Water Res. Vol. 18, No. 11, pp. 1429-1435, 1984 0043-1354/8453.00+0.

00
Printed in Great Britain. All rights reserved Copyright 1984 Pergamon Press Ltd
THE FATE OF CHLORI NE I N RECI RCULATI NG
COOLI NG TOWERS
F I E L D R E S UL T S
G. HOLZWARTH*, R. G. BALMER and L. SONI
Exxon Research and Engineering Co., Clinton Township, Annandaie, NJ 08801, U.S.A.
(Received March 1984)
Abstract--The chlorine added to recirculating cooling towers is consumed by chlorine demand,
blowdown and flashoff (volatilization) to the air flowing through the tower. In order to understand
the relative and absolute importance of these three sinks, we measured the free available chlorine (FAC)
and the rate of chlorine demand by recirculating and makeup waters of a 1,200,000 gallon transverse
fow, forced draft cooling tower. These data, together with known data on the circulation rate,
blowdown rate, chlorine addition rate and flashoff (volatility) factors, allowed us m solve a differential
equation defining the FAC at all times during and after the shock chlorination cycle. No unknown
parameters were required. We found good agreement between observed and calculated FAC throughout
the cycle. The equation showed that for this particular tower about 10% of the added chlorine was
flashed off, 2~o was lost to blowdown and 88~ was consumed by chlorine demand. Operation at pH 6.5
would greatly increase the fraction lost by fashoff.
Key words--chlorine, water, cooling towers, chlorination, residual chlorine, volatility, chlorine demand,
free available chlorine, flashoff, biowdown
INTRODUCTION
Chl ori ne is added t o t he r eci r cul at i ng cool i ng wat er
of process pl ant s and power pl ant s wor l dwi de t o
cont r ol bi ofoul i ng, yet t here appear s t o be no quan-
t i t at i ve anal ysi s of t he fat e of t hi s chemi cal , 50 t ons
of whi ch ar e added annual l y t o a t ypi cal system. As
not ed in t he pr ecedi ng art i cl e ( Hol zwar t h et al.,
1984), t hree possi bl e si nks have been i dent i f i ed in
earl i er st udi es (Dral ey, 1973, 1977; Nel son, 1977).
(1) The ai r flux t hr ough t he cool i ng t ower st ri ps
vol at i l e const i t uent s f r om t he wat er, a process cal l ed
f l a s h o / f ;
(2) The blowdown st r eam carri es off a por t i on of
t he HOCI and its pr oduct s;
(3) A par t of t he HOCI is conver t ed t o ot her
chemi cal species by r eact i on wi t h cont ami nant s of
t he wat er and t he cool i ng system, a process cal l ed
Chlorine demand.
The amount of chl ori ne l ost in each of t hese processes
per uni t t i me is easily par amet er i zed. Let x be t he
t ot al amount (g) of chl or i ne (act ual l y free avai l abl e
chl ori ne, t er med FAC, whi ch is HOC1 4~OCi --) in t he
system. The concent r at i on o f F AC is t hen x/ V, where
V is t he syst em vol ume (1.). I f OL is t he hot r et ur n
wat er flow r at e ( 1 h - ~ ) , t hen OLx/ V is t he r at e o f flow
(g h - ~) of FAC i nt o t he t op of t he t ower. The amount
r emoved as fl ashoff is FOLx/V where F i s t he unitless
fl ashoff fact or.
*Present address; Physics Department, Wake Forest Uni-
versity, Winston-Salem, NC 27109, U.S.A.
The amount of FAC l ost as bl owdown is 0 f / V,
where 0B is t he flow r at e of bl owdown wat er (1 h-m).
The amount o f FAC l ost t o chl ori ne demand of t he
reci rcul at i ng wat er is D V, where D is t he demand per
uni t t i me and per uni t vol ume ( gl - ~h- 1) ; non-
ci rcul at i ng biofilms, whi ch ar e t he source of i mpai r ed
beat - t r ansf er ( Char ackl i s et al., 1981), are pot ent i al l y
a furt her significant source of chl ori ne demand
( Char ackl i s and Dydek, 1976), but we neglect this
possi bi l i t y for now. I t will t ur n out t hat we do not
need t o i nvoke st at i onar y demand. Fi nal l y, i f we let
i desi gnat e t he chl ori ne addi t i on rat e, expressed in g
( FAC) h-~, t hen t he r at e of change of FAC wi t h t i me
must obey t he di fferent i al equat i on,
dx
dt t Fc~Lx/ V- dps x / V- DV. (1)
The par amet er s i, 0c, 0 s and V ar e known oper -
at i ng par amet er s for a given tower. The precedi ng
paper ( Hol zwar t h eta/., 1984) det ermi nes t he fl ashoff
f act or F for HOCI, OCI - and t he chl or ami nes
NH2CI, NHCI2 and NCI3, whi ch ar e r eact i on pr od-
uct s of chl ori ne with t he ammoni a t hat is oft en
pr esent in wat er. The fat e of chl or ami nes is i mpor t ant
because t hey ar e al so bi oci des, t hough less effective
t han HOCI.
A field t r i p was made in November , 1981 t o a U.S.
refinery t o est abl i sh whet her one can account quan-
t i t at i vel y for t he chl ori ne injected i nt o a cool i ng
t ower, usi ng equat i on (1) and measur ed values for t he
chl ori ne i nput , tlashoff, bl owdown and chl or i ne de-
mand of t he reci rcul at i ng wat er. Dat a were col l ect ed
1429
1430 G. HOLZWAKTH et al.
Table 1. Cooling tower 1 operating parameters
Type of tower Transverse flow, forced draft,
covered distribution deck
Volume 1.2 x 106 gal.
Makeup rate 1000 gal. rain -~
Recirculating rate 60,000gal. rain -I
Number of cycles 6-8
Corrosion inhibitor Phosphate base
pH 8.5-8.6 observed, 8.1-8.3 target
Dispersant None
Biockie Chlorine gas
Biocide schedule Shock, MWF A.M.
Program 3h 15001b 24h -~ rate
1.5h 9001b 24h -~ rate
Continuous 200 lb 24 h- ~ rate
Basin temperature 19.5C
Hot return temperature 35C
before, during and after a typical shock chlorination
cycle of a 1.2 million gallon system here designated
as CT1. Some of the important parameters describing
this tower are given in Table 1. The chlorination
procedure at CTI consisted of shocks around 8 a.m.
on Monday, Wednesday and Friday. The shock
consisted of 3 h of chlorine addition at a rate of
15001b day -m (28,000gh-I), then 1.5h at 9001b
day -] (17,000 g h-I). During "ofF' periods a trickle
flow was maintained to prevent water damage to the
chlorinator.
Our procedure was to measure the chlorine de-
mand D of CT1 and its makeup water. Equation (1)
was then solved numerically for the value of x (or
FAC) during the chlorination cycle, using measured
val ues f or all the parameters in equat i on ( I ) ( no fudge
factors). The compl et ed FAC curve was then c om-
pared to the FAC observed in the fieldfor that tower.
Finally, equation (1) was solved to determine at
various times during a chlorine shock the fraction of
the injected chlorine which actually goes to
HOC1 + OCI-, to flashoff or to demand.
MATERIALS AND METHODS
Chl ori ne for chlorine demand det ermi nat i ons was ob-
t ai ned as a commercial NaOCI sol ut i on (Ci orox bleach),
5.25% by weight. All ot her chemicals were reagent grade.
Free available chl ori ne ( FAC) was measured by am-
peromet ri c t i t rat i on wi t h phenylarseneoxide (ASTM, 1979).
A Fi scher - Por t er 17T 2012A t i t r at or was used. FAC was
measured near pH 7; 1 ml of pH 7 buffer was added t o 20 ml
test sol ut i on i f necessary t o reach pH 7.0 + 0.5.
To det ermi ne t he chl ori ne demand of CTI recirculating
water, a large volume of hot - r ct ar n wat er was removed from
t he t ower j ust before shock began on Monday morni ng. The
chl ori ne demand of this wat er was measured in t he field as
follows. First, 200 ml of t hi s wat er was measured i nt o each
of about 20 brown glass bottles. To each bot t l e was added
2-5 ppm chl ori ne bleach, in staggered amount s. The bot t l es
were t hen capped and allowed t o react at ambi ent tem-
perat ure (15-20(3).
The amount of bl each initially added was selected by
prel i mi nary trial. Generally, a set of f our bot t l es yielding
final FAC of 1- 4ppm was used for each react i on time.
React i on times of !, 2, 8 and 20-24 h were employed. The
dat a for a single react i on t i me generally fell on a st rai ght line
wi t h a correl at i on ccelIicient of 0.99-1.00. Ext rapol at i on of
t he dat a to FAC = 0 yields t he br eakpoi nt chl ori ne demand.
The chl ori ne demand of t he makeup wat er was similarly
determined.
RESULTS
The observed FAC in the hot return of CTl during
and after shock is shown in Fig. 1. The FAC concen-
tration was 0.3 ppm before shock; after shock began
it rose steeply to about 11 ppm in 3.5 h. This peak
FAC exceeded recommended practice of 1-3 ppm
FAC. Upon termination of the shock the FAC
dropped more or less exponentially over the next
36 h. The retention of substantial FAC long after the
termination of shock indicates that CT1 had rather
low values of chlorine demand: the system was quite
clean.
The results o f the chl ori ne demand experiment on
recirculating water are shown in Fig. 2. The FAC
r e ma i n i n g i n t he r e c i r c ul a t i ng wa t e r was a c on-
t i nuous l y de c r e a s i ng f u n c t i o n o f t i me even o v e r a
p e r i o d o f a p p r o x . 1 day. Th i s me a n s t h a t t he r eac-
t i ons o f c hl or i ne d e ma n d wer e sl ow. Mo r e o v e r , t he
s l opes o f t he l i nes f or F AC r e ma i n i n g a f t e r fi xed t i me
wer e n o t 45 a n d wer e n o t c o n s t a n t wi t h t i me. Thi s
me a n t t h a t t he a mo u n t o f F AC c o n s u me d d e p e n d e d
o n t he c o n c e n t r a t i o n o f F AC pr es ent .
Th e c hl or i ne d e ma n d is t he di f f er ence be t we e n t he
F AC p u t i n t o t he t es t b o t t l e a n d t h a t me a s u r e d l at er .
Th i s va r i e d f r o m a b o u t 0. 5 p p m f or l ow l evel s a d d e d
a n d s h o r t t i me s (0. 5 p p m, I h) t o 5 p p m f or h i g h e r
l evel s a n d l onge r t i me s (6 p p m a dde d, 21 h).
, oo
: = , 9 0 0
, F N
~-- 0 ~ ' ~ / / / / / / / / / / / / / / / / / / / ~
2 0 0
i I I I I I
1 0 -
0
u
u. 1
0
0
o I I I I I I
0 1 0 2 0 3 0 4 0 5 0
t ( h )
Fig. 1. Response ( FAC) of CTl t o shock chl ori nat i on. The
upper graph shows t he rat e of chl ori ne addi t i on duri ng and
aft er shock. The lower graph shows measured FAC values
( O) . The line drawn t hr ough t he experimental poi nt s is a
visual "best fit".
The fate of chlorine in cooling towers 1431
3
w
~ 2
tL.
l h
~ 2 1 h
V
I
0 I 2 3 4 5 6
e l 2 a d d e d ( p p m )
Fig. 2. Determination of the chlorine demand of CTI
hot-return water removed just prior to chlorination shock
on 11/09/81. After addition of CIz (bleach), samples were
allowed to react for 1, 2, 8 or 21 h, then assayed for
remaining FAC. Two sets of data are shown for 21 h; the
line labelled "21 h" is a least-squares fit to their average.
5
4 20h
~ sh
3
u .
2
1
I I I
0 1 2 3 4 ..5 6 T 8 9 1 0
e l 2 a d d e d ( p p r n l
Fig. 3. Determination of the chlorine demand of refinery
makeup water. Chlorine (bleach) was added to samples of
the water. After 1, 2, 8 or 20 h the FAC remaining in the
water was determined.
Cor r es pondi ng dat a f or t he chl or i ne demand of t he
makeup wat er ar e given in Fi g. 3. I n this case t he
FAC r emai ni ng di d not decl i ne so shar pl y wi t h t i me
and t he slopes of t he lines were cl oser t o 45 . Thi s
means t hat much of t he demand was qui ckl y satisfied.
A maj or r eason for this is t hat t he makeup wat er was
chl or i nat ed (0.1 mg l - t F AC resi dual ) and t hen
clarified bef or e di st r i but i on of t he wat er for cool i ng
t ower makeup. The chl ori ne demand i ncreased f r om
1.3 ppm for 1. 3ppm added, I h r eact i on time, t o
5 ppm for 9 ppm added, 20h r eact i on time. The
br eakpoi nt chl or i ne demand is t he i nt er cept of t he
lines in Fi gs 2 and 3 wi t h t he absci ssa. Thi s i nt er cept
is pl ot t ed in Fi g. 4 as a f unct i on of t he r eact i on time;
for reci rcul at i ng wat er it i ncreased f r om 0.5 ppm at
1 h t o about 3 ppm at 21 h. Fo r t he makeup wat er t he
br eakpoi nt demand was mor e const ant ; it changed
f r om 1.3 ppm at 1 h t o 3.5 ppm at 20 h. However, t he
concept of a unique, si ngl e-val ued chl ori ne demand
was mi sl eadi ng in bot h cases.
I t is wor t h not i ng t hat chl or i ne demand o f t he
makeup wat er was qui t e appr eci abl e compar ed t o
t hat of t he r eei r cul at i ng wat er. I f one assumed t hat
t he chl ori ne demand of t he makeup was concent r at ed
by a f act or of 8 ( "cycl ed up" ) t hr ough evapor at i on,
t hen makeup al one mor e t han account ed for t he
br eakpoi nt chl ori ne demand of a "cl ean" t ower like
CT1.
An at t empt was made t o measure fl ashoff di rect l y
by compar i ng t he F AC at t he t op and bot t om of t he
t ower (in t he spr ay above t he basin). Measur abl e
differences were found, but t hey di d not var y as one
mi ght expect for flashoff, i.e. t he amount l ost was not
a const ant fract i on of t he FAC at t he t op of t he
t ower. Inst ead, t he amount l ost was 0.8 + 0.2 ppm
dur i ng t he rise and fall of FAC wi t h shock. The
rel at i vel y const ant loss regardl ess of FAC for
t < 10 h suggests t hat chl or i ne demand by t he t ower
fill or dest r uct i on by sunl i ght , r at her t han flashoff,
det er mi ned t he obser ved losses. Fi el d det ect i on of
fl ashoff woul d pr obabl y have been easi er for a t ower
oper at i ng at pH 7 or below, where t he fl ashoff is 10-
fol d great er. I ndeed, t he l abor at or y f l as hof f dat a yi el d
F = 0.011 at pH 8.5, 40C, whi ch appr oxi mat e t he
field condi t i ons. Such a 1.1% loss woul d be ext remel y
difficult t o det ect di rect l y in t he field. The observed
field losses were about t en t i mes great er. I n at -
t empt i ng t o account for t he observed FAC dat a wi t h
equat i on (1), t he l abor at or y val ue of F, 0.011, was
used.
Bl owndown was readi l y account ed for, since t he
makeup r at e (1000gal . mi n - ] ) was known and t he
number of cycles (8) was cal cul abl e from measur ed
values for t he concent r at i ons of Sr, K or Mg in t he
makeup wat er and t he reci rcul at i ng wat er.
The chl ori ne addi t i on r at e was l argel y known. As
shown in Fi g. 1 ( upper frame), t he shock epi sode
consi st ed of 3 h at a r at e of 1500 lb 24 h - i, fol l owed
by 1. 5h at a rat e of 9001b 24h - I . These rat es were
accurat el y det er mi ned from fl ow-met er readi ngs.
Dur i ng t he i nt erval between shocks a t ri ckl e flow was
mai nt ai ned. A rat e of 200 lb 24 h - t was assigned t o
this flow, but this figure is a r ough est i mat e onl y,
since t he fl ow-met er fl oat was at t he bot t om end of
t he fl ow-met er scale dur i ng t ri ckl e flow.
The r emai ni ng unknown quant i t y in equat i on (1)
was t he chl ori ne demand. I nspect i on of Fi g. 1 showed
t hat t he FAC of t he reci rcul at i ng wat er var i ed wi t h
time. Fi gur e 2 showed t hat t he chl ori ne demand
depended st rongl y on t he FAC avai l abl e t o cause t he
react i ons of chl ori ne demand, since t he sl opes of t he
~4
/
~ 2 t " "
g l
m I I i I I i f I I I I I
0 2 4 6 8 t O 1 2 1 4 1 6 1 8 2 0 2 2 2 4
t (h)
Fig. 4. Breakpoint chlorine demand of CTI recirculating
water (1"3 t-1) and makeup water ( C) - - O) for reaction
times of 0-24 h.
1432 G. HOLZWARTH e t al .
straight lines fitted to the data (Fig. 2) were much less
than 45 . As a consequence, the determination of the
incremental chlorine demand was complex.
The data of Fig. 2 showed straight lines for each
reaction time t ' which were represented by equations
FAC = k' (FAC0 - Do) (2)
where FAC is measured free available chlorine at
time t' , FAC0 is the chlorine added and Do is the
breakpoint demand. The chlorine demand D = FAC0
- FAC was given by
D -- Do + kFAC (3)
where k =( l - k' ) / k' . Equation (3) was again a
straight line. The values of Do and the slope k were
obtained experimentally (Fig. 2) for reaction times of
1, 2, 8 and 21 h; values for other times were inter-
polated and values for large FAC were extrapolated.
In this way we constructed a family of curves relating
chlorine demand to FAC and time of reaction t ' for
CT1 water; this family of lines gave the fan-like
display in Fig. 5.
To determine the incremental chlorine demand AD
per hour in the cooling tower at various times t
during the shock cycle, we differentiated equation (3)
with respect to time and retained only terms in dD0
and dk:
AD = ADo + FAC Ak. (4)
To use this approximation, we first marked the value
of FAC at various times t onto the constant time line
in Fig. 5 appropriate to the number of hours t ' that
this value of FAC was available. During the first 3 h
after shock commenced the FAC in the tower rose
rapidly; we treated these three intervals as if the
chlorine were being added to previously untreated
water, using the demand between t ' = 0 and 1 h.
After this time the FAC in the tower was steady or
decreased, which better approximated the way in
which the data of Fig. 2 were obtained. Thus for
t = 4 h we determined AD from relationship (4) using
the values of ADo and FAC Ak appropriate for the
time interval t " = 1-2 h. Similarly, for AD at t = 5 h,
we used ADo and FAC Ak appropriate for the time
l o
6
FAC
( : m)
0
0 5 10 15
CHLORINE DEMAND (ppm)
Fig. 5. Determination of the chlorine demand of CTI cooling water. The fan-like lines are based on
experimental measurements of chlorine demand (Fig. 2). Each solid line corresponds to a particular
reaction time of 1, 2, 3 h etc. The experimental data used to construct the fan-like lines are shown as solid
circles: the same data are displayed in different form in Fig. 2. The dashed lines ( - - - ) are the estimated
incremental chlorine demand AD per hour of the recirculating water when subjected to the chlorination
schedule of the real tower. The time t after shock commencement corresponding to each incremental AD
is shown encircled.
The fate of chlorine in cooling towers 1433
i nt erval t ' = 2- 3 h etc. Thi s sounds compl ex but is
gr aphi cal l y qui t e simple. I n pract i ce t he values of
FAC at var i ous t i mes t aft er shock in t he t ower were
mar ked on t he line of appr opr i at e t ' in Fi g. 5 and t he
hor i zont al di st ance f r om this poi nt t o t he line for
t ' - 1 was measured. These i ncrement s AD are
mar ked ont o Fi g. 5. We r ei t er at e t hat t hi s is onl y an
appr oxi mat e pr ocedur e for i ncl udi ng t he effects of
r eact i on t i me and FAC on t he demand of t he re-
ci rcul at i ng wat er in t he t ower. A mor e r i gor ous
det er mi nat i on woul d requi re addi t i onal mea-
surement s.
A si mi l ar pr ocedur e was used t o est i mat e t he
chl ori ne demand of t he makeup wat er, except t hat in
this case we consi dered t hat fresh makeup wat er was
bei ng cont i nual l y added t o t he system. We consi dered
t he makeup wat er added dur i ng each hour separat el y,
t hen added t he cont r i but i ons f r om al l t he 1 h por t i ons
present at a given time. The chl ori ne demand of t he
wat er - i n- pl ace and t he makeup were t hen correct ed
for bl owdown (a mi nor fact or) and added. The
r esul t ant t ot al chl or i ne demand per hour is pl ot t ed in
Fi g. 6; al so shown on t he figure is t he cont r i but i on of
the makeup wat er. The est i mat ed t ot al chl ori ne de-
mand rat e had a peak of 4. Tppm h -~ at 3h; this
exceeded by a f act or of 10 or so t he val ue one woul d
det er mi ne from t he br eakpoi nt chl ori ne demand dat a
(Fi g. 4). The makeup cont r i but i on was smal l except
at l ong times, l argel y because t he makeup wat er
showed much weaker dependence of demand on FAC
t han di d t he wat er - i n- pl ace (cf. Fi gs 2 and 3) and al so
because t he makeup r at e was smal l compar ed t o t he
system vol ume.
Once t he chl or i ne demand was est i mat ed, t he free
avai l abl e chl ori ne was comput ed, usi ng equat i on (1).
"/I
o
o o o o o o o o o o o o ? o o o o ~ o o o o ?
g t I
0 5 10 15 2 0 2 5
t ( h )
Fig. 6, The estimated chlorine demand per hour for CTI
recirculating water during and after shock chlorination. The
open circles ( O) ~ve the total demand of water-in-place and
makeup water, both corrected f or bl owdown. These data are
used to compute Fig. 7. The contri buti on of makeup water
alone is shown by the squares (l'q). The solid line ( ) is
an adjusted curve of total demand per hour; this curve is
used to obtain a better fit to the observed FAC data
(Fig. 8).
Equat i on (1) was si mpl i fi ed t o
dx
- - = - - ax + b ( t) - c( t) ( 5 )
d t
where
x is t he t ot al amount of FAC in t he system (g)
a = C~bl o, / V + F d p L / V (h - l )
b = i (g h -~)
c = D V (g h- l ) .
The sol ut i on t o this equat i on is
= x0 exp( - a t ) + exp( at ) f o
X
e x p ( - - a t ' ) ( b ( t ' ) - c ( t ' ) ) d t ' . (6)
Thi s was sol ved numeri cal l y wi t h a smal l di gi t al
comput er ; we used a Hewl et t - Packar d 9825A. An
i nt egr at i on i nt erval of 15 mi n was utilized. The i nt e-
gr at i on yi el ded a val ue of FAC at var i ous t i me, t,
based solely on t he measured chl ori ne i nput , l abor a-
t or y fl ashoff dat a [ F=0 . 0 1 1 , ph8. 5, 40C
( Hol zwar t h e t a l . , 1984)] and chl ori ne demand of t he
test wat er and makeup wat er (Fi g. 6). Fi gur e 7 shows
comput ed and measur ed FAC values for CTI . The
comput at i on fitted t he observed dat a r emar kabl y well
dur i ng t he rise in FAC, at t he peak, and for about 4 h
aft er t he peak, consi deri ng t hat n o a d j u s t a b l e p a r a m -
e t e r s h a v e b e e n i n t r o d u c e d . At l onger times, t he
cal cul at ed FAC devi at ed, first by di ppi ng bel ow t he
exper i ment al curve for 7 < t < 15 and t hen by cur -
vi ng upwar d unreal i st i cal l y.
The di p is most pr obabl y a consequence of t oo
l arge an est i mat ed chl ori ne demand at shor t times;
t he upwar d cur vat ur e at l ong t i mes means t hat t he
chl ori ne demand for l ong times di d not exceed t he
"t r i ckl e" i nput of chl ori ne. Smal l adj ust ment s in t he
chl ori ne demand, as shown by t he sol i d line in Fi g.
6, were sufficient t o br i ng experi ment and cal cul at i on
1 2
o
o
Obser ved
8
Ca I cu l at ed
\ /
u 6
2 o
o
* %
I I I I I I
0 5 10 15 2 0 2 5 3 0
t ( h )
Fig. 7. Calculated ( ) and observed (O) FAG during and
after shock chlorination of CTI. The chlorine demand data
used in solving equation (1) are those shown by O- - O in
Fig. 6. The observed FAC values (O) are identical to those
displayed in Fig. 1.
1434 G. HOLZWARTH e t al.
1 2
l o
)
w
o,
o
2
o I
0 10 20 3 0 40 50
t ( h]
Fig. 8. Calculated ( ) and observed (O) FAC during
and after shock chlorination of CT1. The chlorine demand
data used to solve equation (1) are shown as a solid line in
Fig. 6.
into excellent agreement at longer times, as shown in
Fig. 8. How significant was the extra chlorine demand
added at longer times t o get a better fit t o the
observed FAC curve? Over 25 h, the unadjusted
chlorine demand (Figs 6 and 7) integrated t o 32 ppm.
Over the same time period, the adjusted chlorine
demand (Fig. 6) integrated t o 35 ppm. The difference
was onl y 3 ppm, or 10%.
The difference mi ght have originated in 5 factors:
inhibitor addition, destruction of chlorine by sun-
light, inaccurate chlorine addition rate, incorrect
temperature of demand measurement and non-
circulating demand. Labor at or y measurement
showed t hat the cont ri but i on of inhibitor t o the
chlorine demand was less t han 0.1 ppm FAC in 24 h:
the first fact or was negligible. Dest ruct i on of FAC by
sunlight was not support ed by obvi ous day- ni ght
effects on the FAC in the system. Moreover, we did
not expect sunlight t o have much effect on CT1
because this t ower had an enclosed distribution deck
designed to keep sunlight out. The third possibility
was t hat the trickle chl ori nat i on rate, measured as
200 lb day -1, was in actuality onl y 100 lb day- I ; the
measurement was performed at the very end of the
flowmeter scale. The fourt h possibility was t hat the
test t emperat ure for chlorine demand determinations
should have been closer t o the hot return temperature
(35C) rat her t han 15-20C. The fifth possibility,
non-circulating chlorine demand by deposits in the
pipes, tower fill and t ower basin, was support ed by
our measurements of a difference in FAC at the t op
and bot t om of the tower; such non-circulating de-
mand is the maj or t arget of the chlorination pro-
cedure (Characklis and Dydek, 1976; Characklis et
al., 1981). I t was not possible with the present dat a
to distingish the role of the last three factors. Now,
we had expected the non-circulating chlorine demand
t o make a maj or cont ri but i on t o the total demand.
Instead, we f ound at most 10% of the chlorine
demand originated in this factor; the chlorine de-
mand of the circulating water dominated.
Tabl e 2. The fract i onal fate of chl ori ne at vari ous t i mes aft er the
begi nni ng of shock chl or i nat i on
Fr act i onal fate of chl ori ne
Ti me
(h) FAC Fl ashoff Bl owdown Demand
4 0.56 0.05 0.01 0.39
5 0.49 0.06 0.01 0.44
10 0.22 0. l 0 0.02 0.66
20 0.08 0.12 0.02 0.78
30 0.03 0.11 0.02 0.84
40 0.00 0.10 0.02 0.88
It is of interest t o examine what fractions of the
injected chlorine were flashed off, blown down and
consumed as chlorine demand, accordi ng t o equat i on
(1). The results at 4, 5, 10, 20, 30 and 40 h, after shock
began, for the comput at i on shown in Fig. 8, are given
in Table 2. The comput at i on showed t hat onl y about
10% of the chlorine was flashed off, 2% went t o
bl owdown, while the bulk of the chlorine went t o
FAC and demand. At the chlorination peak, 4 h, 56%
of the chlorine was doi ng its j ob as FAC; onl y 5% had
been flashed off, but 39% had been consumed t o
satisfy chlorine demand.
DI SCUSSI ON
I t is surprising t hat the fate of chlorine in cooling
towers is not t horoughl y document ed. Probabl y this
is simply because chlorine is cheap; the chlorine used
in CT1 costs about $20,000 yr - L Some experiments
on the rise and fall of FAC and total available
chlorine duri ng and after shock chlorination were
carried out by Dral ey (1973, 1977). He studied the
water of an induced draft cooling t ower at a nuclear
power plant. Dral ey argued t hat the observed long-
term decay of combi ned chlorine required a flashoff
fact or of 0.4-0.5. He suggested t hat dichloramine was
the combi ned chlorine compound t hat was flashing.
The tower he studied had a hot -ret urn t emperat ure of
38C. Our dat a (Hol zwart h et al., 1984) show t hat
F - - 1.00 for di chl oroami ne at this temperature, as-
suming a liquid flow/air flow weight ratio of 1.3 in the
tower. Perhaps other, less volatile compounds made
up part of the measured total chlorine in Dral ey' s
tower.
It is of interest whether flashoff would play a maj or
role as a chlorine sink if CTI were at pH 6.5 rat her
t han 8.5 and the same amount s of chlorine were
added during shock. The question was easily
answered by runni ng the comput er pr ogr am solving
equat i on (1) with F = 0 . 1 0 rather t han 0.011 and
correcting the demand dat a (Fig. 6) for the lower
FAC values. At the peak of shock, flashoff would
consume 30-40% of the chlorine, rather t han the
5-6% loss at pH 8.5 assuming t hat chlorine demand
is independent of pH. We have not examined this
systematically, al t hough we did find it t o be roughl y
true for this cool i ng tower.
Can we answer the questions whether shock or
cont i nuous chl ori nat i on is preferable, once equat i on
(1) can be solved? Unfort unat el y, this question can-
The fate of chlorine in cooling towers 1435
not be addr essed unt i l t he r el at i onshi p bet ween FAC,
t i me and bact er i al ki l l and bi of oul i ng cont r ol are
i ncl uded in t he anal ysi s. However, t he present st udy
suggests t hat t he cont r ol of chl ori ne demand is mor e
i mpor t ant t han t he t ype of chl or i nat i on schedule
used. I f much of t he demand is suspended mat t er ,
r at her t han di ssol ved, a st r ong ar gument coul d be
made for an i n-l i ne or si de- st r eam filter t o remove
part i cul at es.
The maj or concl usi ons of this r epor t ar e as follows:
(1) Fl ashof f consumed about 10% of t he chl ori ne
added t o a t ypi cal cool i ng t ower oper at i ng at pH 8.5.
(2) The fl ashoff of free avai l abl e chl ori ne ( FAC)
woul d be much fast er at pH 6 t han at pH 8.5; 30-40%
of t he FAC may be st r i pped at pH 6.
(3) Chl or i ne demand was a st r ong funct i on of
cont act t i me and cont act level ( FAC concent rat i on).
The use of hi gh FAC concent r at i ons ( > 1 ppm)
in cool i ng t owers i ncreased t he chl ori ne demand.
(4) Wi t h t he fl ashoff dat a in our previ ous paper
( Hol zwar t h et al., 1984) pl us mesurement s of t he
chl ori ne demand of t he reci rcul at i ng and makeup
wat ers of a given cool i ng t ower, t he rise and fall of
FAC in t he cool i ng t ower were comput ed di rect l y
wi t h a smal l di gi t al comput er .
Acknowledgements--We are grateful to John DeGroff, Na-
talie Holzwarth, Allen Laskin, Lars Nalund, Max McCoy,
Jim Mossberg and Ed Baker for helpful discussions, to Judy
Krieg for an inspired literature search, to the Refinery
operating crew for patient help during our field trip and to
Linda Sigafoos for her patience and skill in preparing the
manuscript.
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