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ACID CLEANING OF SOME DESAL UNITS


AT AL-JUBAIL PLANT

A. U. Malik , Shahreer Ahmad, Ismail Andijani, Nausha Asrar


Research And Development Center
Saline Water Conversion Corporation
P. O. Box 8328, Al-Jubail 31951, Kingdom of Saudi Arabia
Abdul Salam Al-Mobayed , Abdullah M. Al-Jardan, Anwar Ahsan
Al-Jubail Desalination & Power Plants, Al-Jubail
SUMMARY
The scaling or deposition on the heat exchanger tubes of an MSF desalination plant is a
phenomenon of common occurring. If the proper cleaning or descaling is not carried
out then it would greatly affect the efficiency of the plant. Acid cleaning is so far the
most reliable way to clean the heat exchanger tubes. In SWCC desalination plants,
IBIT 570 inhibited sulfamic acid has been used frequently for cleaning, demisters and
other components due to its efficient and safe cleaning. However, due to high cost and
slow action of this combination, the application of some low cost and fast reacting
inhibitor - acid combination was considered. The main concern was that the inhibited
acid should have corrosive action within allowable limits.
The Corrosion Department of RDC with collaboration of Al-Jubail plant carried out a
systematic study on testing of CP-20 inhibited H2SO4 and HCl on plant component
materials, namely carbon steel (flash chamber), stainless steel (flash chamber,
demister), 70-30 and 90-10 cupronickel (heat transfer tubes) and Ni resist D2 (recycle
brine pump). The interaction behavior of materials with inhibited acids was studied by
carrying out laboratory dynamic testing in open atmosphere and deaerated conditions.
The results of the testing indicate that inhibited H2SO4 or HCl could be used for
cleaning cupronickel (70-30 and 90-10), Ni-Resist D2 and carbon steel without any

1
Issued as Technical Report No. TR3804/APP95007 in February 1997,
A paper from this report entitled " Corrosion Behavior of some MSF Plant Materials in Inhibited Sulfuric Acid and Hydrochloric
Acid was presented in VIII - IDA Conference , Madrid, Oct.6-9, 1997.
Another paper entitled " Effectiveness of inhibited H2SO4 and HCl in Cleaning Some Desal Plants at Al-Jubail Plant was
presented in Second Acquired Experience Symposium on Desalination Plants O&M, SWCC, Al-Jubail, Sept.29 - Oct.3, 1997.

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possibility of significant corrosion if applied under deaerated conditions. Stainless


steel AISI 316L could be used both under open atmospheric and deaerated condition.
The second phase of the study was to apply the results of lab test studies in cleaning the
desal tubes of some of the units of Al-Jubail desalination plant. On the basis of
laboratory results, Al-Jubail plant authorities agreed to carry out the cleaning of some
of phase-II desal units by using inhibited H2SO4.
Acid cleaning of the desal units of C4, #27 and 29 was carried out by applying Brine
Recycle Pump procedure using CP 20 inhibited deaerated H2SO4 (prepared in
seawater). The operation was consisted of recirlculating the acid through evaporator
and heat exchangers including water boxes and brine heater. For whole operation 3
charges were used and after every charge, the system was flushed thoroughly. The
Ca++, Cu++, pH and acid concentration was monitored. The post cleaning inspection of
the desal units and performance data (GOR, PW, HTC) indicate that acid cleaning has
enhanced the efficiency of the plant. No significant corrosion was observed during
cleaning.
1.

INTRODUCTION

1.1

BACKGROUND

The inhibitor IBIT 570S and sulfamic acid have commonly been used for descaling heat
transfer tubes in desalination plants and also for cleaning demisters.

The main

advantage of this combination is the safe cleaning operation of the tubes. The principle
disadvantages are its slow action and high cost. In order to assess the capability of a
new acid inhibitor CP-20 which is less expensive, the Manager, Al-Jubail plant, in
January 1995, asked R&D Center to test the efficiency of the chemical and its
performance vis-a-vis sulfuric acid cleaning IBIT 570S. Subsequently, studies based on
dynamic testings were carried out on CP-20 inhibited H2SO4 or HCl on cupronickel and
titanium metals. The results of the test studies are given in Table 1 and 2 and are
illustrated in Fig. 1. The main conclusion of the studies was that although CP-20 was
inferior to IBIT for inhibiting corrosion of cupronickel and titanium in HCl and H2SO4
but it could be used as an alternative to IBIT due to its allowable corrosion rates.

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To consider the evaporator cleaning in the Al-Jubail Plant, a committee named as


Evaporator Tube Acid Cleaning Committee (ETACC) was formed by the Manger, AlJubail Plant and corrosion department of RDC was asked to provide its expertise in this
matter.

In its meeting on May 1, 1995, the ETACC requested R&D Center to carryout Phase -2
Evaporator Flash Chamber Materials Corrosion Evaluation by using CP-20 inhibited
HCl and H2SO4. Subsequently, R&D Center Al-Jubail submitted a project entitled "The
Corrosion Behavior of Flash Chamber and Recycle Pump Materials During Acid
Cleaning of the MSF heat Transfer Tubes". The project was approved by the Director
General, R&D Riyadh in June 1995. The work was carried out in the Corrosion
Department and a report was submitted in the last week of August 1995. The report
was reviewed by the R&D Department, Riyadh and the Director General in his letter
dated September 16, 1995 advised Manager, R&D Center that the report could be sent
to the Al-Jubail plant and they may carryout acid cleaning of some units of the plant as
per the recommendation of the report. The Director General further advised that after
obtaining the acid cleaning results from the plant, a comprehensive report from R&D
Center could be issued.

The ETACC agreed to accept the recommendation of R&D Center aforementioned


report and decided to test the inhibited sulfuric acid in some of the desal units of AlJubail plant. The project of acid cleaning of desal tubes in Al-Jubail plant was started in
April 1996. The acid cleaning of several desal units of C4 was completed by the end of
December 1996.

This report presents the results of acid cleaning project-using CP-20 as an acid inhibitor,
for cleaning desal tubes of Al-Jubail Plant. The report is divided into 2 parts : (i)
Laboratory Studies and (ii) Plant Studies.

Laboratory studies are comprised of testing the corrosion behavior of flash chamber and
recycle pump materials in 2% HCl and H2SO4 solutions prepared in natural Gulf
Seawater with 0.7% Nevamin CP-20 under deaeration or open atmospheric conditions.

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Plant studies are consisted of testing the performance of acid inhibitor CP-20 in
acidified brine (pH 1.5-2) as a cleaning agent in desal units #27 and 29 of C4 in AlJubail desalination plant.
1.2

LITERATURE REVIEW

Scale deposition in heat transfer tubes is a unique feature in multistage flash (MSF)
evaporators of seawater desalination plant. The scales are mainly consisted of calcium
carbonate and magnesium hydroxide and occasionally of CaSO4. The scaling induces
insulation in heat exchanger tubes resulting in lowering of heat transfer efficiency and
in consequence, significant losses in production and high-energy consumption.

Mechanical cleaning by balls does not remove the entire scales and some residual scales
are always present in the tubes and there is a progressive build up of the scales with
time which make it essential for the plants to clean the heat transfer tube periodically by
chemical means. Acid cleaning is by far the most effective way to descale the tubes
periodically by chemical means.

The application of dilute aqueous solutions of

sulfamic acid, sulfuric acid or hydrochloric acid containing some inhibitor, has been a
standard practice to clean the tubes in desalination plants [Hanbury, et. al., 1993]. 3%
HCl with 0.5% corrosion inhibitor was used successfully as a descalant in heat transfer
tubes of a 100 tons/day flash evaporation plant [Noguchi, Hamada 1969].

Japan

titanium society [1994] reported that the H2SO4 solution with IBIT 570S and HCl
solution with IBIT 2S prevent the corrosion and hydrogen absorption of titanium and
copper alloys. Sulfamic acid solution with IBIT 570S has been used for descaling of
tubes in MSF plants. Inhibited sulfamic acid and sulfuric acid have been used since
long as a descalant in heat exchanger tubes in Al-Khafji and Al-Khobar desalination
plants, respectively.

The function of an acid inhibitor is to diminish the corrosive action of acid on metals
[Metal Hand Book 1987]. The organic inhibitors show its inhibiting action by surface
adsorption forming a thin film on the metal surface with no significant reaction with the
substrate [Nathan 1973]. It has been observed that one particular type of inhibitor
effective in one system may not be effective in another. ARMOHIB 28 inhibitor has
been effectively used with HCl for cleaning fouled demisters (SS 316L with mesh pads)

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without deterioration of demister metal whilst the same inhibitor has been found
corrosive for cupronickel alloys [Malik et. al. 1994].

Rocchini [1994] discussed at length the application of polarization resistance technique


for corrosion rate monitoring during acid cleaning. A reliable evaluation of the true
corrosion rate of tubular specimen can be made using appropriate calibration charts for
the given environment and geometry of the electrochemical probe.
2.

OBJECTIVES

(i)

To determine the corrosion rates of SS 316 L, 90-10 Cu-Ni, 70-30 Cu-Ni,


Carbon steel and Ni Resist D2 in 2% (HCl and H2SO4) inhibited with 0.5%
Nevamine CP20 in deaerated or normal (non deaerated) seawater, in
laboratory.

(ii)

To establish the acid cleaning process for desal units by recirculation pump
method.

(iii) To determine the pH, Ca++, Cu++ and acid concentration during acid
charging, circulation and flushing for some of the selected desal units.

(iv) To determine the evaporator performance data after acid cleaning and
comparing with pre-cleaning data.

(v)

To provide recommendation regarding acid cleaning of the heat transfer


tubes in the plant.

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3.

EXPERIMENTAL

3.1

CORROSION BEHAVIOR OF SOME MSF PLANT MATERIALS IN


INHIBITED H2SO4 AND HCl - A Laboratory Study

3.1.1

Summary

Effects of addition of inhibitor to the acid solution under deaerated and open
atmospheric conditions were studied in order to control the corrosion of alloys used in
flash chambers, recycle pumps and MSF heat transfer tubes during acid cleaning
Corrosion behavior of carbon steel, Ni-resist, SS 316L and cupronickel alloys was
studied in 2% HCl and H2SO4 aqueous solutions (prepared in Gulf Seawater) with and
without inhibitor Nevamin CP-20 under deaeration and open atmospheric condition.
Immersion and polarization resistance tests show that corrosion rates of carbon steel and
Ni-Resist alloy in 2% HCl and H2SO4 solutions with inhibitor are higher in open
atmosphere as compared to the deaerated condition. However, inhibited acid solutions
in both deaerated and normal atmospheric conditions show good corrosion resistance
towards stainless steel 316L and cupronickel alloys. Results of this study indicate that
the addition of 0.5% inhibitor along with the deaeration of the acid solution (dissolved
oxygen < 20 ppb) is the best condition for acid cleaning with negligible corrosion of
heat exchanger tubes, evaporator and recycle pump materials.

3.1.2

Experimental

3.1.2.1

Materials

Commercially available sheets of carbon steel, 316L stainless steel and 70-30, 90-10
cupronickel alloys were used for making test specimens. Specimens of Ni-Resist D2
were cut from blocks obtained from casings of used brine recycle pumps. Hydrochloric
acid and sulfuric acid of commercial grades and corrosion inhibitor Nevamin CP-20
were obtained from Al-Jubail desalination plant. 2% solutions of HCl and H2SO4 were
prepared in natural seawater and 0.5% inhibitor was added to these acid solutions.

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3.1.2.2

Immersion Tests

Corrosion rates of materials by immersion test were determined following ASTM


method (G 31-72; reapproved 1990).
Polished coupons of carbon steel, 316L stainless, Ni-resist and 70-30, and 90-10
cupronickel alloys of 60x40x2 mm dimensions were immersed in one liter each of 2%
hydrochloric and sulfuric acid solutions after taking their initial weight. Recommended
amount (0.5%) of Nevamin CP-20 inhibitor (5 ml inhibitor/liter of acid solution) was
added to each of the aerated and deaerated acid solutions kept at room temperature
under dynamic condition. The deaeration in the test solution was done by purging
nitrogen gas (99.99%) in an air tight experimental set up. The traces of oxygen present
in the nitrogen gas were removed by bubbling through an alkaline solution of
pyrogallol. In these aqueous acid solutions, 2 coupons were immersed for 6 hrs. After
taking out the coupons from the acid solution, they were cleaned, dried and weighed and
weight loss was calculated.

This experiment was repeated three times for each

condition and means of corrosion rates were calculated.

3.1.2.3

Electrochemical Polarization Studies

Liner polarization resistance experiments were carried out using an EG&G


Electrochemical Corrosion measurement System following procedure ASTM-G59-78
(Reaproved

1984).

The

Corrosion

System

is

consisted

of

Model

273

potentiostat/galvanostat; model 342-softcorr software and model 30 IBM PS/2


computer. All the experiments were carried out using a corrosion cell with saturated
calomel as reference and graphite as counter electrodes. Flat circular test specimens
were used. The test specimens were screwed in the sample holder and the exposed area
was 1 cm2.
The polarization resistance measurements were conducted at a scan rate of 0.1 mV/s
with starting and final potentials corresponding to -20 mV and +20 mV as open circuit
corrosion potential (OCP), respectively. Before starting the experiments, the specimens
were left in the acid solution for about 1 hour to attain a steady state, which was shown
by a constant potential.

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3.1.2.4

Measurements of Dissolved Oxygen

Dissolved oxygen in the deaerated test solution was measured by Dissolved Oxygen
Measurement-System model 273 of Orbisphere Laboratories, Geneva. The sensitivity
of this system is one microgram per liter (1 ppb).

3.2

ACID CLEANING OF SOME DESAL UNITS AT AL-JUBAIL PLANT

Al-Jubail desal and power plant Phase II A & B combined has forty (40) evaporators
with base design distillate production capacity of 5.25 MGPD each unit. One set of acid
cleaning system has been provided for twenty (20) desalination units, i.e., each phase
has one set of acid cleaning facility. Location of the acid cleaning system in each phase
is in the center of the area covering ten evaporators in each side. Facilities for pumping
and transportation of acid solution have been provided at the suction of each recycle
brine pump. The designed acid cleaning procedure requires circulation of acidified
brine at pH 2-2.5 through the recovery, brine heater tubes and the flash chambers. AlJubail Phase-II evaporators do not have 'tubes only cleaning facility' as some other
plants do have as designed and built in components.
3.2.1

Acid Cleaning With Sulfuric Acid

For evaporator acid cleaning, acid to the circulating brine was injected directly from
acid tanker through an acid resistant flexible pipe connected to the drain valve of the
last stage flash chamber. The tanker was fully vented to atmosphere and connected to
the drain valve of last stage. Acid inhibitor to the circulation brine was charged through
a sample collection point was approximately 0.7% of the acid charged. A higher charge
of the inhibitor than the recommended one (0.5%) was used to take care of the possible
fluctuations in the dozing system and to ensure homogeneity of mixing under plant
operation conditions. Acid injection was regulated to maintain circulating brine pH 1.52.0 at the discharge of recycle brine pump. Circulating acidified brine temperature was
maintained at 48-50 oC and brine velocity at about 0.7 m/sec. The acid cleaning of
evaporators was conducted in three charges. After completion of the acid cleaning
process, rinsing and draining of the evaporators were carried out. During the acid

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cleaning process laboratory analysis of the brine samples from recycle brine (RB) pump
discharge, brine heater outlet (BHO) and brine blow down (BB) pump were carried out
for pH, % acid, Ca2+ and Cu2+.
After the acid cleaning operation was completed, brine heater inlet and outlets, water
boxes manhole, heat recovery north-side water box manholes (stage 1-17) and flash
chamber stages # 1-4 and 16-19 were opened for inspection.
4.

RESULTS AND DISCUSSION

4.1

IMMERSION TESTS

4.1.1

Immersion Test Under Atmospheric Conditions

Table 3 summarizes the mean corrosion rates of 6 hrs duration immersion tests for
carbon steel, SS 316L, Ni-resist and cupronickel alloys in 2% of HCl and H2SO4 with
and without inhibitor under dynamic condition. In HCl acid solution, 316L stainless
steel showed low corrosion rate (< 1 MPY) in presence and absence of inhibitor.
However, high corrosion rates were found for cupronickel (53-66 MPY), carbon steel
(101 MPY) and Ni-resist (46 MPY) in absence of inhibitor. Although, the addition of
inhibitor decreases the corrosion rates of the alloys, viz., cupronickel (1.5-2.5 MPY),
carbon steel (46 MPY) and Ni-resist (33 MPY) but the corrosion rates of the carbon
steel and Ni-Resist remain high. Similar trend was found in inhibited H2SO4 acid
solution but this acid solution was found less corrosive than HCl (Fig. 2 and 3).

Cupronickel 90-10 and 70-30 alloys have shown good corrosion resistance in 2%
H2SO4 acid environment (5 MPY) and poor corrosion resistance in 2% HCl acid
environment (53-66 MPY). This is because of the fact that in the presence of an
oxidizing agent (e.g., dissolved oxygen) HCl becomes more corrosive than H2SO4
[ASM Metal Handbook 1987]. The results also indicate that 70-30 cupronickel is less
corrosion resistant than 90-10 cupronickel. Nickel is more active than copper in the
electrochemical series. The passive film of nickel in not particularly stable and, hence,
nickel cannot generally be used in oxidizing environments such as nitric acid [Sridhar
and Hodge, 1989].

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Table 4 summarizes the inhibitor efficiency in open atmospheric condition.

The

efficiency of inhibitor can be calculated from the following equation.

Ieff =

Ro Ri
x 100
Ro

Ieff

Inhibitor efficiency

Ro

Corrosion rate without inhibitor

Ri

Corrosion rate with inhibitor

Tables 4 shows that in both the acid media, inhibitor Nevamin CP-20 is very effective
in suppressing the corrosion of cupronickel alloys (efficiency 80%) while its
efficiency is comparatively low (28 to 54%) for carbon steel and Ni-resist alloys. This
may be due to the fact that the mode of adsorption of an inhibitor depends on chemical
structure of the molecule, chemical composition of the solution, nature of the metal
surface and the electrochemical potential at the metal-solution interface.
4.1.2

Immersion Test Under Deaeration Condition

Table 5 lists the corrosion rates of alloys in acid solution with and without inhibitor
under deaeration and dynamic conditions. The dynamic conditions were simulated by
shaking vigorously the solution through a magnetic device. For acid solution without
inhibitor, results show high corrosion rates for carbon steel (10-17 MPY), and low
corrosion rates for cupronickel alloys (2-4 MPY) while Ni-resist alloys occupy the
middle position (4.5-6.8 MPY). No perceptible weight change was recorded for 316L.
The overall corrosion rates of alloys are in the allowable range. Therefore, deaeration
appears to be more effective than addition of inhibitor in lowering the corrosion rate in
2% acid solution environment.

After passing N2 at the rate of 150 ml/min for 30 minutes in the acid solution, < 10 ppb
dissolved oxygen was found.

For acid solution with inhibitor, results show no

perceptible weight loss and no change in the surface appearance of the coupons of SS
316L, Ni-resist, 90-10 and 70-30 cupronickel alloys. Even the carbon steel specimens
show a low corrosion rate of 3.5 MPY without any remarkable change in the surface

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appearance of the coupons.

The efficiency of inhibitor increases under deaerated

condition (Table 6); for all the alloys except carbon steel have efficiency approaching to
100% even the latter has a good efficiency performance of 65% and 79% in HCl and
H2SO4 solutions, respectively. This indicates that the addition of inhibitor along with
the removal of oxygen provide good corrosion protection to the above alloys in both the
2% HCl and 2% H2SO4 acid medium.

4.1.3

Polarization Resistance Tests

Table 7 lists the corrosion rates of alloys in 2% HCl and H2SO4 acid solutions (prepared
in seawater) with 0.5% CP-20 inhibitor in open atmosphere and deaeration under
dynamic condition. The corrosion rates are computed from the Liner Polarization
Resistance (LPR) plots. These results show that in HCl acid solution in atmospheric
condition, the corrosion rates of carbon steel (50 MPY) are higher as compared to Niresist (31 MPY) and much higher than that of cupronickel alloys (< 0.50 MPY). AISI
316L occupies the middle position (5 MPY). Same trend was found in the case of
H2SO4 acid solution but in general all the alloys show comparatively low corrosion rate.
Corrosion rates of alloys in inhibited acid solution under deaeration condition are lower
than that found under open atmospheric condition. It was interesting to note that the
corrosivity of HCl acid solution is higher than H2SO4 acid solution for carbon steel and
Ni-resist alloy in open atmospheric condition but in deaerated condition this behavior is
just opposite.

Figure 4 shows the anodic and cathodic polarization's curves (Tafel plots) of carbon
steel in inhibited acid solution at open atmosphere and deaeration under dynamic
conditions. Icorr (corrosion rate) is determined by the extrapolation of the liner region
of the Tafel plots. In case of inhibited 2% HCl acid solution under open atmospheric
condition, the corrosion current is 100 A/cm2, however, the deaeration effectively
reduced the corrosion current by around two orders of magnitude. 2% H2SO4 acid
solution results show similar trends as those observed in HCl acid solution. Figure 5
shows a typical LPR plot for carbon steel in inhibited sulfuric acid deaerated condition.
The slope of the plot represents the corrosion rate of the alloy.

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4.2

Acid Cleaning of Desal Units # 29 and 27

4.2.1

Acid Cleaning of Desal # 29

The test cleaning of this unit was done to evaluate the cleaning procedure. A cleaning
procedure which has been detailed in the above section 3.2.1, was followed.

The acid cleaning of heat exchanger tubes in evaporators of desal #29 was conducted in
three charges. During acid cleaning the brine flow was kept at 5000-6000 m3/hr. The
temperature of the acidified brine was maintained 47-49 oC at the brine heater outlet.
The amounts of acid, inhibitor and antifoam are given below.:

First Charge

Second Charge

Third Charge

Total

Consumed Day 1

Day 2

Day 3

Sulfuric acid (tons)

28.8

28.8

29

86.6

Acid inhibitor (kg)

200

200

400

800

Anti-Foam (kg)

10

10

10

30

Figures 6 to 9 show plots computed from the data obtained from Ca2+, Cu2+, acid
concentration and pH determinations during acid cleaning of the evaporators.
Variation in Ca2+ ion during cleaning in all the three charges vs time is shown in Fig. 6
Figures 7-9 show the variation in Cu2+ ion, acid % and brine pH vs time respectively.
Figures 10 and 11 show the variation in Cu2+ ion and pH of the recirculating acidified
brine in BHO samples during rinsing.
In first 3-5 hrs of acid injection in each charge, an increase in Ca2+ concentration is
observed. After 3-5 hrs, the Ca2+ concentration becomes almost constant, which shows
that the dissolution of scales became negligible. This represents the stage where it
would be advisable to blow-down the brine and add acid to fresh seawater. A similar
trend has been for Cu2+ ion also. After 5 hrs of dosing in the I charge, the Cu2+ ion
concentration reached to its maximum value of 32 ppm, which is an indication that the
heat exchanger tubes (with or without protective oxide film) are almost free from scales
and are in direct contact with the acid. The value of Cu2+ ions in following II and III

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charges reached to higher levels than charge I. In charge III, the concentration of Cu2+
ion is less as compared to charge II due to the use of double amount of inhibitor, In Fig.8
a sharp decrease in acid percentage is also observed after 3-5 hrs of injection
indicating that all the acid injected has been consumed within this period. An increase
in pH (Fig. 9) of the brine supports this viewpoint. However, in the subsequent II and
III charges, the pH of the brine does not rise to the same level as that was noted in the
Charge I and the rate of increase in pH is also very slow as compared to charge I.
During flushing (rinsing) decrease in Cu2+ ions to a minimum level (1.0 ppm) in 8 hrs
and increase in pH up to a maximum level of 8.05 in 15 hrs has been observed (Fig. 1011). Therefore, a minimum of 15 hrs to flushing should be carried out before putting the
system on load. However, a minimum of 8 hours of flushing is necessary while
changing over from one charge to another.

During the acid cleaning process, laboratory analysis of the sample was carried out as
follows:

S. No.
Operation
1
Acid charging
2
3

Acid circulation
Rinsing

Kind of Analysis
pH, Cu
pH, Acid % and Cu
pH, Ca and Cu

Sample Collection Point


RB pump discharge and
brine heater outlet
Brine heater outlet
Brine blow down

When the evaporator was back to production after inspection, monitoring of copper
values both in the blow down and product water was continued until the values became
normal.

The results of the post cleaning observations and the performance data for the tubes
cleaned with H2SO4 solutions containing inhibitor CP-20 are given in Tables 9 to 10.
The results indicate much better performance of heat exchanger tubes after acid
cleaning.

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13

4.2.2

Acid Cleaning of Desal # 27

The visual observations of the desal unit # 27 before and after acid cleaning operation
are presented in Table 11. The different sections of the unit were also photographed
before and after acid cleaning. A brief description of the photographs is as follows:

Figures 12A and 12B show water box wall, tubes and tube sheet of brine heater inlet
before and after acid cleaning, respectively. Uniform thin scales were found on the
walls of the water box, tube sheet and tubes in the inlet of brine heater (Fig. 13A).
Similarly, slightly thicker scales were observed in the outlet of the brine heater (Fig.
14A). Figures 12B, 13B and 14B show the water box wall, tube sheet and close up
view of the tubes in the inlet and outlet of the water box of brine heater after acid
cleaning. Some small pieces of scales can be seen scattered on the tube sheet in the
outlet of the brine heater. All sections of the brine heater were satisfactorily cleaned
after acid cleaning.

Figures 15A and 15B show a close up view of the tubes of water box stage#1 before and
after the acid cleaning, respectively. Figure 16 represents the level of thickness (in %)
of scales in the tubes of heat recovery section and brine heater before the acid cleaning.
This graph has been drawn on the basis of visual observations of scale thickness. Heavy
scale deposition was found in the tubes of water box # 7, 8, 9, 10 and 11 (Figures 17
and 21). In general, the deposition of scales on the tubes of water boxes # 12-17 was
higher than the tubes of the water boxes # 1-6. Figure 19A shows a close up view of the
tubes and detached scales in the outlet of the water box # 9 before acid cleaning,
appeared in the center of the photograph. Figure 19B shows the presence of residual
scales in the same section after acid cleaning. Partial cleaning of the tubes of the water
box # 7, 8, 10 and 11 can be seen in Figures 17, 18, 20 and 21. Figure 22A shows the
presence of sludge, debris (scales) and tubes plugged with balls at 6-9 O'clock position
in water box # 14 and 16 also. Figures 22B shows a overall view of the water box # 14
after acid cleaning.

Figure 23 shows partial cleaning of tube sheet of the water box # 15 and Figure 24
shows satisfactory cleaning of the tubes and tube sheet in the water box # 17. Bluish

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color stains are seen on the tubes of the water box # 15 and 17. It was observed that
cleaned tubes exposed to atmosphere for long periods (for inspection) develop blue
stains on the inner surface for the tube .The bluish stains would have formed as a result
of dissolution of copper oxide protective film on the inner surface of tubes and
subsequent attack of acid on bare metal. Such stains are likely to disappear after the
formation of a fresh copper oxide protective film. Figures 25A and B show the acid
injection site (drain of flash chamber # 18) before and after the acid injection. Partial
removal of scales in the vicinity of the hole and a uniform iron hydroxide thin layer can
be seen (Fig. 14B).

The physical inspection and study of the photographs of desal # 27 before acid cleaning
showed:
(a)

Very thin scales were present in the tubes of brine heater inlet.

(b)

Thin scales were found in the tubes of water box # 1-9 and brine heater outlet.

From the post acid cleaning inspection, the following important observations were
emerged:
(a) Scales were removed satisfactorily from the tubes, tube sheet and walls of the
water box of brine heater inlet and outlet and water boxes # 1-6 and # 12-17.
(b) Partial cleaning of scales in the tubes, tube sheet and walls of the water box # 711was observed.
(c) In general, brine heater inlet and outlet tubes and most of the heat recovery stage
tubes were cleaned satisfactorily. The results of pre- and post acid cleaning
performance for desal Unit # 27 are summarized in Table 12.

Tables 10 provides plant analysis data for desal cleaning samples collected at certain
intervals at 3 locations:
(i) During Acid Charging:

Brine recycle pump inlet and brine heater outlet


(pH)

(ii) During Acid Circulation:

Brine heater outlet (pH, % H2SO4)

(iii) During Flushing:

Brine blowdown (pH, Ca2+)

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A general pattern emerges from analytical data, which is summarized as follows:


(a)

During acid charging, pH was maintained around 1.5-2.0 in inlet (RB). In


outlet (BHO), pH goes down slowly in the beginning and rises sharply at the
later stages showing consumption of acid.

(b)

During circulation, pH in the brine heater outlet increases gradually with


increase in time and H2SO4 concentration decreases showing the process of
acid cleaning is under completion.

(c)

During flushing, in blow down, pH increases and Ca2+ concentration


decreases with time showing the process of flushing is under completion.

The cleaning procedure was first evolved by carrying out test cleaning of desal # 29
unit. Besides pH, acid concentration and Ca2+, Cu2+ concentration was determind in the
brine heater outlet during the three charges. During first charge, amount of copper
leached out during the first 2 hrs or so is quite low (< 2 ppm) but after this period, there
is tremendous increase in copper concentration (22 ppm) which increases gradually with
time reaching a value of 32 ppm after 7 hrs circulation. The amount of the copper
leached out during second charge (> 50 ppm) was much higher than that in the first
charge. This indicates that the acid has now in direct access to descaled or undeposited
desal surfaces leaching out significant amount of copper. Lower values of leached
copper in the third charge might be attributed to the formation of passive Cu2O film
formed during post charge II flushing.

Post acid cleaning results of the different desal units of C-4 indicate satisfactory
cleaning of units under study. For example, there is a significant improvement in water
production. Similarly, in gain output ratio (GOR) value there is an immense
enhancement on acid cleaning in different units. This is shown below:

1590

Unit #

Water Production (m3/hr.)

Gain Output Ratio (GOR)

Pre
Cleaning

Post
cleaning

Improvement
%

Pre
Cleaning

Post
cleaning

Improvement
%

27

920

1120

20.7

6.3

8.6

36.5

29

820

1010

23.1

6.0

8.8

47.1

The values of heat transfer coefficient (HTC) of brine heater and heat recovery section
were determined for desal unit # 29 before and after acid cleaning, an improvement of
53.3 and 62.3%, respectively was noted as shown below:

Heat Transfer Coefficient

Brine Heater

Heat Recovery

HTC, W/m2/oC (Before Acid Cleaning)

1908

1663

HTC, W/m2/oC (After Acid Cleaning)

2925

2700

% Improvement

53.3

62.3

5. CONCLUSION
5.1

Laboratory Studies

(i)

Addition of 0.5% CP-20 inhibitor along with deaeration of 2% HCl or H2SO4


solution provide good corrosion control of the evaporator and brine cycle pump
materials.

(ii)

The corrosion rates of MSF plant materials namely carbon steel, AISI 316L,
Ni-Resist D2 and cupronickel (90-10 and 70-30) in CP-20 inhibited HCl or
H2SO4 solutions under dynamic and deaerated conditions are much below the
allowable range. Therefore, a 2% HCl or H2SO4 solution prepared in seawater
and inhibited with 0.5% Nevamin CP-20 under deaerated (O2 ~ 10 ppb) and
dynamic conditions can be utilized for cleaning heat exchanger tubes of the
plants. Table 8 provides a comparative study of the corrosion rates.

(iii)

H2SO4 appears to be a better choice provided the CaSO4 scales formed by


H2SO4 could easily be removed during cleaning otherwise HCl can be used as
a cleaning agent.

1591

(iv)

For acid cleaning following steps must be followed :


Acid solution should be free from oxidizing contaminants.
Full deaeration of the acid solution.
Inhibited acid solutions should be under dynamic condition.
Post acid cleaning procedures should be strictly followed.

5.2

Plant Studies

The analysis of pre-and post cleaning operations data obtained from C4 desal units #27
and 29 provides the following information:
(i)

In general, the acid cleaning of the desal tubes and water boxes in different units
appears to be effective in the sense that the scales are removed without producing
any significant corrosion attack.

(ii)

In all the units, acid cleaning resulted in satisfactory improvement in evaporator


performance.

6.

RECOMMENDATION

The usefulness of inhibited H2SO4 solution (under deaerated condition) in cleaning heat
transfer tubes of desal units #27 and 29, C4 in Al-Jubail phase-II is firmly established
and the cleaning operation may be extended to other units of the plant.
7.

FUTURE WORK

In order to have better understanding of the nature of meal dissolution (corrosion)


process involved during acid cleaning, it is recommended to carry out further work
stated as follows :
(a) Corrosion monitoring of closely spaced segments of inside of the entire length
of desal tube. This would provide information about the segments which
contribute most to carryover copper and nickel.

1592

(b) Effect of cleaning agent (acid) velocity on the corrosion of desal tubes and
other components.
(c) Effect of dissolved oxygen level in acid solution on the dissolution of scales
and corrosion of components.

(e) Investigation to the cause of much heavier scaling in the tubes of later (lower
temperature) heat recovery stages.
REFERENCES
1. Fontana M. G., (1987) "Corrosion Engineering, Mc Graw Hill International, 3rd Edition,
p. 172.
2. Hanbury, Hodgkiess and Moris, (1993) "Desalination Technology '93', Porthan,
Glasgow, UK.
3. Japan Titanium Society (1994) "Countermeasures Against Deposit of Scale Oceanic
Lives - Light Gauge Titanium Tubes for Seawater Desalination Plants - 3 Q&A
Practical Application", p. 14.
4. Malik A. U., Mayan Kutty P. C., Nadeem Siddiqi A., Ismaeel Andijani N. and Shahreer
Ahmed (1992) Corrosion Science, 33, 1810.
5. Malik A. U., Andijani, I. N., Nadeem Siddiqi A., Shahreer Ahmed and Al-Mobayaed A.
S., (1994) "Studies on the Role of Sulfamic Acid as a Descalant in Desalination
Plant. Proc. VI Middle East Corrosion Conference, Bahrain, 24-26. Jan., pp. 6578.
6. Metal Hand Book (1987) Vol. 13, Corrosion, Specific Industries and Environments,
American Society of Metals, p. 1140.
7. Nathan, C. C. (1973) "Corrosion Inhibitor", Betz Laboratories, Inc. National
Association of Corrosion Engineers, Houston, Texas, NACE Publication.
8. Noguchi N., T. Hamada (1969) "Prevention of Scale and Corrosion of Flash
Evaporators", Nuclear Desalination, International Atomic Energy Agency Vienna,
p. 879.
9. Rocchini G., (1994) Corrosion Prevention and Control, 41, 108.
10.Uhlig. H. and R. Revie, (1985) "Corrosion and Control", John Wiley and Sons, 3rd
Edition (1985) p. 13.

1593

Table 1. Corrosion Rate (MPY) of Heat Exchanger Tube Materials in 2%


Inhibited Acid Solutions under Dynamic Condition
Acids

Duration (hrs)

Hydrochloric
+
0.3% IBIT
Sulfamic
+
0.3% IBIT
Sulfuric
+
0.3% IBIT

6
24
72
6
24
72
6
24
72

90-10
Cupronickel
0.09
0.03
0.04
0.06
0.04
0.03
0.09
0.09
0.04

70-30
Cupronickel
0.09
0.05
0.02
0.06
0.03
0.03
0.1
0.1
0.05

Ti
0.07
0.03
0.02
0.02
0.03
0.01
0.02
0.02
0.06

Table 2. Corrosion Rate (MPY) of Heat Exchanger Tube Materials in 2%


Inhibited Acid Solutions Under Dynamic Condition
Acids

Duration (hrs)

Hydrochloric
+
0.3% CP-20
Sulfamic
+
0.3% CP-20
Sulfuric
+
0.3% CP-20

6
24
72
6
24
72
6
24
72

90-10
Cupronickel
2.58
1.85
1.37
0.55
0.31
0.5
0.66
0.6
0.6

70-30
Cupronickel
3.25
2.23
3.66
0.41
0.73
0.2
0.73
0.5
0.6

Ti
0.37
0.28
0.06
0.02
0.02
0.02
0.06
0.08
0 .03

Table 3. Corrosion Rates (MPY) of Different Alloys Immersed in inhibited (CP20-0.5%)


Acid Solutions (Prepared in Gulf Seawater) Under Dynamic and Open
Atmospheric Condition for 6 hr.
2% Acid
Solution

Alloys
Ni-Resist
Cupronickel
D-2
90-10

C. Steel

SS 316 L

HCl

101

<1

46

53

66

H2SO4

81

<1

45

HCl + CP-20

46

<1

33

1.5

2.5

H2SO4 + CP-20

40

<1

22

1594

Cupronickel
70-30

Table 4. Efficiency (%) of Inhibitor Nevamin CP-20 in Controlling the Corrosion


of Different Alloys in Acid Solutions Under Dynamic and Open
Atmospheric Conditions
2% Acid
Solution

Alloys
Ni-Resist
Cupronickel
D-2
90-10

C. steel

SS 316 L

HCl

54

~ 100

28

97

96

H2SO4

50

~ 100

51

80

80

Table 5.

Cupronickel
70-30

Corrosion Rate (MPY) of Different Alloys Immersed in Deaerated


inhibited (CP-20-0.5%) Acid solutions (Prepared in Gulf Seawater) Under
Dynamic Condition for 6 Hrs.
2% Acid
Solution

C. steel

SS 316 L

Alloys
Ni-Resist
D-2

HCl

10

<1

4.5

H2SO4

17

<1

6.8

HCl + CP-20

3.5

<< 1

<1

<1

<1

H2SO4 + CP-20

3.5

<< 1

<1

<1

<1

Cupronickel
90-10

Cupronickel
70-30

Table 6. Efficiency (%) of Inhibitor Nevamin CP-20 in Controlling the


Corrosion of Different Alloys in Deaerated Acid Solutions Under
Dynamic Condition
2% Acid
Solution

Alloys
Ni-Resist
Cupronickel
D-2
90-10

C. Steel

SS 316 L

HCl

65

~ 100

~ 100

~ 100

~ 100

H2SO4

79

~ 100

~ 100

~ 100

~ 100

1595

Cupronickel
70-30

Table 7. Corrosion Rate (MPY) of Different Alloys Immersed inInhibited Acid


Solutions (Prepared in Gulf Seawater) Under Dynamic Condition by LPR
Technique
2% Acid
Solution

C. Steel

SS 316 L

Alloys
Ni-Resist
D-2

HCl + atmospheric

50

31

0.4

0.5

H2SO4 + atmospheric

32

21

0.1

0.2

HCl + deaeration

0.2

0.2

0.3

H2SO4 + deaeration

0.1

0.03

Table 8.

Cupronickel
90-10

Cupronickel
70-30

Corrosion Rate (MPY) of Different Alloys in Inhibited Acid Solutions Under


Atmospheric or Deaerated Condition
0.5 % CP - 20 Inhibited
2% H2SO4
Corrosion Rates, MPY
Max. Allowance*
Found
Max. Allowance*

2% HCl
Test Condition
Atmospheric
Deaerated
Atmospheric
Deaerated
Atmospheric
Deaerated
Atmospheric
Deaerated
Atmospheric
Deaerated

Alloy
C. S
SS 316 L
Ni-Resist
90 Cu 10 Ni
70 Cu 30 Ni

Found
46
3.5
<1
<< 1
33
<1
1.5
<1
2.5
<1

20-50 Fair
1-5 Excellent
< 1 outstanding
< 1 outstanding
20-50 Fair
< 1 Excellent
1-5 Excellent
< 1 outstanding
1-5 Excellent
< 1 outstanding

40
3.5
<1
<< 1
22
<1
1
<1
1
<1

* Represent maximum allowable corrosion rates in corrosive environments


[Fontana 1987, Uhlig and Revie 1985]

1596

20-50 Fair
1-5 Excellent
1-5 Excellent
1-5 Excellent
20-50 Fair
< 1 outstanding
1-5 Excellent
< 1 outstanding
1 Excellent
< 1 outstanding

Table 9.
S. No

Post Cleaning Observations Desal # 29

Components subjected
to cleaning
Brine heater inlet
Brine heater outlet

State of
Cleaning
Very good
Good

Heat recovery tubes


Stage 1-6

Fully cleaned

Some tubes
plugged

Stage 7-12

Good

Stage 13-17

Good

Scale debris were found at the


bottom of the tube sheet which
blocked tube opening.
Some tubes were found
plugged with scale debris
and/or cleaning ball blockage at
tube inlet/outlet.

Flash chambers

Acid injection point #18


flash chamber drain
point

Uniform
minor
descaling
Cleaned to base
metal

1
2

Remarks
Cleaned to base metal.
Center tubes were not as clean
as the lower tubes. Upper row
tubes cleaned to bare metal.
were

found

No visible sign of corrosion

Table 10: Post Acid Cleaning Performance Data for Desal # 29


Description

Design

Before

After

Improvement

90.6

87.5

89.9

2.4

988

820

1010

190

23%

LP steam consumption M /hr

129.4

142

118.5

23.5

16.5%
(reduced)

P. R. Kg.Dist./1000 KJ

3.44

2.64

3.88

1.24

47%

7.9

5.98

8.8

2.82

47%

2467

1908

2925

1017

1663

2700

1037

12480

10500

11300

800

TBT C
3

Dist. Prod. M /hr


3

G. O. R. KgDist../KgSteam
2 0

HTC brine heater W/M / C


2 0

HTC recovery W/M / C


Recycle brine flow at max.
v/v opening M3/hr.

1597

Table 11A. Before Acid Cleaning Observations Deasl#27


Location
Brine Heater
Inlet & Outlet
Tubes
Tube sheet
Water box
Heat Recovery Section
Water Box #1 Outlet
Tubes
Tube sheet
Water box
Water Box #3 - 7
Tubes
Tube sheet
Water box
Water Box #8-11
Tubes
Tube sheet
Water box
Water Box #12-17
Tubes
Tube sheet
Water box

Scale Presence

Remarks

Very Thin Scales


Very Thin Scales
Very Thin Scales

At outlet the scaling


was slightly more than
the inlet

Very Thin Scales


Very Thin Scales
Very Thin Scales

Similar scales were


found as were in brine
heater outlet.

Thin Scales
Thin Scales
Thin Scales

Few tubes were found


blocked either by balls
or debris (scales).

Heavy Scales
Heavy Scales
Heavy Scales

Few tubes were found


blocked either by balls
or debris (scales).

Thick Scales
Thick Scales
Thick Scales

Few tubes were found


blocked either by balls
or debris (scales).

1598

Table 11B. Post Acid Cleaning Observations Desal #27


Location
Brine Heater
Inlet & Outlet
Tubes
Tube sheet
Water box
Water Box #1-5
Tubes
Tube sheet
Water box
Water Box #6
Tubes
Tube sheet
Water box
Water Box #7,8,9,10 &11
Tubes
Tube sheet
Water box
Water Box # 12, 15
Tubes
Tube sheet
Water box
Water Box #13, 14
Tubes
Tube sheet
Water box
Water Box #16, 17
Tubes
Tube sheet
Water box

Scale Presence

Remarks

Satisfactorily Cleaned
Satisfactorily Cleaned
Satisfactorily Cleaned

No sign of corrosion
was observed.

Satisfactorily Cleaned
Satisfactorily Cleaned
Satisfactorily Cleaned

No sign of corrosion
was observed.

Satisfactorily Cleaned
Partially Clean
Satisfactorily Cleaned

Few tubes were blocked.

Partially Clean
Partially Clean
Partially Clean
Satisfactorily Cleaned
Partially Clean
Partially Clean
Satisfactorily Cleaned
Satisfactorily Cleaned
Partially Clean
Few tubes were blocked.

Satisfactorily Cleaned
Satisfactorily Cleaned
Satisfactorily Cleaned

Table 12. Evaporator Performance Summary After Acid Cleaning


Unit
No.

Acid
Used
(Tons)

Evap
Off.
Prod. Hr.

Pre Cleaning Values


P. W. Cond GOR
M3/hr M3/hr

D-27

91

928

147

6.31

1120

130

8.61

192

2.3

D-29

87

116

820

142

5.98

1010

118.5

8.8

190

2.82

1599

Post Cleaning Values


P. W. Cond GOR
M3/hr M3/hr

Improvement
P. W. GOR

0.8

90-10: IBIT
70-30: IBIT

0.7

Corrosion Rate (mpy)

Ti: IBIT
90-10:CP-20

0.6

70-30: CP-20
0.5

Ti: CP-20

0.4
0.3
0.2
0.1
0.0
6

24

72

Immersion Time (Hours)

Figure1. Corrosion rate (mpy) of Titanium and Cupronickel alloys in 2% Sulfuric


(H2SO4) acid solution inhibited with IBIT and CP-20 inhibitors.

1600

120
HCl
HCl + Inhib.

100

Corrosion Rate (mpy)

HCl + Inhib. + Deaeration


80

60

40

20

0
C.S

Ni-Resist

90-10

70-30

Alloys

Fig.2

Corrosion rate (mpy) of different alloys in 2% Hydrochloric (HCl) acid


solution (prepared in Gulf seawater) inhibited with 0.5% CP-20 inhibitor
under dynamic condition by immersion test method.

1601

90
H2SO4

80

H2SO4 + Inhib.
H2SO4 + Inhib. + Deaeration

Corrosion Rate (mpy)

70
60
50
40
30
20
10
0
C.S

Ni-Resist

90-10

70-30

Alloys

Fig.3

Corrosion rate (mpy) of different alloys in 2% Sulfuric (H2SO4) acid


solution (prepared in Gulf seawater) inhibited with 0.5% CP-20 inhibitor
under dynamic condition by immersion test method.

1602

1603

-5 15

-520

-525
E( CQRR)
-530

-535

I ( UA/CMAZ)

Fig. 5

Typical polarization resistance curve for carbon steel in inhibited 2%


sulfuric acid solution under deaerated condition.

1604

3000
BHO
BRP

Ca++ (ppm)

2500
2000
1500
1000
500

I - Charge

II - Charge

III - Charge

0
0

10

15

20

25

30

35

40

45

Time (Hrs.)

1st. Fig 6 Plots of Ca++ Vs Time in BRP and BHO samples for all charges.

Cu++ (ppm)

60

I - Charge

II - Charge

III - Charge

50

BHO

40
30
20
10
0
0

10

15

20

25

30

35

40

45

Time (Hrs.)

Fig. 7

Plot of CU++ Vs Time in BHO samples for all charges; BHO: Brine Heater
Outlet

1605

0 .3 5

I - C h a rg e

A c id (%

0 .3 0

III - C h a rg e

II - C h a rg e

BRP
BHO

0 .2 5
0 .2 0
0 .1 5
0 .1 0
0 .0 5
0 .0 0
0

10

15

20

25

30

35

40

45

T im e (H rs.)

Fig.8

Plot of Acid% Vs Time in BRP and BHO samples for all charges.

6
BRP
BHO

Brine (pH)

5
4
3
2
1
0
0

10

15

20

25

30

35

40

45

Time (Hrs.)

Fig. 9

Plot of pH Vs Time in BRP and BHO samples for all charges. BRP:
Brine Recycle Pump; BHO: Brine Heater Outlet.

1606

25
I-charge
II-charge

20

Cu++ (ppm)

III-charge
15

10

0
0

12

16

Time (Hrs.)

Fig. 10 Plots showing the variation in Cu++ ion in BH outlet samples


time for each Charge during flushing.

versus

Variation in pH during Flushing

pH

9
8
7
6
5

I-charge
II-charge
III-charge

4
3
2
1
0
0

12

16

Time (Hrs.)

Fig. 11

Plots showing the variation in pH in BH outlet samples versus time


for each Charge during flushing.

1607

[A]

[B]
Fig. 12

box wall, tubes and tube sheet showing scale deposition in the inlet of
brine heater of desal #27, C4, phase-II, Aljubail plant: A-before acid cleaning
and B-after acid cleaning.

1608

[A]

[B]

Fig.13

A close-up view of the tubes and tube sheet in the outlet of the brine heater
of desal #27, C4, Phase-II, Al-Jubail Plant : A-before acid cleaning and Bafter acid cleaning.

1609

[A]

[B]
Fig.14

A close-up view of the tube and tube sheet in in the outlet of the brine heater
of desal #27, C4, Phase-II, Al-Jubail Plant: A-before acid cleaning and Bafter acid cleaning.

1610

1611

Fig. 16

Reltive thickness of scale deposition in the tube of heae recovery section


and brine heater of desal #27, C4 area Al-Jubail desalination and power
plants, SWCC, - Evaluated on the basis of visual examination only.
(Maximum scale deposition in the tubes of stage #08 = 100%)

1612

Fig. 17

A close-up view of the tubes and tube sheet in the outlet of the water box
#07 of desal #27, C4, Phase-II, Al-Jubail, after acid cleaning.

Fig. 18

A close-up view of the tubes and tube sheet in the outlet of the water box
#OS of desal#27, C4, Phase-II, Al-Jubail, after acid cleaning.

1613

1614

40

1615

Fig. 22

[B]
A general view of the tubes and tube sheet in the outlet of the water box
#14 of desal #27, C4, Phase-II, Al-Jubail Plant : A-before acid cleaning
and B-after acid cleaning.

1616

1617

1618