Desalmatron, 71 (1989) 313-324 313

Elsevler Science Publishers B V , Amsterdam - Prmted m The Netherlands

The Problem of Alkaline Scale Formation from a

Study on Arabian Gulf Water

A M SHAMS EL DIN and RIZK A MOHAMMED

Material Testrng Laboratory, Water and Electric@ Department, P 0 Box 219, Abu Dhabl
(U A E ), Telex 22369 WATELCEM
(Received June 7, 1988, m revised form October 20, 1988)

SUMMARY

An experimental procedure is developed to study alkaline scale formation

from Arabian Gulf water. The brine is refluxed at mcreasmg temperatures
under N2 bubblmg for five hours After cooling to room temperature the water
is analyzed for HCO; , CO:- and OH- m solution and for precipitated CaCO,
and Mg(OH), The results indicate the presence of appreciable quantities of
soluble CO:- exceeding the hmits of the solubihty product of CaC03, and re-
veal the inadequacy of thermodynamic approach for studymg scale formation
Solid CaC03 formation in measurable quantities starts above ca. 65’ C, reaches
a maximum at 80°C and declines to a constant value at 90°C. Mg( OH), pre-
cipitation starts around 75 a C and increases steadily with rise m temperature
The OH- ions necessary for the precipitation of Mg(OH)2 originate from
the thermal decomposition of the CO:- moiety of the CaCO, supersaturatmg
the brine.
Experiments with water ennched with additional NaHC03 result m a marked
increase m the deposition of CaCO, In the meantime the supersaturation with
CaCO, and the formation of Mg( OH), decrease to constant values Factors
leading to the formation and stabihzation of CaCO,-supersaturated solutions
are considered to determine the nature and composition of alkaline scales
Keywords, Arabian Gulf water, alkalme scales, supersaturation

INTRODUCTION

One of the mam problems encountered m the operation of multi-stage flash

(MSF) distillers IS that of scale formation inside the condenser tubes. The
scales impair heat transfer and necessitate the apphcation of special additives
either alone or coupled with ball cleanmg. The past two decades have shown
an intensified activity m developmg [l-5] and testing [ 6-91 anti-scale agents
By comparison, very httle work has been devoted to the understandmg of the
mechanism of scale formation It is well agreed upon that the HCO; ion m
311

water IS the key factor m the process of scale formation Two views are found
m the literature regarding the role of thus Ion. Accordmg to Langeher [lo] and
later to Hrlher [ 111, the HCO; ion decomposes thermally at moderate tem-
peratures according to

2HC0, =CO;- +CO, +H,O (1)

This causes the precrprtatron of CaC03 once Its solubrhty hmrts are reached
At still higher temperatures, the CO:- ion hydrolyzes as

CO;- +H,O =20H- +CO, (2)

The resulting OH- ions lead to the precrprtatron of Mg( OH )* Hllher’s scheme
for alkaline scale formation has been accepted by varrous workers [ 12-141 We
have experrmentally confirmed the correctness of reactions ( 1) and (2 ) from
a study on the behavrour of solutrons of NaHCO, and Na2C03 [ 151
Dooly and Glater [ 161, on the other hand, suggested a different sequence of
scalmg. According to them, the HCO; ion breaks down followmg a ummolec-
ular reaction as

HCO, =OH- +CO, (3)

allowmg the primary precrprtatron of Mg (OH ) 2 at low temperatures Parallel

to reaction (3 ) neutrahzatron of HCO; takes place as

OH-+HCO, =CO,2- +H,O (4)

causing the subsequent precipltatron of CaC03 Dooly’s results find support m

the work of Harris et al [ 171 Accordmg to these authors the primary step m
scale formatron IS the decomposition of HCO; mto CO;- and OH- This
produces an nntral deposit of hydromagnesrte [ 3MgC03 Mg (OH )* 3H20] m
preference to CaCO,. The hydromagnesrte then undergoes a solid state chem-
ical change to Mg(OH)? On the other hand, Cooper et al [ 181 proposed the
characterrzatlon of the scale-forming properties of the brine m terms of satu-
ration pH values for the varrous scaling species, m a manner similar to that
suggested by Langeher m hrs classrcal work [lo]
The present study was started wrth two mam ObJectives m mmd. First, to
estabhsh the scale-formmg propertres of Arabian Gulf water which, as far as
we are aware, has not been done before Gulf water &ffers from that of the
open sea In many respects, the most rmportant of which are a high and contm-
uously changing salt content, a hrgh surface temperature and a high biological
actlvrty The results of this part of the study 1s expected to be of interest and
value to all other Gulf States who srmilarly depend on desalmatron for obtam-
mg potable water
The second arm of the study was to shed more light on the mechamsm of
alkaline scale formation from seawater. Apparently the success of any ap-
 315

preach to overcome the problem of scaling must be based on a thorough knowl-

edge and appreciation of all the factors affecting the process

EXPERIMENTAL

Samples of Arabian Gulf water were collected from near-the-sea water In-
takes of the Umm Al Nar Desahnatlon Plant, away from the chlorme mJectlon
point The water was filtered through No 42 Whatman filter paper to remove
any suspended material The first few centlhtres of the filtrate were reJected.
The rest of the water was stored in laboratory glassware or plastic bottles A
preliminary study showed that this &d not affect the Ca2+ and Mg” content
of the water [ 191 Analysis of the Gulf water for relevant scale components
gave the followmg results. HCO; , 115 ppm, CO:- (soluble ), 15 ppm, Ca’+,
543 ppm, M$+, 1780 ppm, and pH 8 15 at 25°C
Previous workers who dealt with the problem of scale formatlon focused
their attention on the determmatlon of the masses [ 11,161 or composltlon
[ 17,201 of the scales In the present mvestlgatlon we focused our attention on
the fate of the HCO; Ion, since this IS the hmltlng factor In the process of
scaling Material balance of this ion was determmed m all tested solutions
The experiments were carried out with 250 ml of Gulf water contamed m 4-
necked flasks These were provided with an efficient condenser, a thermometer
and an inlet for CO,-free N2 The gas was bubbled through the solution at a
rate of 70 ml/mm Purgmg with the gas ensured the removal of CO, and the
shlftmg of the equlhbrla of reactlons (1) and (2) to the right--hand side Heat-
ing of the brme was done m the temperature range 25-lOO’ C, for 300 mm with
an adjustable, electrically operated mantle At the end of the expenment, N,
bubbling was stopped, and the reactlon flask was cooled In Ice water overmght
The whole solution was then filtered through Gelman type GN-6 Metrlcal FlI-
ter Paper The preclpltate, together with the sohds remammg on the wall of
the reaction vessel, on the thermometer stem and on the bubbhng tube were
dissolved In a total volume of 100 ml of HCl solution Samples thereof were
analyzed complexometrlcally for Ca2+ and for total hardness, MgZ+ was estl-
mated by the difference between total hardness (Ca” +Mg’+ ) and Ca2+
hardness [ 211 The filtrate was analyzed for HCO; , CO:- and eventually OH-
by titration against standard 0 01 M HCl using the glass m&cator electrode
The pH value of the solution was also determmed At each test temperature
three experiments were carried out under ldentlcal con&tlons and the results
were averaged Agreement was better than 2 2%
Experiments were slmdarly carried out on Gulf water enrlched with NaHC03
Three sets of such experiments were conducted m which the added HCO, ion
amounted to 50,100 and 150% of the amount naturally found m the water (115
ppm)
Material balance of the HCO; was carried out on the basis that
2HC0, E CO:- = 20H-, and that the calcium of the deposit 1s m the form of
CaC03, and the magnesium m the form of Mg(OH),.

Temperature, ‘C
Fig 1 (A) Varlatlon of the weights of CaC03 ( 1) and Mg (OH) 2 (2 ) and of pH (3 ) in Arabian
Gulf water as fun&on of treatment temperature (B) VaHatlon of HCO; matenal balance m
percent of Arablan Gulf water as function of treatment temperature ( 1) HCOJ , (2 1 CO:-, (3)
CaCO,, (4) Mg(OHh, (5) OH-
 317

RESULTSANDDISCUSSION

The curves of Fig 1A represent the varlatlon of the weight of CaCO, and
Mg ( OH ) 2 formed m Gulf water upon heatmg for 5 h at temperatures between
25 and 1OO’C The curves exhibit a number of mterestmg features which de-
serve to be mentioned. For example, both compounds are detected m small
amounts at temperatures conslderably lower than 1s commonly accepted for
their formation. This findmg substantiates our recent conclusion that Gulf
water contains CaCO, and Mg (OH ) 2 m solution, probably m the form of ion
pairs [ 191. As the temperature IS raised, appreciable preclpltatlon of both scale
compounds starts at ca. 70°C At first the deposltlon of CaCO, predominates
over Mg( OH), (curve 1) In this respect the results of this lnvestlgatlon are
in agreement with those of Hllher [ 111 The formatlon of CaC03 reaches Its
maximum at 8O’C, then declines to attain a constant value between 90 and
100°C On the other hand, preclpltatlon of Mg( OH), steadily Increases with
rise of temperature (curve 2 ) . Above 90’ C Mg (OH ) 2 represents the maJor part
of the formed scale As can be seen, curves 1 and 2 In Fig 1A cross at 87 5”C,
as compared to 79.5-82 ’ C pven by Hllher [ 111 and 90.5’ C reported by Dooly
[ 161 Later we will argue that no large emphasis should be even to this factor,
as it changes with the prevailing condltlons
Curve 3 of Fig 1A represents the variation m the pH value of the brine after
heating for 5 h at &fferent temperatures. As a result of the dsappearance of
CO, the pH rises progressively Interesting 1s the observation that there 1s httle
change m the pH value of brines that were heated between ca 60 and 75°C As
will be shown presently, these solutions contam HCO; and CO;- m approx-
imately 1-l ratio, and would accordingly possess some buffer capacity With
further temperature rise the pH of the water mcreases agam to attain con-
stancy above 85”C, apparently comcldmg with the complete decomposltlon of
HCO, [15].
Previous workers who have stu&ed scale formation from seawater have paid
no attention to the fate of the HCO; ion during scahng The curves of Fig 1B
show the percentage dlstrlbutlon of HCO; amongst the various entitles re-
sulting therefrom. These are: HCO, remammg m solution, CO:- and OH-
found m solution, CO:- precipitated as CaC03 and OH- preclpltated as
Mg(OHJ2 At all temperatures examined the sum of the various species, ex-
pressed as ppm HCO, , agreed to better than 2 2% of the content of this Ion
in the untreated water
Curve 1 m Fig 1B shows that the HCO; content contmuously decreases
with rise m temperature, with a step between 55 and 70°C. The slmllarlty
between this step and that m the pH-temperature curve (curve 3, Fig 1A) 1s
quite apparent and supports the conclusion that both effects are related The
318

most strlkmg feature of the results of Fig. 1B 1s the presence of large quantltles
of CO:- in solution. The amount of soluble CO;- increases steadily between
25 and 60°C Between 60 and 90°C it represents between 40 and 50% of the
total alkahmty of the Gulf water Above 90°C the CO:- drops abruptly and at
100°C it completely disappears Surprlsmgly enough, the CO<- found m so-
lution exceeds by far that determined by the solublhty product, K_, of calcite
(4 7 x lo-’ at 25°C ) [ 221. Thus, for example, m a solution that has been heated
at 60-C and cooled to room temperature, the molar concentrations of Ca”+
and CO:- are 136x lo-* and 7 OX lo-” M, respectively Takrng the corre-
spondmg activity coefficients of both ions as equal to that of standard seawa-
ter, namely 0 28 and 0 2 [ 231, the ion product aCaL+ace;- =5.3x lo-‘, which
IS ca 110times larger than Ksp This shows that the brine can acquire a state
of high supersaturation m respect of CaCO, It 1s to be noted that supersatur-
ation exists side by side with solid CaC03 One IS bound, therefore, to conclude
that the formation of the solid phase IS mhlblted for some reason Slmdarly,
the exact nature of supersaturation 1s not known with certainty, It might exist
either as neutral molecules or as ion pairs [ 241
Appreciable preclpltatlon of CaCO, commences at ca 65”C, curve 3 m Fig
1B This occurs on the expense of the ongmal HCO; and not from the su-
persaturated solution Maximum preclpltatlon occurs at 8O’C and declines
thereafter to a constant value between 90 and 100’ C Preclpltatlon of Mg (OH )2
starts likewise at 65°C and Increases progressively with temperature rise, curve
4 Note also that Mg(OH)2 1s mltlally formed through the disappearance of
HCO; and as this Ion 1s totally consumed, the production of Mg(OH)* IS
accompanied by the sharp decrease m the soluble CO:- content of the solution
Curve 5 of the same figure exhlblts St.111one further pomt of interest, namely
the presence of detectable amounts of OH- m solutions that have been re-
fluxed at 95 and lOO’C, despite the presence of abundance of Mg2+ Ion to
exceed the solublhty hmlt of Mg( OH)* Similar to CaCO,, the preclpltatlon of
Mg( OH )z appears to take place from supersaturated solutions
It must be pomted out that scale formation under the con&tlons of the pres-
ent mvestlgatlon 1s more rigorous than what IS actually takmg place Inside a
normally operating evaporation umt In this latter case, dlstlllatlon IS carried
out under vacuum created by the eJector system of the &stiller Vacuum helps
to shift the HCO, -CO:- and the CO;- -OH- equlhbrla to the right-hand side
to extents depending on number of cells In this study the same IS effected, and
to a much greater extent, through the contmuous bubbling of N, Furthermore,
one should remember that water cycles through the MSF units In a period of
3 5-4 mm Durmg this short period the HCO, content of the water 1s not
reduced to the same degree as IS achieved by refluxmg the same sample of
water, under Nz-bubbling, for 6 h
LIkewise, the analysis of the solutions for the various components of interest
was carried out after coohng to room temperature overnight This allowed am-
 319

ple time for the crystallization of CaCO,. It 1s surprlsmg that under these con-
drtlons one was still confronted with an abundance of CO:- m solution. One
must, therefore, expect supersaturation inside the MSF unit to be still high
Our unpublished results on the analysis of brines taken from the various cells
of an B-stage MSF unit m Umm Al Nar confirm this conclusion.
To gam a clearer insight into the mechamsm of scale formation, experiments
were carried out on Gulf water to which extra HCO; was added The effect of
raising the natural HCO; content of the water ( 115 ppm) by 50,100 and 150%
on material balance was established m the same manner as described above
The curves of Fig. 2 represent the variation of the weights of deposited CaCO,
and Mg (OH )2 with temperature from the HCO; -enriched brines The corre-
sponding curves for the natural water are included for comparison As is clear,
raising the HCO, content of the water favours the precrpitation of CaC03
This occurs m two distinct ways first, the temperature at which deposition
takes place is lowered and secondly, the maximum amounts of the scale in-
creases correspondingly. The effect of the first 50% HCO; increase 1s more
pronounced than that of later additions

TEMPERATURE ‘C

Fig 2 Varlatlon of the welghtaof CaC03 (1,2,3,4) and Mg(OH)P (1’,2’,3’,4’) formed m Arablan
Gulf water as function of treatment temperature and extra HCO; ad&tlons ( 1) No HCO, , (2 )
+58 ppm HCO, , (3) + 115 ppm HCO,, and (4) + 173 ppm HCO;
320

The strlkmg feature of the curves of Fig. 2 1s that the amount of deposlted
Mg( OH), decreases as extra HCO, 1s added to the brine, to reach a virtually
constant value. Note also that m none of the HCO; -enrIched waters do the
curves of Mg (OH), formation cross those of CaC03, as is the case with natural
seawater. One can safely conclude that this crossing 1s only a partlculanty of
the untreated water and, as will be shown later, can also vary with the type of
treatment the water receives
In Fig 3 curves are pven representing the HCO; material balance of Gulf
water containing 100% extra HCO; , after 5 h heating at temperatures between
40 and 100” C. Curves having qualitatively the same features were obtained
when the HCO; content of the water was raised 50 and 150% above Its natural
value
The free HCO; progressively decreases with rise m temperature and Its
dsappearance 1s accompanied by appreciable preclpltatlon of CaCO, Maxl-
mum formation of CaC03 occurs between 85 and 90” C, and represents ca 70,
77 5 and 85% conversion of HCO, In solutions contan-nng 50,100 and 150%
extra HCO,

loo-

Temperature , l
C
Fig 3 Vanatlon of HCO, matenal balance III percent of Arabian Gulf water ennched mth
HCO< as function of treatment temperature (1)HCO,, (2) CO’,-, (3) CaCO,, (4) Mg(OH),
 321

In contrast to the behavlour of natural Gulf water, water that has been en-
riched with HCO; contains relatively little of soluble CO:- The curve rep-
resenting the variation of percentage of this component with time IS practically
the mirror image of that of CaCO, precipitation Both parameters are mter-
related m such a manner that an increase m one is accompanied by a decrease
in the other
The conditions prevailing during the precipitation of Mg(OH)* from
HCO, -enriched waters give a clue to the mechanism of its formation As IS
the case with natural Gulf water, Mg;(OH)* is detected m measurable quan-
tities at low temperatures allowing the existence of HCO; . The thermal de-
composition of this ion produces the CO:- ion which, upon hydrolysis, yields
the OH- ions necessary for precipitation As IS seen from the curves of Figs 1
and 2 and the like, the formed CO:- is present either as precipitated (sohd)
CaCO, or as soluble CaC03 in the form of ion pairs In view of the low reactivity
of sohds, it is unlikely that precipitated CaCO, would be the source of OH-
ions This conclusion is supported by the results of experiments with sohd
CaCO,.
In one such experiment, 1254mg of powdered CaC03 (Merck, pro analysis)
were refluxed with 250 ml distilled water at 100°C for 5 h under N,-bubbling
After coolmg the mixture was analyzed and 1232 mg of CO;- (98 25% ) were
recovered unchanged. For the filtrate 4 mg of Ca’+, 2.41mg of soluble CO;-
and 1 71 mg of OH- were detected. These figures correspond to 10 mg of the
missing solid (080% );the remauung 12 mg (0.96%)were lost in the analysis
The thermal stability of solid CaCO, was further substantiated by the results
of tests in which the mixtures contamted additions of Mg( NOJ)* The analysis
of the recovered solid showed only traces ( < 15% ) of magnesium, part of which
was probably held by adsorption
On the basis of the above findmgs, one must conclude that the OH- ions
necessary for the precipitation of Mg(OH)2 originate from the soluble CaCO,
present in supersaturated solution Support to this conclusion comes from the
way the CO:- content of the water varies with the amount of precipitated
Mg(OH)L
In Table I are listed the results of analysis for soluble CO:- and for deposited
Mg(OH)2 at various temperatures, from natural Gulf water and from water
containing additions of HCO, Examination of the table reveals the following
(a) The amounts of soluble CO;- determined in natural Gulf water are in
general higher than those found in waters contammg additional HCO, This
occurs despite the fact that the heatmg of the Gulf water produces measurable
quantities of solid CaC03 (Fig. 1) which can act as nucleation centres The
formation of the sohd seems to be inhibited for some reason On the other
hand, the addition of extra HCO; to the water produces appreciable preclpi-
tation of CaCO, (Fig 2) This leads not only to a decrease in the extent of
supersaturation with soluble CaCO,, but also to its attannng a constant value
independent of the HCO, content of the brine
TABLE 1 w
iz
pH Values and weights (mg/l) of soluble CO:- and of Mg(OH), In Gulf water contammg mcreasmg addlhons of HCO; , as fun&Ion of treatment
temperature

Temperature Extra HCO;

(“C)
0 ppm 58 ppm 116ppm 174 ppm

co:- Mg(OH), PH co:- WOH), PH co:- MdOHh PH co;- Mg(OH),, PH

25 18 1 01 842 -
40 205 15 847 - 55 0 22 8 55
45 45 0 28 856
50 259 15 860 417 17 841 40 5 32 8 29 25 9 14 8 24
60 42 1 10 8 83 506 24 8 53 21 1 45 822 21 9 36 8 27
70 40 9 47 885 267 43 8 54 172 31 8 26 183 34 8 39
80 37 4 75 905 20 9 57 8 55 16 9 65 832 18 8 41 861
85 39 7 16 9 9 15 212 112 8 69 21 4 78 8 49 19 7 92 8 67
90 403 19 7 9 20 22 8 123 880 17 1 II 8 846 22 1 88 8 78
95 22 9 35 2 9 19 30 7 14 4 9 18 22 6 185 8 69 24 3 16 3 887
100 120 43 1 9 19 27 3 23 4 9 23 38 1 43 7 9 09 28 3 14 7 921
 323

(b ) The weights of Mg (OH ) 2 precipitated from natural Gulf water are also
noticeably larger than those from waters contammg additional HCO, It IS of
interest to note that solutions which sustain a higher CO:- supersaturation
produce a larger crop of Mg( OH )2 The variation in the amount of Mg(OH )*
with the CO:- content of of the solution is quite evident, although no direct
parallehsm between the two parameters is established This, however, is to be
expected in view of the fact that this relation is one of a number of independent
but interconnected equlhbrla prevaihng in solution, for which httle basic In-
formation IS available
(c ) The pH values of the various brines, devoid of and containing mcreasmg
amounts of extra HCO; , increase with rise m temperature, apparently due to
the loss of CO, gas When precipitation occurs, it will reduce the alkahmty and
counter the pH tendency to increase No definite pH value for precipitation
can be pointed out, since this depends on the amount of added HCO, and the
CO:- m supersaturation state
On the basis of the above results, we believe that supersaturation with CaCO,
IS the key factor in the process of alkaline scale formation As shown, an In-
crease in supersaturation decreases the amount of deposited CaC03, but m-
creases that of Mg( 0H)2. On the other hand, when conditions allow excessive
precipitation of CaCO,, supersaturation decreases, and the extent of Mg (OH )2
formation correspondingly reduces These results may explain some of Dooly’s
findmgs which reveal that under certain conditions Mg (OH )* formation pre-
ceeds that of CaCO, [ 161. Similarly, the present results shed much doubt on
the validity of the thermodynamic approach which assumes the preclpltation
of CaCO, and Mg( OH), once their respective solubihties are exceeded. For a
better understanding of the problem of alkaline scale formation from seawater
basic studies addressing the questions of the stability of supersaturated solu-
tions, of the kinetics of CaCO, crystallization, of the thermal stability of the
CO:- moiety of soluble CaCO,, and the effect of additives thereon are needed
Work IS in progress on some of these problems

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324

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