SCALE INHIBITION UNDER CRITICAL WETTING CONDITIONS IN

MULTIPLE-EFFECT DISTILLERS FOR SEAWATER DESALINATION

Authors: Heike Glade1, Maximilian Waack2, Stephan Nied3

1
Engineering Thermodynamics, University of Bremen, Germany, heike.glade@uni-bremen.de
2
Engineering Thermodynamics, University of Bremen, Germany, maximilian.waack@uni-bremen.de
3
BASF SE, Germany, stephan.nied@basf.com

Presenter: Heike Glade, Dr.-Ing.

Head of Research Group – Engineering Thermodynamics, University of Bremen - Germany

ABSTRACT
Multiple-effect distillation (MED) plants with horizontal tube falling film evaporators are widely used for
desalination applications. In each evaporator, spray nozzles shall evenly distribute the seawater on the top of a
horizontal tube bundle. The seawater trickles down as a thin film from the top tube rows onto the tube rows arranged
below. The thickness of the thin liquid film and its waviness greatly depend on the liquid load. Thin films are
necessary to achieve high heat transfer coefficients.

The fragile film on the outside of the evaporator tubes is susceptible to any disturbances. An inhomogeneous liquid
distribution is induced, for example, by clogging of the spray nozzles, the conical shape of the spray nozzles and
the triangular pitch of the tube bundle. Dry spots decrease the effective heat transfer area and significantly increase
scale formation. Thus, film breakdown needs to be prevented under all circumstances, what makes tube wetting a
crucial design and operation aspect.

Recently, an innovative approach to enhanced tube wetting and scale inhibition based on the combined use of a
wetting agent and an antiscalant was introduced. Wetting agents stabilize the liquid film, enhance tube wetting and,
thus, contribute to scale prevention. In this study, the impact of a novel wetting agent on film flow and scale
formation was investigated under critical wetting conditions such as very low wetting rates and inhomogeneous
falling film flow. Scaling experiments were performed in a horizontal tube falling film evaporator at pilot plant
scale.

Novel insights into tube wetting and scale formation in horizontal tube falling film evaporators under critical wetting
conditions will be given. The beneficial impact of a wetting agent on scale reduction under critical film flow
conditions will be presented and discussed and synergistic effects of a wetting agent and an antiscalant will be
revealed. The wetting agent leads to a reduction of scale formation when being applied alone and contributes to
effective scale inhibition both on the main tube body and at the tube edges when applied in combination with the
antiscalant.

Keywords: Multiple-effect distillation, scale formation, tube wetting, wetting agent, antiscalant

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I. INTRODUCTION

Horizontal tube falling film evaporators are commonly used in multiple-effect distillation (MED) plants
for desalination applications. Due to their robustness they are also suitable for feed waters with high
salinities and a great amount of solid matter – conditions which are harmful for membrane technologies.
A very important design aspect of falling film evaporators is the seawater distribution. A homogeneous
liquid film on the horizontal tubes is crucial, otherwise film breakdown may occur. The evaporator tubes
need to be fully covered by seawater at all times. Dry spots decrease the effective heat transfer area and
significantly increase scale formation [1, 2]. Scaling preferably starts at the meniscus surrounding a dry
spot. In this area, high surface temperatures are present which induce high evaporation rates and therefore
high local supersaturation, representing the driving force of the crystallization process. Scale formation
reduces the heat transfer performance and promotes corrosion which will shorten the plant lifetime [3].

In order to achieve a homogeneous seawater distribution, wide-angle full cone spray nozzles are usually
used. Several nozzles are aligned on a header and several headers are arranged in a triangular pitch nozzle
array or square pitch nozzle array [4]. In general, systems are not readily available and most likely the
designer will have to come up with an own solution [5]. Although the seawater is filtered before it enters
the evaporator stages, spray nozzles often clog. Additionally, the nozzle arrangement and the triangular
pitch of the tubes boost seawater distribution inhomogeneities [6].

The wetting rate is a crucial design and operation parameter in falling film evaporators. In the following,
the wetting rate is expressed as the mass flow rate on both sides of the tube per unit tube length:
𝑚̇
𝛤= . (1)
𝐿

In falling film evaporators for seawater desalination, the initial wetting rate on the first tube row commonly
ranges between 0.06 kg/(s m) and 0.14 kg/(s m).

Scale control is usually achieved by dosing polymeric antiscalants [7]. Common dosing rates range
between 2 and 3 ppm in MED plants [8]. The inhibition of scaling is achieved by different mechanisms
such as threshold inhibition, crystal distortion, dispersion and sequestration [9]. Antiscalants have been
proven to mitigate crystallization fouling very effectively [10, 11]. However, severe scale formation may
take place under critical wetting conditions such as inhomogeneous film flow and low wetting rates [12].

It is well known that surface-active substances stabilize thin liquid films by damping the wave formation
on the surface [13-15]. The surface-active substance adsorbs at the liquid/gas and liquid/solid interface
and lowers the interfacial tensions, respectively. Effects on wetting are directly measurable in form of a
contact angle, which forms at the three-phase point at the liquid tip. Significant differences in static,
advancing and receding contact angles may be observed. The equilibrium properties as well as the
dynamic adsorption behavior need to be considered in order to evaluate the effects of surface-active
substances on falling films.

Recently, an innovative approach for enhanced scale inhibition based on the combined use of a surface-
active substance (in the following referred to as wetting agent) and an antiscalant was introduced. The
addition of a novel wetting agent developed by BASF to a falling liquid film at a very low concentration
affects the film flow characteristics, improves tube wetting and contributes to scale inhibition.

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The objective of this study is to give new insights into the effects of a wetting agent on falling films under
critical film flow conditions and to explore the synergistic effects of a wetting agent and an antiscalant in
MED plants under such critical wetting conditions.

II. EXPERIMENTAL

In order to study tube wetting and scale formation under conditions that are close to those prevailing in
real multiple-effect distillers, a horizontal tube falling film evaporator at pilot plant scale was employed.
In the following, the experimental set-up, the materials and methods are described.

2.1 Test Rig

The core element of the test rig is an evaporator fitted with a bank of six horizontal tubes arranged below
each other, as shown in Fig. 1. The wetted length of the tubes amounts to 453 mm and the tube pitch is
50 mm.

Fig. 1: Drawing of the horizontal tube falling film evaporator

Saturated steam is provided by an electrical steam generator. The steam is introduced into the six tubes
and condensed under vacuum conditions. The condensation temperature/pressure of the steam inside the
tubes can be varied between 45°C/0.1 bar and 97°C/0.9 bar. The condensate flows back to the steam
generator for reuse. Artificial seawater is evenly distributed onto the first tube by means of a toothed
overflow weir and trickles down by gravity forming a thin film flow over the horizontal tubes. The
enthalpy of condensation allows the feed water to be preheated to the saturation temperature on the upper
tube and then part of it to be evaporated on the lower tubes. The evaporation temperature/pressure of the
solution can be varied between 40°C/0.074 bar and 90°C/0.7 bar. The generated vapor is condensed in a
plate heat exchanger. After leaving the evaporator, the concentrated test solution flows into a collecting
tank. The condensate is mixed with the concentrated solution and the test solution is recirculated by a

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pump. Carbon dioxide released from the evaporating artificial seawater and ambient air potentially
penetrated into the evaporator are extracted by means of a vacuum pump which maintains the saturation
pressure in the evaporator shell. The pilot plant provides conditions for CO2 release from seawater very
similar to those in real multiple-effect distillers. CO2 release shifts the pH value of the seawater to higher
values and influences the carbonate system.

Measurement instrumentation and automation of the test rig allow systematic studies by varying the
process parameters and simulating process conditions in different stages of MED plants. The tubes can be
removed from the tube sheets in order to renew the tubes, to test different tube materials, and to analyze
the adherent scale. On both sides of the evaporator shell, inspection glasses are installed which allow for
a visual observation of the wetting behavior during the experiments.

2.2 Tube Material

Experiments were performed with tubes made of aluminum brass, which is an established evaporator
tubing material in MED plants. The aluminum brass tubes (CW702R) were supplied by MPG Mendener
Präzisionsrohr GmbH (Menden, Germany) and had an outer diameter of 25.0 mm and a wall thickness of
1.0 mm. For studying the wetting behavior and scale formation, the tubes were used with their typical
surface topography as delivered by the tube supplier. The surface roughness was determined using a tactile
stylus unit (perthometer). Tube data are summarized in Table 1.

Table 1. Tube data

Alloy UNS No. Effective tube Outer diameter Wall thickness Surface
length roughness Ra
/ mm / mm / mm /µm
Aluminum C68700 453 25.0 1.0 0.44
brass

2.3 Test Liquid

For investigating scale formation, test series were performed with artificial seawater rather than natural
seawater to minimize biological effects and to provide a reproducible solution of known composition. The
preparation of artificial seawater was based on salt mole fractions for standard artificial seawater as
suggested in the formulation by Kester et al. [16]. After mixing the salts and stirring the solution, the
artificial seawater was aerated. The aeration tended to equilibrate the solution with atmospheric gases and
removed the excess CO2 resulting from the conversion of HCO3- to CO32-. The pH of the artificial seawater
after aeration was between 8.1 and 8.3.

The salinity of ocean surface waters throughout the world is fairly uniform about 35 g/kg. In areas with a
high level of rainfall or river runoff, the salinity is less. In areas with higher rates of evaporation, the
salinity is higher. In seawater, the relative proportion of the major ions compared to the salinity remains
constant [17]. The composition of artificial seawater is within 1 mg/kg of natural seawater for all the major
constituents [16]. Therefore, the composition of the artificial seawater used in the experiments is
representative for natural seawater with respect to the salts.

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The lower part of a tube bundle is most prone to scale formation since the highest supersaturation of
inversely soluble salts and the lowest wetting rate are present. In order to mimic this part of the tube
bundle, artificial seawater with a high salinity of 65 g/kg was applied representing the concentrated
seawater on the bottom tubes in MED plants taking into account a typical concentration factor between
1.3 and 1.6. Seawater with a salinity of 65 g/kg has an ionic strength of 1.39 mol/kg. For comparison,
average seawater having a salinity of 35 g/kg has an ionic strength of 0.72 mol/kg.

2.4 Qualitative and Quantitative Characterization of the Scale Layers

The local scale layer thickness and the amounts of calcium and magnesium in the scale layers on all six
evaporator tubes were measured. The local scale layer thickness was measured by means of a gauge
(MiniTest 2100, ElektroPhysik, Germany) in combination with the probe FN 1.6 using the eddy current
method. The measuring range of the probe is between 0 µm and 1600 µm and has a high resolution of
0.1 µm. The tolerance amounts to ±1 µm due to the calibration standard. For each tube, a two-point
calibration was performed using a calibration foil with a thickness of 96 µm (± 1 µm). The scale layer
thickness was measured at four different circumferential angles around the tube, namely 0°, 90°, 180° and
270°, and at 33 positions along the tube at each circumferential angle. The measurements were repeated
ten times at each position.

The scale on each tube was dissolved in hot 0.1 vol.% acetic acid and the concentrations of Ca2+ and Mg2+
ions in the solution were measured using inductively coupled plasma atomic emission spectroscopy (ICP-
AES).

2.5 Test Procedure

The experiments were conducted with a shell-side evaporation temperature of 65 °C and a tube-side
condensation temperature of 70 °C, representing the process conditions in the first stage of an MED plant.
In order to mimic critical wetting conditions, a very low wetting rate of  = 0.02 kg/(s m) was chosen in
the test runs.

The impact of an innovative wetting agent developed by BASF was investigated by applying a very low
wetting rate of  = 0.02 kg/(s m) and a high seawater salinity of 65 g/kg in order to reveal the performance
of the wetting agent at critical wetting conditions and high supersaturations. A low wetting agent
concentration of 1.0 ppm was chosen. For the investigation of the combined use of the wetting agent and
an antiscalant, a commercial antiscalant based on polycarboxylic acid developed and manufactured by
BASF under the trade name SOKALAN® PM 15 I was used. The antiscalant concentration was set to
1.5 ppm.

All experiments were performed with 240 liters of artificial seawater for a test period of 50 hours. In
previous experiments, different volumes of test solution and time periods were tested. Experiments with
240 liters of test solution and time periods of 50 hours were found to be favorable because supersaturation
levels are still high enough [18, 19].

For each test run, new tubes were used. Before installation, the tube surfaces were thoroughly cleaned
with deionized water, isopropyl alcohol and acetone. After every test run, the evaporator shell was
dismantled and the tubes were removed in order to analyze the adherent scale. Before a new test was

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started, an extensive cleaning procedure was conducted. The evaporator was cleaned manually with
deionized water and with diluted acetic acid solution. The collecting tank was cleaned with water jets. The
whole circuit was cleaned by flushing with deionized water for several days.

III. RESULTS AND DISCUSSION

Experiments were performed in the horizontal tube falling film evaporator without any additive, with the
novel wetting agent, with the antiscalant and with both the wetting agent and the antiscalant at a very low
wetting rate of 0.02 kg/(s m). In the following, the results are shown and discussed.

Figure 2 and Fig. 3 show the calcium mass per unit tube surface area and the magnesium mass per unit
tube surface area, respectively, in the scale layer of the six evaporator tubes based on the ICP-AES
measurements described in Section 2.4. Strong scale formation occurred without using any additive during
the test period of 50 hours. The tube surfaces were covered with a scale layer comprising a high calcium
content ranging between 13.8 and 33.7 g/m² and a relatively low magnesium content ranging between
0.14 and 0.20 g/m². In previous studies by the authors (e.g. [20]), it was shown that the tubes in falling
film evaporators for seawater desalination were covered with a two-layer scale comprising a thin, flaky
magnesium-rich and calcium-free base layer underneath a thick layer of calcium carbonate crystals in the
form of aragonite. X-ray diffraction (XRD) analyses mainly indicated Mg(OH)2 (brucite) or iowaite
(layered double hydroxide, also known as hydrotalcite-like compound) in the magnesium-rich scale. A
shift of pH to high values in the seawater film due to CO2 release and, additionally, cathodic reactions on
the metallic tube surface resulting in a locally enhanced OH- concentration may promote a high degree of
supersaturation of Mg(OH)2 to drive its rapid precipitation on the tube surface. It is assumed that the Mg-
rich base layer forms in the early stages and its growth ceases and aragonite crystals start to precipitate
once the tube surface is completely covered with the Mg-rich scale layer [20]. Furthermore, the authors
[21] found that the calcium scale content significantly increases with decreasing wetting rate, whereas the
magnesium scale content does not notably change and remains on a low level. Thus, calcium carbonate
crystallization on the heat transfer surface is massively increased by lowering the wetting rate, whereas
magnesium hydroxide precipitation is unaffected by hydrodynamics and rather determined by
electrochemical effects [21].

Calcium carbonate scale formation increases from the top to the bottom tube, as shown in Fig. 2, while
the magnesium-containing scale remains on a relatively low level, as depicted in Fig. 3. During steady-
state operation, the seawater is preheated to saturation temperature on part of the first tube and then it
partly evaporates. Thus, calcium carbonate scale formation increases from the top tube to the bottom tube
due to an increasing salt concentration and therefore higher supersaturations.

Figure 2 clearly shows that the sole use of the novel wetting agent with a concentration of 1.0 ppm leads
to a significantly reduced calcium carbonate scale formation. The magnesium scale content remains on a
low level, as illustrated in Fig. 3. The effects of the wetting agent are very complex because the wetting
agent adsorbs at the liquid/vapor interface and at the liquid/solid interface, it affects the liquid properties
such as the surface tension, the wetting properties such as the contact angles and the film flow
characteristics such as liquid film thickness and wave motion.

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 45
w/o additive tCO = 70 C
40 wetting agent (1.0 ppm) tEV = 65 C
 = 0.02 kg/(s m)
antiscalant (1.5 ppm) S = 65 g/kg
35
Calcium scale content / g/m2

antiscalant (1.5 ppm) + wetting agent (1.0 ppm) t = 50 h

30

25

20

15

10

0
1 2 3 4 5 6
Tube No.
Fig. 2: Calcium scale content in the scale layer of the six tubes without additive, with wetting
agent, with antiscalant and with the combined use of the antiscalant and the wetting agent

0.30
w/o additive tCO = 70 C
tEV = 65 C
wetting agent (1.0 ppm)
0.25  = 0.02 kg/(s m)
antiscalant (1.5 ppm)
Magnesium scale content / g/m2

S = 65 g/kg
antiscalant (1.5 ppm) + wetting agent (1.0 ppm) t = 50 h
0.20

0.15

0.10

0.05

0.00
1 2 3 4 5 6
Tube No.
Fig. 3: Magnesium scale content in the scale layer of the six tubes without additive, with wetting
agent, with antiscalant and with the combined use of the antiscalant and the wetting agent

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When using the antiscalant with a low concentration of 1.5 ppm, the calcium carbonate mass per unit tube
surface area drops down to very low values ranging between 1.0 and 2.5 g/m² and the magnesium mass
per unit tube surface area drops down to values between 0.11 and 0.14 g/m², as shown in Fig. 2 and Fig. 3,
respectively. Figures 4 to 6 exemplarily show that the scale was practically prevented on the main tube
body, whereas a thick scale layer formed at the tube edges.

Even though scale formation was reduced to a great extent by the sole application of the antiscalant, the
combined use of the novel wetting agent and the antiscalant decreased the calcium and magnesium scale
content further on, as shown in Fig. 2 and Fig. 3.

The local scale layer thickness was measured on each of the six tubes as described in Section 2.4.
Exemplarily, the average local scale layer thickness along the third tube on the upper crown line (0°),
bottom crown line (180°C) and at the tube side (270°) is shown in Figs. 4, 5 and 6, respectively.

700
w/o additive tCO = 70 C
tEV = 65 C
Average local scale layer thickness / µm

600
wetting agent (1.0 ppm)  = 0.02 kg/(s m)
S = 65 g/kg
500 antiscalant (1.5 ppm) t = 50 h
tube No. 3
antiscalant (1.5 ppm) + wetting agent (1.0 ppm) 0
400

300

200

100

0
0 10 20 30 40 50
Distance from the heating steam entrance / cm

Fig. 4: Average local scale layer thickness along tube No. 3 on the upper crown line (0°) without
additive, with wetting agent, with antiscalant and with the combined use of the antiscalant and the
wetting agent

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 50
w/o additive tCO = 70 C
45 tEV = 65 C
 = 0.02 kg/(s m)
Average local scale layer thickness / µm
wetting agent
40 S = 65 g/kg
antiscalant (1.5 ppm) t = 50 h
35 tube No. 3
antiscalant (1.5 ppm) + wetting agent (1.0 ppm) 180
30

25

20

15

10

0
0 10 20 30 40 50
Distance from the heating steam entrance / cm
Fig. 5: Average local scale layer thickness along tube No. 3 on the bottom crown line (180°)
without additive, with wetting agent, with antiscalant and with the combined use of the antiscalant
and the wetting agent
300
w/o additive tCO = 70 C
tEV = 65 C
 = 0.02 kg/(s m)
Average local scale layer thickness / µm

250 wetting agent (1.0 ppm)

S = 65 g/kg
antiscalant (1.5 ppm) t = 50 h
tube No. 3
200
antiscalant (1.5 ppm) + wetting agent (1.0 ppm) 270

150

100

50

0
0 10 20 30 40 50
Distance from the heating steam entrance / cm
Fig. 6: Average local scale layer thickness along tube No. 3 on the tube side (270°) without
additive, with wetting agent, with antiscalant and with the combined use of the antiscalant and the
wetting agent

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The strongest scale formation occurred at the sides (90° and 270°) of the tube, followed by the tube top
(0°), as shown in Fig. 6 for 270° and Fig. 4 for 0°. Least scale precipitated at the tube bottom (180°), as
shown in Fig. 5. This scale distribution around the tube can be explained by the seawater film thickness
profile around the tube and the wave motion characteristics (wave amplitudes and wave frequencies) as
found in film thickness measurements by the authors [21]. Film thickness measurements revealed that the
mean film thickness as well as average minimum film thickness are smaller at the top of the tube compared
to those values at the bottom. Additionally, impinging droplets and jets agitate the film. Wave frequencies
are high and amplitudes are about half of the size of the mean film thickness. On the bottom of the tubes,
films are thick and the dominant wave motion exhibits a low frequency [21]. Therefore, scale formation
is less severe at the tube bottom. The film thickness is smaller at the tube sides compared to the top and
bottom [22-24]. Thus, scale formation is strong at the tube sides. Detailed information about the results of
the film thickness measurements is given by Waack et al. [21].

Without using any additive, a thick scale layer formed on the upper crown line, on the bottom crown line
and at the side of the tube, whereas the scale thickness was particularly high at both tube edges, as
illustrated in Figs. 4, 5 and 6.

Figures 4, 5 and 6 show that the sole use of the wetting agent resulted in a considerably lower scale
thickness on the main tube body as well as at the tube edges. The sole use of the antiscalant practically
prevented scale formation on the main tube body. However, very thick scale layers formed at the tube
edges, as shown in Fig. 4 and Fig. 6. The combined use of the wetting agent and the antiscalant practically
prevented scale formation both on the main tube body and at the tube edges at the very low wetting rate
of 0.02 kg/(s m), as depicted in Figs. 4, 5 and 6.

IV. CONCLUSIONS

Falling film flow massively affects scale formation in horizontal tube falling film evaporators, which are
commonly used in multiple-effect distillation plants for seawater desalination. Scale inhibition was
investigated under critical wetting conditions in a horizontal tube falling film evaporator at pilot plant
scale. Experiments were performed with artificial seawater having a high salinity of 65 g/kg representing
the concentrated seawater on the bottom tubes in MED plants taking into account a typical concentration
factor between 1.3 and 1.6. The shell-side evaporation temperature was 65 °C and the tube-side
condensation temperature was 70 °C as commonly prevailing in the first stage of an MED plant. In order
to mimic critical wetting conditions, a very low wetting rate of  = 0.02 kg/(s m) was chosen in the test
runs. The scale layer was analyzed on each of the six evaporator tubes. The calcium and magnesium
quantities in the scale layer were measured using inductively coupled plasma atomic emission
spectroscopy (ICP-AES). The local scale layer thickness was measured at four positions around the tubes
and at 33 positions along the tubes using a gauge based on the eddy current method.

Without using any additive, the six evaporator tubes were densely covered with a thick crystalline scale
layer, particularly at the tube edges. Calcium carbonate scale formation increased from the top tube to the
bottom tube, whereas the magnesium hydroxide scale remained on a relatively low level. Dosing the novel
wetting agent with a low concentration of 1.0 ppm resulted in a considerable reduction of scale formation
in terms of calcium content and scale layer thickness on the main tube body and at the tube edges.
Applying the antiscalant with a concentration of 1.5 ppm drastically reduced the calcium carbonate scale
content down to a very low level. The magnesium hydroxide scale content was also notably lowered. The

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scale layer thickness on the main tube body was reduced to practically zero. However, a thick scale layer
formed at the tube edges. The combined use of the wetting agent and the antiscalant was found to be most
effective in terms of scale inhibition. The scale layer thickness was practically zero both on the main tube
body and at the tube edges.

The effects of the wetting agent are very complex because the wetting agent adsorbs at the liquid/vapor
interface and at the liquid/solid interface, it affects the liquid properties such as the surface tension, the
wetting properties such as the contact angles and the film flow characteristics such as liquid film thickness
and wave motion. A comprehensive study based on measurements of the film thickness as well as on
analyses of the wetting properties and adsorption characteristics is currently being performed to better
explain the beneficial effects of wetting agents on tube wetting and scale formation.

Combining the wetting agent and the antiscalant effectively prevents scale formation at critical process
conditions, e.g. very low wetting rates, and, thus, may lead to less down-time for cleaning, higher plant
availability, reduced production losses during plant shut-down as well as improved heat transfer and
thermal performance. Furthermore, the combination also offers the possibility to design and operate future
MED plants at reduced wetting rates without the risk of surface dryout and of severe scale formation.
Thus, better heat transfer and thermal performance as well as reduced electrical energy consumption of
MED plants may be achieved.

V. REFERENCES

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11. Wildebrand, C., Glade, H., Will, S., Essig, M., Rieger, J., Büchner, K.-H. and Brodt, G., Effects
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The International Desalination Association World Congress on Desalination and Water Reuse 2019/Dubai, UAE
REF: IDAWC19-Glade
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