub- Kharazmi Award for fundamental research in 2001. He is a member of the
Cooled Flow Boiling for Electrolyte Solutions, Ph.D. Thesis, De- Editorial Board of Iranian Chemical Engineering.

heat transfer engineering vol. 28 no. 4 2007