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New anti-scalant performance evaluation for MSF technology

Article in Desalination and Water Treatment · January 2012

DOI: 10.1080/19443994.2012.704701

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New anti-scalant performance evaluation for MSF

technology
a a a a
Amr Mohamed , Justin Robert , Abdel Nasser Mabrouk , Imteyaz Ahmad , Ahmed Nafey
a a a b b
, J.S. Choi , J.K. Park , Stephan Nied & Jurgen Detering
a
Doosan Water R&D Center, Monarch Office Tower, Level 29th, Sh. Zayed Road, Dubai, UAE
Phone: Tel. +971 509758938
b
BASF SE, Care Chemicals & Formulators, D-67056, Ludwigshafen, Germany

Version of record first published: 13 Jul 2012

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Treatment, DOI:10.1080/19443994.2012.704701

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 Desalination and Water Treatment iFirst (2012) 1–6
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1944-3994/1944-3986 Ó 2012 Desalination Publications. All rights reserved
doi: 10.1080/19443994.2012.704701

New anti-scalant performance evaluation for MSF technology

Amr Mohameda,*, Justin Roberta, Abdel Nasser Mabrouka, Imteyaz Ahmada, Ahmed
Nafeya, J.S. Choia, J.K. Parka, Stephan Niedb, Jurgen Deteringb
a
Doosan Water R&D Center, Monarch Office Tower, Level 29th, Sh. Zayed Road, Dubai, UAE
Tel. +971 509758938; email: [email protected]
b
BASF SE, Care Chemicals & Formulators, D-67056 Ludwigshafen, Germany
Downloaded by [Dr Abdel Nasser Mabrouk] at 06:54 15 August 2012

Received 29 February 2012; Accepted 15 June 2012

ABSTRACT

The desalination industries are looking for the reduction in the unit cost of desalinated water
through developments in the technologies, process optimization, etc.; multi stage flash (MSF)
technology has a proven track record for high reliability in the tough seawater condition. One
of the technical barriers to improve the MSF system performance is the scale formation phe-
nomena. This phenomenon can be manipulated by nanofiltration or by chemical treatment
(anti-scalant). A pilot plant was constructed to evaluate the performance of a novel anti-scalant,
under high top brine temperature (TBT) condition. Techniques such as atomic absorption spec-
troscopy and X-ray diffraction are used to measure the scale deposition in the test sections. Dif-
ferent operation parameters such as TBT, salinity, dosing rate, and operation with/without ball
cleaning are considered. The experimental results indicate that the scale inhibition shows good
performance after 72 h even for a low dosing rate of 2.5 ppm.

Keywords: Multi stage flash; Anti-scalant; Top brine temperature; Scale formation

1. Introduction production capacity of the MSF plant as shown in

Fig. 1. Further in the process of increasing the unit pro-
Doosan Heavy Industries & Construction is a world
duction capacity and reducing the specific water pro-
leader in building large-scale desalination plants by
duction cost, Doosan is focusing on developing large-
multi stage flash (MSF), multiple-effect desalination,
scale MSF plants with increased efficiency.
and reverse osmosis (RO) process as per the market
One of the main parameters which is always an
needs. Consistent R&D effort has been performed by
obstacle in scale-up of unit capacity of MSF desalination
Doosan to maintain the market lead and to meet the
process is top brine temperature (TBT). Increasing the
increasing demand. MSF desalination process is con-
TBT will result in scale deposit inside the tubes, and
sidered to be the most reliable and mature technology
this will affect plant performance in turn the water cost.
for producing high-quality desalinated water on large-
The presence of scale in the tube will increase the foul-
scale production for harsh seawater conditions persist-
ing factor, which leads to reduction in overall heat
ing in Middle East. The reliability of MSF desalination
transfer coefficient. This will result in increased heat
process has motivated Doosan to increase the unit
transfer area which directly affects the CAPEX. On the
other hand, the presence of scale in the tube will
*Corresponding author. increase the pressure drop in turn the pumping power,

Presented at the International Conference on Desalination for the Environment, Clean Water and Energy, European Desalination
Society, 23–26 April 2012, Barcelona, Spain
 2 A. Mohamed et al. / Desalination and Water Treatment

drate (CaSO4 · 1/2H2O), or gypsum (CaSO4 · 2H2O).

Most of the scale deposition is in the form of hemihy-
drate [1] as shown in Fig. 3.
Skillman et al. [2] developed a simple sulfate solu-
bility index for estimating the likelihood of calcium
sulfate scaling. Skillman index is a ratio between the
actual concentration, [i]actual, of either calcium or sul-
fate and its theoretical or equilibrium concentration
whichever is the limiting species.

½iactual
Fig. 1. Doosan MSF desalination plant unit capacity Skillman index ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
ð x þ 4KSP  xÞ103
2
evolution.

where x is the absolute value of the excess common

Downloaded by [Dr Abdel Nasser Mabrouk] at 06:54 15 August 2012

ion concentration of calcium and sulfate ions:

5
x ¼ j2:5½C2þ   1:04½SO2
4 j10

Fig. 2. Heat transfer resistances in MSF condenser. According to Linke et al. [3], the solubility product
constant (KSP) can be calculated as follows:
the frequency of ball cleaning, and the chemicals dosing
rate and steam consumption, which will lead to S ¼ 2:91 þ 0:003173T  8:193105 T 2
increase in OPEX. Fig. 2 shows typical heat transfer
resistances in an MSF condenser which consist of inner
(Ri) and outer (Ro) thermal resistances, wall thermal Several attempts have been made in the past to
resistance (Rw), and fouling (FF) water, and it is very increase the TBT of MSF desalination process, and
clear that fouling factor is the key element to enhance some of them are highlighted here. Al-Shammiri et al.
overall heat transfer coefficient. [4] reported that the nanofiltration inhibits CaSO4 scal-
Scale deposition in MSF consists of two types of ing by 99.1–96.98% according to recovery ratio with-
scale: hard scale and soft scale. The soft scale formed out adding any chemicals, nanofiltration has low
from CaCO3 which is amorphous and can be removed prevention for CaCO3 (5.3–23%), and also for all other
using sponge ball cleaning. The hard scale is mainly scaling salts, a great scaling inhibition was found
calcium sulfate resulted from the direct crystallization about 97.7% for BaSO4, 99.8% for SrSO4 scaling, and
due to supersaturation of anhydrite (CaSO4), hemihy- 94.86% inhibition for CaF. The reliability of this nano-

Fig. 3. Phase diagram of CaSO4.

 A. Mohamed et al. / Desalination and Water Treatment 3

filtration system is tested in gulf seawater and found

to be satisfactory.
The Saline Water Research Institute, Saudi Arabia
(SWDRI), handled the problem of increasing the TBT
with dihybrid nanofiltration (NF)/MSF and trihybrid
NF/RO/MSF [5]. The experimental results of dihy-
brid system NF/MSF showed the excellent perfor-
mance of nanofiltration process to remove the
divalent ions, and even it is experimentally verified
up to a TBT = 128˚C in their pilot plant. Such system
can be worked safely through the use of a MSF
makeup formed of a blend of NFP (nanofiltration Fig. 4. Experimental setup to study the scale deposit.
permeate) and seawater in the ratio of 1:2 and 1:1 up
to 130˚C. The test results on the trihybrid NF/RO/
decreased unit water production cost. This higher
MSF configuration showed that it was possible to
temperature operation is possible only if a new reli-
Downloaded by [Dr Abdel Nasser Mabrouk] at 06:54 15 August 2012

operate the MSF pilot plant with a makeup which

able anti-scalant is developed. In the above contest,
was entirely formed of the reject of the reverse
DOOSAN made a collaborative R&D work with BASF,
osmosis unit, operated in the NF/SWRO mode, up
Germany, to develop a new anti-scalant.
to 130˚C of TBT. It can also be operated with a
makeup formed of a blend of brine reject of the RO
unit and seawater in the ratio 2:1 and 1:1 safely up 2. Experimental setup
to a TBT of 128 and 122 ˚C, respectively.
The last three decades have witnessed serious To prove the reliability of the new anti-scalant at
efforts by developers of chemicals attempting to high TBT (between 120 and 130˚C), an experimental
increase the top brine temperature where effectiveness setup was developed in Changwon, South Korea. The
of chemicals used in suppressing formation and deposi- experimental setup was designed in such a way that
tion can be prolonged. Inhibition of scale formation is it simulates the real operating condition inside the
achieved by one of the following treatment methods [6]: MSF condenser tubes to study the scale deposits at
Use of acid causes depletion of carbonate present different operating conditions. It consists of concentric
in seawater, this is known as acid treatment method. tubular heat exchanger (40 tubes) inner tube diameter
Use of commercially available scale inhibitor. (OD) 20 and 50 mm outer tube diameter. It has the
Combined use of the above two, that is, use of facility to collect scale deposits in the heated seawater
scale inhibitors at reduced dosing rate with partial through a coupon (metal chip) and tube section for
depletion of carbonate by acid, this is known as both with and without ball cleaning. The reverse
hybrid treatment method [7]. osmosis system in the pilot plant helps in achieving
The commercially available anti-scalants are per- the gulf seawater condition by concentrating the
forming safely up to 112˚C in BR-MSF plants, and incoming Korean seawater (33 g/l). It also has the pro-
they are working well up to 118˚C in OT-MSF plants vision to test the scale deposit on the test sample piece
[8]. Only few published work is found in the area of with ball cleaning mode of operation. Fig. 4 shows the
MSF operating at TBT higher than 112˚C. Hamed el experimental setup to study the scale deposit in the
al. [6] conducted experiments with different scale MSF plant.
commercially available inhibitors up to 119˚C of TBT
using the MSF pilot plant available at SWDRI. The
3. Experimental plan
experiments are conducted for a period of one month
for a dose rate of 1 ppm and the concentration factor Sets of experiments (with and without ball clean-
of 1.9. The results showed positive indication for the ing) were conducted to investigate the performance of
possibility to increase the TBT with anti-scalant. the new anti-scalant at TBT of 120, 125, and 130˚C for
A techno-economical study [9] was performed by a varying seawater salinity of 50 and 65 g/l (corre-
DOOSAN R&D center for OT-MSF configuration sponding to OT-MSF and BR-MSF conditions). The
where the concentration factor equals to 1 instead of dosing rate was varied between 2.5 and 10 ppm (2.5,
1.4 in brine recycle mode. Increase in TBT will 4, 6, 8, and 10) for 24 h of continuous operation. Since
increase flash range, and the unit water production the experiments are focused toward the anti-scalant
cost is decreased. Also, the study made with BR-MSF performance against scale formation, the entire
system at increased TBT up to 120˚C has resulted in planned tests are conducted with titanium tubes and
 4 A. Mohamed et al. / Desalination and Water Treatment

stainless tubes with and without ball cleaning opera-

tion.

4. Results and analysis

Visual inspection and chemical analysis were per-
formed for the test samples to evaluate anti-scaling
performance. The visual check gives a qualitative idea
on the extent of scale deposits and the anti-scalant per-
formance. Chemical analysis by the BASF lab indicates
that calcium and magnesium are the major content in Fig. 6. Coupon and tube samples––with ball cleaning.
the scale; the others were neglected from the analysis.
This analysis was performed by atomic absorption
Also the scanning electron microscope (SEM) was used
spectroscopy (AAS) in the units of g/m2 of tube area.
to understand the microstructure of the scale.
Downloaded by [Dr Abdel Nasser Mabrouk] at 06:54 15 August 2012

Figs. 5 and 6 are photographs of the coupon sam-

ple during visual inspection. This gives a qualitative
measure on the anti-scalant performance and the
extent of scale deposits, before doing the chemical
analysis.
From Figs. 5 and 6, it is understood that the scale
deposit is less, when the experiments are conducted
with ball cleaning comparing with the experiments
without ball cleaning. Similar trend is seen for all the
conducted experiments irrespective of the TBT,
salinity, and dosing rate.
The SEM was used to understand the microstruc-
ture of the scale. The result obtained from SEM for a
particular experiment conducted without ball cleaning
system at TBT = 120˚C, salinity 60 g/l, and dosing
Fig. 5. Coupon and tube samples––without ball cleaning. rate = 2.5 ppm is presented in Fig. 7.

Fig. 7. SEM result at TBT = 120˚C, salinity 60 g/l, and dosing rate = 2.5 ppm.
 A. Mohamed et al. / Desalination and Water Treatment 5

5. Fouling factor evaluation

In order to calculate the fouling factor, the scale
thickness needs to be calculated first and then the
corresponding fouling factor is calculated. The fol-
lowing assumptions are made to simplify the calcu-
Ca lations.

5.1. Assumptions

• Ca and Mg scales are in layers.

• The scales are in homogenous distribution.
4.00 6.00 8.00 • High-density scales (Ca) stick at the bottom layer
Dosing Rate, ppm
(i.e. at the tube surface), and the lighter-density
scale (Mg) sticks above the Ca.
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Fig. 8. Ca participation at TBT = 125˚C and salinity = 50 g/l.

Base on the above assumptions and the fundamen-
tals of heat transfer, the following set of formulas
were derived and these equations are used to calcu-
From the SEM image, it is understood that the late the thickness of the scale and in turn the thermal
coupon surface is covered with an amorphous (1) and resistance by the scale (Fig. 10).
crystalline precipitation, Mg(OH)2-Crytals3 shaped
ð1Þ Ca scale voulme ðVCa Þ
sand rose (3). This precipitation is easily removable. g
The calcium and magnesium in the scale deposit Ca scale Tube surface area 3
¼ m2   ðm Þ
are estimated by AAS, and the same is represented in Ca density mkg3  1000 g
kg
Figs. 8 and 9, corresponding to a test condition of
TBT = 125˚C and salinity = 50 g/l without ball cleaning
ð2Þ Mg scale volume ðVMg Þ
system in operation. Ca and Mg participation is repre- g
sented in gram per unit area (g/m2). Mg scale Tube surface area 3
¼ m2   ðm Þ
From the analysis, it is understood that the cal- Mg density mkg3  1000 g
kg
cium and magnesium deposits reduce with an
increase in anti-scalant dosing rate. Similar trend is
seen in all the experiments. Also the precipitation is
low, when the plant is operated with ball cleaning
system.

Mg

4.00 6.00 8.00

Dosing Rate , ppm

Fig. 9. Mg participation at TBT = 125˚C and salinity = 50 g/l. Fig. 10. Schematic diagram inside the scaled tubes.
 6 A. Mohamed et al. / Desalination and Water Treatment

The performance of the new anti-scalant is prom-

ising for 24- and 72-h operation, and long-time
experimental operation (10 days test) is under
processing.

6. Conclusion
To study the performance of a new anti-scalant at
higher TBT corresponding to a once through and
brine recycling configurations of MSF desalination
Fig. 11. Fouling factor at 50 g/l salinity without ball system, an experimental setup was constructed in
cleaning. Changwon, Korea. Several experiments are conducted
for a set of operating conditions. It is understood from
ð3Þ Scale thickness ðmmÞ the experiments that the scale deposit is less, with ball
2 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi3 cleaning system compared to without ball cleaning.
Downloaded by [Dr Abdel Nasser Mabrouk] at 06:54 15 August 2012

di  d2i  pl4  VCa Similar trend is seen for all the conducted experiments
¼4 5
irrespective of the TBT, salinity, and dosing rate. The
2
Ca
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi scale precipitate obtained in the experiments is easy to
2 3
ðdi  2tCa Þ  ðdi  2tCa Þ2  pl4 VMg remove (amorphous) by ball cleaning. The
þ4 5 performance of the new anti-scalant is promising for
2 24- and 72-h operation, and long-time experimental
Mg
operation (10 days test) is under processing.
 
2 C
ð4Þ Fouling factor m 
W
2  3 2  di  2tCa
3 References
di
ln ln [1] A.E. Alrawajfeh, Influence of nanofiltration pretreatment on
6 di  2tCa 7 6 di  2ðtCa þ tMg Þ 7
¼6 4
7 þ6
5 4
7
5
scale deposition in multi stage flash thermal desalination
2pkl 2pkl plants, Thermal Sci. 15 (2011) 55–65.
[2] L. Skillman, J.P. McDonald, Jr., A. Simple, Accurate, fast
Ca Mg method for calculating calcium sulfate solubility in oil field
brine, Paper No. 906–14-I, Spring Meeting of the southwestern
District, Division of production, American Petroleum Institute,
Lubbuke, TX, USA, 1969.
where do, tube outer diameter; di, tube inner diameter; [3] W.F. Linke, A. Seidell, Solubility of Inorganic and Metal
t, tube thickness; l, tube length; tMg, magnesium scale Organic Compounds, 4th ed., Van Nostrand-Reinhold, New
thickness; tCa, calcium scale thickness. York, NY, 1965.
[4] M. Al-Shammiri, M. Ahmed, M. Al-Rageeb, Nanofiltration and
From AAS results, the Ca scale is mainly calcium sulfate limitation for top brine temperature in Gulf
formed from CaCO3 and magnesium is present as desalination plants, Desalination 167 (2004) 335–346.
Mg(OH)2. The following property values are used [5] O.A. Hamed, K.A. Shail, Khalid B. Mardouf, H.A. Otaibi,
A.M. Hassan, A.M. Farooque, S. Al-Sulami, A.Al-Hamza,
in the above set of equations while calculating the Nanofiltration (NF) membrane pretreatment of SWRO feed
fouling factor. & MSF make up, SWCC, 2005.
[6] O.A. Hamed, H.A. Al-Otaibi, Prospects of operation of MSF
desalination plants at high TBT and low anti-scalant dosing
• Density of Mg(OH)2 is 2,344 kg/m3. rate, Desalination 256 (2010) 181–189.
• Density of CaCO3 is 2,710 kg/m3. [7] M.A.K. Al-Sofi, F.E. Essam, M. Imam, G.M. Mustafa, Heat
• Thermal conductivity of Mg(OH)2 is 8 W m1 K1. transfer measurement as a criterion for performance evaluation
of scale inhibition in MSF plants, IDA Abu Dhabi, 1995.
• Thermal conductivity of CaCO3 is 2.2 W m1 K1. [8] G.F. Tusel, R. Rautenbach, J. Widua, Sea water desalination
plant “Sirte”––An example for an advanced MSF design, Desa-
The fouling factor value based on the above equa- lination 96(1–3) (1994) 379–396.
[9] A.A. Mabrouk, I. Ahmad, A. Mahmoud, A.S. Nafey, J.K. Park,
tions is presented in Fig. 11 corresponding to 50 g/l Techno-economic analysis of high capacity once through MSF
salinity without ball cleaning. desalination plants, IDA Australia, 2011.

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