POLYMERS THAT TNHTIBIT THE DEPOS’ITIUN OF CALCtUM SUT..

PHATE

During the distillation of saline waters scale is deposited on the heat transfer surfa@%
of the tt~gorator. This s&e towers the overz.dt heat transfer c*acient of t&z appa-
ratus and reduces the thermal efficiency. SC& deposition can be reduced by adding
certain compounds, which are ~ener&y prtiye&rof;vtcs. to the feed water. Typicaf
additives are starch, Iignin sulphonic acid. and polyphosphates tit concentrations of
f tu tCt parts per million; t&se are satisfactury at temperatures up to about !?WC.
Such additives act as crystal @Roth inhibitors by being absorbed onto the growing
faces of submicroscopic crystals or crystdlities. This gives a stabk colfoid which
can be carried out of the reaction zone by the water.
Tn the panicuiar case of the desalination of sea water by distifiation is is desirable
to operate at temperatures above 90°C; this improves the plant performance and
makes the process more attractive economic&y. However, at these temperatures
the common additit-es art nut suikientfy efi;rctive in preventing scale deposition.
lucre are two main reasons why the norn3aS additives lose their effectiveness with
increasing temperatures. Firstly, some are decomposed either the~~~~y or by hydra-
lysis above 9O”C, and secondly, the composition of the deposited scale changes with
tern~ra~ure and the concentration factor, Lip to 80°C the s&e is ~~dorn~~~nt~~
calcium carbonate, whereas from 80°C ta 9WC the scale chan@s in com~siti~~
and at 90°C and above homes mainly rn~~~~iurn hydroxide. C&ium sufphatc
in various sta_w of hydration starts to coprexzipitate (X,2) with the magnesium
hydroxide at higher temperzxures and as concentration of the sea water pr~eeds
e.g., at tO05C 23nd concentration factors of 3 : i simifarfy at higher temperatures
<e.g., KlWc) with lower concentration factors, c.aIc$um sulphate is depositLd in
 PCXYMERS THAT INHlBfT THE UEi’OSITIO*‘ OF CALCIUM SULPHATE 261
sutlicient quantities to cause serious problems in evaporators. The alkaiinc scales
(calcium carbonate and magnesium hydroxide) can be prevented bq’ the addition
of acid, but this treatment does not remove calcium sulphate. Therefore, an
additive is required which is stable at temperatures of 100°C and above (e.g., IIB’C),
in slightly alkaline and acid solutions, and is effkctive in minimizing cakium sutphate
deposition.
This paper describes the synthesis and characterization of a range of acrylic acid
polymers and copolymers and their evaluation as dispersants for calcium sulphate.

EXPERlMENT.%L

Acrylic acid was purified by distillation under reduced pressure. The purity, esti-
mated b;r titration with potassium hydroxide, was greater than 99.S %, Ethyl acrylntc,
methyl mcthncrytate and styrene were washed free of inhibitor, dried, and distilled
under reduced pressure. Isopropanof was shaken with ferrous sufphate, and distilled
imm~i3tcly before use.
The molecular weights of the polymers were measured on a Spinco Modci E
ultra centrifuge at speeds of about 25,Oi.W rpm. Initial determinations were made
at 20°C in conventional long columns (12 mm) using isopropanol as the solvent
and required sedimentation times of’ about 20 hours. There was no evidence of a
dependence of the results on polymer concentrations in the range of 0.5 to 1.5 per
cent. To reduce the time for subsequent measurements, the rapid short column
(I mm) method of Yphantis ($1 was used. This gave sedimentation tima of about
3 hours at steeds of about 20.000 rpm at 2O’C.
Acid valu~cs of the polymers wxc measured by titration with potassium hydroxide
dissolved in isopmpanoi. Saponification values were meacured by heating the
polymer under rcflun with excess isopropanolic potassium hydroxide solution and
bttck titration with standardized sulphuric acid.

The polymers were prepared by heating isopropanol (200 g) to refiux in 3 one

Iitrc fask equipped with a stirrer, thermometer, and dropping funnel. A solution
of azodiisobutyronitrite (7.8 g) in the monomer. or monomer mixture, (200 $ was
added via the dropping funnel at a uniform rate over 1.3 hours. After approximately
30 minutes under reflux, the reaction became cxothermic and external cooling was
necessary to keep the temperature of the solution at 87’C. The mixture was kept
under reflux for 12 hours. The yield of polymer, measured by the solids content of
the solution, was greater than 95 percent.
Polyacrytic acids of higher molecular weights were prcpartrf by reducing the
initiator concentration in the formula given nboke. The polymers were isolated either
by precipitation into chloroform or ethanol, or by removing the isopropanol and
unchanged monomer at 40°C under reduced pressure, dissolving the polymer in
water, and freeze-drying.
262 D. H. SOLOMOK AND I’. F. ROLFE

T~IC evaluation of polymer.s as scale inhibitors

Tests of polymer additions to prevent the formation of alkaline scale (i.e. CaCO,
or Mg(OH)2 according to temperature) during the evaporation of sea water were
carried out in a pilot scale evaporator, the design of which has been described
previously (4).Polyacrylic acids. which varied in molecular weight from 15,000 to
250,000, were tested at concentrations of around 3 ppm. (The higher molecular
weight polymers were commercially a\ail;tblc materials.) The tests showed that the
effectiveness of these polymers diminished when the molecular weight exceeded
about 30,000 and subsequent work was restricted to molecular weights of about
20.000.
The suppression of alkaline scale formation in sea water evaporators appears to
be due at least partly to the formation of a self-stripping film on the heating surface
(d). This mechanism is different from that incvolved in the suppression of precipi-
tation. which is the only effect occurring with calcium sulphate, but nevertheless the
molecular weight of the polymers used was restricted to about 29,000 in all of this
work.
A laboratory evaporation test was developed for screening purposes. to determine
the effectiveness of polymers in suppressing alkaline scale precipitation. This test
was also found to be useful for evaluating the effect of polymer concentration on the
suppression of calcium sulphate precipit, :n.
Solutions containing 2,000 ppm of calcium sulphate were prepared at 20% by
reacting stoichiometric amounts of sodium sulphate and calcium chloride. The
purifird polymers were re-dissolved in isopropanol and these solutions added to
200 ml aliquots of the calcium sulphate solution and the mixtures boiled for 15
minutes, in $X30ml beakers covered with watch glasses so that 40 g of water was evapo-
rated. (This corresponds to concentration factor of 3.25). The liquid mixture of
colloidal and dissolved calcium sulphate was removed from the precipitated calcium
sulphate by filtration through a glass crucible (porosity 4) and each precipitate re-
turned to the original beaker. The precipitated calcium sulphate was dissolved in
distilled water (100 ml) by heating to WC; triethauolamine (1.0 ml) and 5N KOH
(1 ml) were added, and then, after 3 minutes, 5 drops of Calcon indicator were
introduced. CaIcium was estimated by titration with 0.01 M EDTA to the blue end
point. The Results are in given in Table I.
In these experiments, special care was taken to clean all glassware thoroughly by
washing it with hot 20 pcrccnt alkali, hot 20 pcrccnt nitric acid, and then several
volumes of distilled water.

DISCUSSION

The influence of the molecular wxight of the polyacrylic acids on calcium sulphate
precipitation follows a similar pattern to that shown by other polyelectrolytes in
preventing scale formation fZ’). Above the mo!ecular weight range of 15,00&3@,WO
the polymers become progressively worse for inhibiting scale formation, probably
Desdina~ion, 1 (1966) 26%X6
 POLYMERS THAT INHIBIT THE DEPOSITION OF CALCIUM SULPHATE 263
TABLE I
CHARAC~WUZAT~OS OF ACRYLlC ACID WLYMEWi AND THEIR INFUJEKCE
OS CALCIUM SULPHATE PRECIPITATION

Calcium sulphare drpasircrl (mg)

.\I. WI. Pdper In screenhq resr. (42 mg depas-
RCSitl (cilrra- commuitiun~d). ifed when no wlsnrer used.)
No. cekrifuge) Polwner conc&r~arion tppftrj
-... .- .- -- .__.
--_- ----..-.--__-_~ -._--. --_ 1.0 3.0 5.0 7.0
-_-_-- -----
1. Awlic Acid 18,000 Acrylic acid/isopropyl 6.01 4.4 3.92 3.75
ilcrylate - w3-3
2_ Acrylic acid”’ 20.000 Acvlic acid/isopropyl 10.88 6.3 5.14 -
ncrylate = 6S/32
3. Resin Itb) - Acrylic acid/isopropyl 6.25 3.25 2.38 2.25
acrylatc - SVj41
4. R&n Itb’ - AZ&C acid,Gsoprop>l 6.60 420 3.70 3.25
acrylate = 52/48
s. Resin Ifc’ - Acrylic acid/isopropyl 933 6.21 5.35 5.00
acryhtc = 82:18
6. Resin I(‘) - Acrylic acid - SST/, 7.00 5.24 4.75 4.5
7. R&n 2te’ - Acrylic acid = 9772 - 9.75 7.35 6.5
8. Aczgic acid/ 18.500 Aqlic acid/ethyl 7.50 4.25 3.55 3.25
ethyl acryhte acrylate&opropyl
= 95:s acrylatc = 65j5/30
9. AC&c acid! 19.ooo Acrylic acidlcthll 6.45 3.1 2.77 2.40
ethyl acryhtc acrylate,Gopropyi
- 9OjlO acrylate = 6l:lOj29
10. Acrylic acid Ii,00 Aq!ic acid:ethbl 6.68 4.40 3.64 3.93
ethyl mtate scrylatc’isopropyl
z #/!Q acrylate = 56!20,?4
11. Acrylic xidj 16,000 6.85 5.12 4.55 4.50
erhyl acrylate
-1 70!30
1’. Acryiis acid/ 18.ooO - 8.71 5.20 4.74 4.60
ethyl acryiate
= 5O.G
13. Acrylic acid! 19.ooo Acrylic acid,Qyrcne! 7.02 4.30 3.50 3.10
styrene == 90.‘10 isopropyl acrylate
: 63/10;‘7
14. Ac~lic acid! x?.oal Acrylic acid/methyl 5.75 4.05 3.50 3.25
meth>I mcrha- meth;tcr?.Lte$scpropyl
crylate = 90110 acrylste = 64c1:‘I6.‘26
15. Amlic acid/ 17,aJO Acrylic acidjmcthyl 5.70 4.75 4.10 3.74
methyl tnetha- ntethacry;ate,%opropyl
crylate = 80:20 xrylate = 60:2Oi20
16. Acrylic acid; 17.ooo Acrylic acid!mcthyl 5.70 5.20 4.62 4.40
mcthjl mctha- mcthacrylatejisopropyl
clytte = 70130 acrylatc = G/30/18
(a) Fknzo)-I peroxide w-z. used as the initiator for this polymer.
(b) A solution of Resin I in isopropanol was heated under rellux with benzene and a trace of
sulphuric acid (0 increase further the ester content.
(c) The resin solution uas hydmlyzd to various degrees by controlling the amount of alkali used.
After hydrolysis in ethylene glycol. isopropanol was detected in the mother liquor by gas
chromatography.
(d) The polymer composition was calculated from the acid equivalent and confirmed (Resins 1, 2.
8 and 9) by saponification
_._-____._____ number.
‘_---‘--_-.-_--_--~--_-_~_-- .--;--..----.-------- --.:-
Note: Copolyntcrs prepared from monomer mtxtures whlrh contam ethyl acrylate/acryhe
acid = 60:40, styrenejacrylic acid = 20/80. and methyl methacrylatejacrylic acid = 4W0,
were insoluble in the calcium sulphate solution.
Descdinarion, 1 (1966) 26266
264 D. H. SOLOMON AKD P. P. ROLE

as 3~result of the increased cldsorptior. onto surfam, increased bridging effects, and
decreased solution mobility associated with the higher molecular weightsf5f. In
sea water evaportltion (41, the higher molecular weight polymers r\!so promoted the
formation of 3 different type of scale which tended to remain on the heat transfer
surfaces; polymers wi:h molecular weights 15,000-30,000 resulted in the formation
of a brittle scale which continually stripped away from the surface and exposed a
clean surface with gcod thermal conductivity.
The conditions used to prepare the low molecular Height poiymcrs from scryiic
acid 3130 influenced the effectiveness of the polymer in reducing calcium sulphate
deposition. Polymers prepared from benzoyl peroxide (Resins 2 and 7 - Tabte I).
were not as eflicient as those in which azodiisobutyronitrile was used {Resins 1 and
6). A likely cause of this ir chain branching and/or oxidation by attack of the radicals
derived from benzoyl peroxide on tertiary hydrogens of the polyacrylic acid chains
(G, F ). Azodiisobutyronitrilc was therefore used in all subsequent polymcrimtions.
The use of isopropanol as 3 water-so;ubte chain transfer agenr and solvent resulted
in polymers in which only 66-58~; (Resins 1 and 2) of the calculated acid groups
were avaihble for saIt formation. The saponification vaIues of the polymers, and
the presence of isopropyl alcohol in the saponified solutions shows that the pal} mers
contain isopropyl acq4rtte residues; these are more like!y to form in theearly stages
of the polymerization, since the monomer is a stronger acid than the polymer and
would be a mom powerful esterification catalyst. Saponification of the pol_vmers
gave polyacqlic acids. The %ponifed polymers were used in the original experirncnls
to determine the effect of m&y&r weight on calcium sulphnte deposition.
The isopropyl acrylnte!acrylic acid copolymers formed by polymerization of
acrylic acid in isopropanol were more effective in preventing calcium sulphatc depo-
sition than the homopolymers obtained by saponification of these copolymers
(compare Resins 1 and 6, _ 7 and 7). To study further the influence of isopropyl scqlate
as a component of the polymer, copoiymers with a range of isopropyl acrylate
contents were prepared by partial hydrolysis and essterification of the base polymer
formed in isopropanol. This approach w3s preferred to the rzIternative of making
a number of copolymers from isopropyl acTlate monomer, as the one backbone
polymer was used and al1 the copotymers wouid, therefore. have the same chain
length distribution. The optimum polymer composition (Figure 1) was acrylic acid;
isopropyl acryylate = i;o;‘ltt (approx.). The superiority of this copolymer over thos_=
with higher and Ioucr comonomer contents is probably related to a number of
factors: higher ester cantents eventuafly render the copolymer insoluble in sea water
or calcium sulphate solution, whereas molecules with lower levels do not have such
a desirable hydrophilic~hydrophobic balance and are less etfective 3s surface active
agents. Also. the comonomcr might increase the strength of the acid groups by
reducing interactions between adjacent monomer:uaitslf8); it wouldhlso render the
polymer lmotecule more flexibie than polyacrylic acid (the second aider transition
temperature Tg is reduced from 106’C for polyacrylic acid to a calculated value of
57°C for Resin 3) (9, IO).
Zksalit7ufion.
1 (1966) 260-266
 POLYMER? THAT INHIBIT THE DEPOSITION OF CALCIUM SULPHATE 265

c~=4mcl
DEPOSITEDFROfl
A S0LUlLON WHICH

CONTAINEO S PP?l OF cl1

POLYHER J

1
C I I -I
50 60 70 00 90 Kv3

“; ACRYL:C ACID IN COPOLY?lER

Fig. I. The Rbtionship bctwccn copolmer composition ad calcium sulphatc deposition for
acryhc acid iwpropyl xa-ylate copolymrrs.

Alternative methods for preparing a suitable polymer were also studied in an

attempt to lower the formula andjor manufacturing cost by eliminating the need
for 3 further ezterification of the original.copo!ymer (Resin 1). Ethyl ncrylate, styrene,
and methyl methac~llate, were used as comonomcrs; each of these gave a polymer
which was superior to that given by acqlic acid alone but only ethyl acrylate gave
a copolymer (Resin 9) equivalent to the 60,‘4I acrylic acidjisopropyl acrylate copo-
lymer_ This obscrv3tion is in agreement with the suggestion that the ability oi the
copolymer to inhibit calcium sulphate deposition is related, among other things,
to the chain flexibility 3s shoun by the second order transition temperature, since
of the comonomcrs studied on!y ethyl acrylate gives a polymer with a p$ significantly
iower than polyacryiic acid (polystyrene hrts a Kg of 100°C and polymethyl
mcthacrylate a Tg of IOYC) (II). During the preparation of the copolymers, the
number of isopropyl ester groups introduced into the polymer chain was approxi-
mately proportional to the acrylic acid content; this observation supports the
contention that the acid is acting as an esterification catalyst.
Studies in a pilot plant for the desalination of sea water (4) showed that Resin
9 had cxcrllent scale prevention properties at temperatures in the vicinity of 120°C
where the scaling phase was Mg(OH)r. The present tests indicate the usefulness of
this polymer in preventin g calcium sulphate deposition so that polyacryiic acid
type polymers may find wide applicability in evaporators operating under a variety
of conditions and with a range of feed water compositions.

ACLSOWLEDGEMENTS

The authors wish to thank Mr. L. S. Herbert and Mr. U. J. Stems for the pilot-
scale evaluations, and Dr. B. S. Harrap for assistance with the molecu!ar weight
determinations. The suggestions made by Mr. L. S. Herbert, Mr. F. A. Sweett and
Dr. D. Willis are gratefully acknowledged.
Dedimtion, 1 (1966) 260-266
265 D. If. SOLO~¶ON AND P. F. ROLFE

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Desaiimation. 1 (1966) _260-266