Methods for Removing Detergents from Waste
C. A. BRUI'~ER, U.S. Department of Heakh, Education and XWelfare; Public Health Service;
Division of Water Supply and Pollution Control, Robert A. Taft Sanitary Engineering Center, Cincinnati, Ohio
Abstract
A n u m b e r o f processes have been investigated
or are b e i n g investigated f o r r e m o v a l o f alkyl-
benzene sulfonate (ABS) from waste waters.
These can be divided into processes applicable
to launderette wastes and processes applicable
to municipal waste w a t e r although there is over-
lap. Launderette waste t r e a t i n g methods include,
floeeulation, flotation, adsorption on activated
earbe.n or ion exehange mateNMs and filtra-
tion. In munieipal waste w a t e r t r e a t m e n t any
ABS removal method must be ve~T inexpensive.
Two methods t h a t have been used to remove most
of the residual ABS a f t e r conventional sewage
t r e a t m e n t are foaming and a d d i n g of cationic de-
tergents. Both methods are capable o f renmving
ABS down to levels of 0.5 p p m or less. A n u m b e r
of o t h e r t r e a t m e n t methods t h a t will remove or-
ganics, including ABS, from municipal wastes
are being studied. Their costs are, in general, too
high to make t h e m applicable f o r ABS removM
alone. Processes u n d e r s t u d y i n c l u d e adsorptior~,
chemical oxidation, ion exchange, electrochemical
degradation and e v e n distillation.
Introduction
created a n u m b e r o f w a t e r q u a l i t y problems. The
nmst obvious, as f a r as the public is concerned, is the
aesthetic p r o b l e m of f o a m formation on ~a~terways
and in ground w a t e r as a result o f waste-water pollu-
tion. IZoamhlg is also a p r o b l e m at, m a n y munieipal
waste-water t r e a t m e n t planls.
Until r a t h e r recently there was little positive evi-
dence t h a t more readily degrad~d)le detergmlt m a t e -
rials would be devdoped. The c h i e f solution to ~ke
p r o b l e m of detergent foaming appeared to be t r e a t -
ment processes t h a t remove detergents from waste
waters. A n u m b e r o f process development studies were
undertaken in this a r e a . It now appears, however, that
" s o f t e r " o r more degradable detergents will be avail.
able and will be widely used in this country. While
lhis will no doubt greatly alleviate the detergent p o l l u -
tion problem, most probably it will not solve it com-
pletely. Detergent r e m o v a l methods may very like]y
still be necessary a t some locations.
Detergent Pollution in Waste Water
Two waste w a t e r sourees t h a t have been suflieiently
important contributors to detergent pollution f a r re-
m o v a l studies to have been u n d e r t a k e n are municipal
waste t r e a t m e n t plants and launderettes. On a nation-
wide basis, the volmne o f launderette waste is i n s i g -
nificant in comparison to the volmne of municipal
waste, b u t there are locations such as Suffolk County,
N.Y., where launderette waste causes intensive l o c a l
pollution problems by mixing with the g r o u n d w a t e r
used as the source o f drinking water.
The ABS cohen (as determined by the methylene
blue analysis) of municipal w a s t e w a t e r is o f t e n ca.
5 rag/liter a n d is seldom raueh above 10 mg/Iiter.
813
L a u n d e r e t t e wastes, on the o%er h a n d , oftqn have
ABS eonen o f 50 rag/liter and several hundred r a g /
liter is not uncommon. [n addition, launderette wastes
c o n t a i n eonvn o f phosphate a n d of suspended m a t t e r
t h a t are as high as several h u n d r e d rag/liter. Because
o f differences in the over-all composition and the vol-
un'm o f the two waters, different t r e a t m e n t methods
have been suggested f o r each.
I n d u s t r i a l wastes art another source o f detergent
pollution, especially nonionics. These wastes are ex-
tremely variable in n a t u r e . In m a n y eases their be-
h a v i o r with respeet to detergent r e m o v a l is similar
to that of nnmicipal waste water.
Methods for Treating Launderette Wastes
A n u m b e r of p r i v a t e companies have designed l a u n -
derette waste-treatment equipment (1). Beem~se it is
desirable f o r this e q u i p m e n t to remove phosphate and
suspended m a t t e r in a d d i t i o n to ABS, a n u m b e r o f
operations usually are r e q u i r e d . These i n e l u d e floeo
eulation, adsorption o r absorption, ion exchange, fil-
t r a t i o n and flotation. A n excellent discussion of a
n u m b e r o f systems is g i v e n by Flym~ a n d Andres (2).
The most efficient o f these f o r ABS r e m o v a l is eap~)le
o f r e d u e i n g the ABS eonmt to less t i t a n 3 rag/liter.
T h e t o t a l cost (d t r e a t m e n t i n c l u d i n g amortization
o f equipmm~t, o p e r a t i n g costs a n d w a s t e eone o r resi-
due disposal is likely to be somewhat more than $1.00/
1000 gal. In some cases, chemical eos/~ alone are
more t h a n $1.00/1000 gal. It might a p p e a r t h a t t r e a t -
i n e n t f o r only ABS renmvaI would be considerably
ehe~tper. This is not necessarily t r u e , however, because
processes would still be r e q u i r e d t h a t would Mlow the
waste residue containing the removed ABS to be
coned to a small volume. Small-scale processes tl~at
aeeomplish this are costly.
Methods of Treating Municipal Waste Water
for ABS Removal
Since l/he amt of .ABS in eompletely t r e a t e d muniei-
p a l waste w a t e r is o f t e n less than 1% o f the t o t d con-
taminants a n d less t h a n 10% o f the organic contami-
n a n t s , any r e m o v a l m e t h o d f o r ABS None must b e
very inexpensive in contrast to launderette waste
t r e a t m e n t . Costs o f a few t e n t s o r less/thousand gM
are all t h a t might be tolerated. Only a few methods
a t present can be eonsidered. These i n c l u d e a d d i t i o n
of eationie detergents, biodegradation o f the ABS on
soils and foaming.
The use o f cationic detergents f o r removM o f ABS
has been studied by SamNes (3). MateriNs sneh as
a n alkyl d i m e t h y l benzyl ammonium chloride r e a c t
with ABS to produce a precipitate. Removal of the
p r e c i p i t a t e by ~.um floeeulation followed by filtration
o r even b y filtration a l o n e results in ABS cohen of ca.
1 rag/liter o r less. F o r the p a r t i c u l a r secondary efflu-
e n t studied it was f o u n d t h a L in a d d i t i o n to ABS, one-
half or n:mre of the t o t a l organic pollution as measured
by chemicalo x y g e n d e m a n d ( C O D ) also was removed.
B a s e d upon present prices, the cost o f cationic de-
t e r g e n t f o r this process is ca. $0.006/1000 g d f o r each
mg of ABS/liter of waste water. F o r nmst municipal
wastes, this represents a rain chemical cost o f ea.
814 THE ,JouRNAL OF TIlE ASIERI(~AN OIl~ ( lIE.lISTS
TABLE I
Foaming of Secondary Effluent
~ olume of air/n'~ass of ABS ~,BS e(men of product
in feed (liter/rag) uater (mg/|iter)
1.0 ~)57
20 0.:~6
3.0 0.~9
$0.03:1000 gal. The t o t a l operating cost o f the t r e a t .
mere method a p p a r e n t l y would be barely within the
r a n g e o f acceptability. T h e I)riee o f the cationic de-
t e r g e n t might decrease significantly, however, if the
material were widely used. The process would then be
nmre attractive.
T h e use o f soils t(~ remove organics from waste
w a t e r has been known and practiced f o r some time.
Robeek e t al, (4), recently made a detailed lysimeter
study of the ability o f s a n d y soils to remove ABS and
o t h e r organic eontaminants from domestic waste water.
By a p p l y i n g tile w a t e r intermittently so as to main-
lain aerobic conditions in the soil, they f o u n d that
ABS could be biologically degraded to a 0.5 rag/liter
level even when the ABS eonen h a d been artifieally
increased to levels h i g h e r than usually f o u n d in waste
effluents. Radioactive t r a c e r tests with Sas tagged
ABS indicated that much o f the ABS degraded f a r
enough to produce s u l f a t e ion. Most of the t o t a l
organic material fed was actually removed. Alth(mgh
this t r e a t m e n t method is technically promising, it has
the disadvantage of requiring large infiltration area~.
Based on the lysimeter s u r f a c e area used, the r a t e of
applieation was, a t most, 3.5 g p d / f t ~. A t this rate
ca. 60(1 level acres of suitable soil might be r e q u i r e d
f o r the waste w a t e r of a city of 500,000 population.
The cost o f ABS r e m o v a l by spreading the waste
w a t e r on soil would certainly depend upon the cost
of l a n d . In addition, there would be cost f o r bed p r e p -
a r a t i o n and maintenance o f the s p r e a d i n g and poauibly
any undcrdrain system required. T h e t o t a l cost is
di~cult to estimate a t present, but might be reason~
able in some areas,
Foaming o f m u n M p a l waste w a t e r f o r ABS r e .
moval has been investigated and is presently being
used in several t r e a t m e n t p l a n t s as a supplementary
proeess a f t e r secondary o r biological treatment. The
s m ess of the method results from adsorption o f sur-
factants to the water-air interface. When bubbles o f
air are blown through the w a t e r a large amt of inter-
face is produced, w h i c h is conveniently removed as
foam. Table I shows average results from continuous
laboratory runs in which secondary effluent samples
from <me t r e a t m e n t p l a n t were used (5). P r o d u c t
w a t e r with the ABS conch a l m o s t as low has been
obtained with pilot scale equipment a t a different
waste t r e a t m e n t p l a n t . Organics in a d d i t i o n to ABS
are removed from both l)rimary and secondary effluent.
U n d e r p r o p e r conditions, 40% of the amt in the feed
can be removed.
T o t a l operating costs are estimated to be $0.02/1000
gal, o r 1c.~% f o r p l a n t s lreatiug as little as 1 mgd. The
disposal o f ABS-rich eollapsed f o a m could cause added
expense. It may, however, be possible to recycle this
coned solution back through the biological t r e a t m e n t
step to give a longer residence time f o r the resistant
types o f ABS molecules. This foam recycle scheme
has been found successful on a laboratory scale (6).
Other Processes Capable of Removing ABS
from Municipal Waste
O t h e r processes f o r more complete removal of con-
taminants from waste w a t e r than is possible with the
SOCIETY VoL. 41
present conventional l reatment methods a r e u n d e r
study by tim Advanced Wash, T r e a t m e n t Research
Program of the tLS. Public Ilealth Service. Although
most of these processe~ will remov(! A B e , the gross re-
moval of organics, inorganies or both, is lheir primary
function. Those that remove ABS include adsorpliou
on activated carbon, chemical oxidation, distillation,
reverse osmosis and solvent extractiou with seeondary
amines. These t r e a t m e n t nmthods are, in general, too
expensive to be considered f o r ABS removal almle.
Adsorptinu, which is very promising f o r r e m o v a l of
many organics, can be carried out with g r a n n l a r or
powdered carbon. Ca. 0.75 Ib of g r a n u l a r carbon/1000
gal is required. The exhausted carbon must be reac-
tivated for eeonomical opcration. The total eost f o r
t r e a t m e n t of secondary effluent to produce w a t e r hav-
ing a maximum ABS conch o f 0.5 rag/liter might be
less than $0.10/1000 gal f o r plants t r e a t i n g 10 mgd.
Chemical oxidation with hydrogen peroxide o r ozone
can also be employed f o r removal o f organic materials.
In the process, ABS appears to be oxidized p r e f e r e n .
tially; cohen of less than 0.5 rag/liter are achieved.
The cost of the process a p p e a r s to be g r e a t e r than the
cost of carbon adsorption, however.
Distillation removes nearly all the contaminants
from waste water. With care to prevent f o a m c a r r y .
over, ABS can bc reduced to negligible levels at (,osts
probably comparable with those f o r sea w a t e r con-
version.
Reverse (~smosis is a relatively new t r e a t m e n t method
that effects removals eomparable to those o f distilla-
tion. Ill the process, w a t e r is freed from impurities
by being f o r c e d through a special type of membrane
t a m e r high pressure. F o r waste-water t r e a t m e n t , pre-
liminary results suggest t h a t operating costs may be
competitive with those for distillation.
Like distillation and reverse osmosis, the solvcm
extraction process referred to here is capable o f sepa-
r a t i n g both organic and inorganic materials from
waste water. W a t e r molecules f o n n a loose complex
with certain amines. By raising the temp of the (.om-
plex, the w a t e r can be sel)araled and recovered. I:'urity
of the p r o d u c t w a t e r is not as high an in distillation.
ABS removal down to ca. 1 rag/liter is all that is
usually obtained. O p e r a t i n g costs can not yet be p r e .
dieted with any degree o f accuracy.
Future of Advanced Waste Treatment Processes
After Use of Degradable Detergents
Becomes Widespread
Municipal waste w a t e r that has been given conven-
tional prilaary and secondary t r e a t m e n t contains an
average of ca. 3()0 rag/liter mor~ dissolved organic and
inorganic material than does tile w a t e r supplied to
the c i t y . The waste w a t e r frma a lmmderette contains,
besides ABS and certain u t h e r materials, large amt
of various forms of s o d i u m phosphate. ]n addition,
both waste waters contain suspended matter. Obvi-
ously this t o t a l amount o f material added d u r i n g use,
not just the. ABS, wmfld have to be removed if man-
made pollution were to be eliminated. In a closed
system with continued reuse of the w a t e r f o r an in-
definite period, complete r e m o v a l of the contaminants
added d u r i n g each use would be necessary. Even
with the degree of reuse presently practiced, removal
of a t least a fraction of the added contaminants is
desirable. Any process, therefore, t h a t removes a sig-
nificant amt of organic o r inorganic material could
be of v a l u e now and shouhl be of g r e a t e r v a l u e in the
future when increased reuse wilI be necessary.
DECE.~BE~, 1964 B R U N N E R : METItODS FOR REMOVING D E T E R G E N T S
All the processes discussed here remove significant
amt of impurities o t h e r than ABS. They might, there-
f o r e , be used whether or not ABS were present. Most
of the processes would, in f a c t , operate more efficiently
if ABS were not present. Foaming is a possiMe excep-
tion. The synergistic action between small amt of ABS
and o t h e r organic materials in waste w a t e r is, in many
instances, very effective in producing stable foam.
I I o w strong the foaming tendency of waste w a t e r
might be in 1he absence o f the presently used ABS is
not well known. A reduction in foamability would
eertahdy be expected. This might be overeoro~ partly
by ehanges in the design o f foaming equipment. It
might also be possible t o add small amt of foaming
agents to produce a more stable foam.
Products and environmental patterns change with
time. W e cannot expect to tailor waste t r e a t m e n t f o r
each new p r o b l e m compound l h a t comes along. W a t e r
reuse considerations will demand that only a very
Performance of Straight-Chain
(LAS) in
W. A. S W E E N E Y and A. (2. O L S O N ,1 California Research Corporation, Richmond, California
Abstract
Tile foamability (dishwashing and washing ma.
t h i n e ) and detergmiey of L A S in heavy-duty de-
tergents is directly emnpared with polypropylene
ABS ( P P A B S ) a t various reel wt, Cohen, w a t e r
hardnesses and t e m p . In every case a peak in
performance is obtained in the Cn to C17 side
chain r a n g e . The peak is shifted to l o w e r reel wt
as w a t e r hardness is hmreased, especially a t low
detergent cones. L A g opt performanee is gener-
ally e q u a l to P P A B S , except in dishwashing foam
in soft water. The I~AS peaks, however, are
shifted to ca. one carbon l o w e r m(fl wt than the
PPABS. Therefore, best eve>all performaIme is
obtained f o r L A S whose average reel wt cor-
responds to a 3.2.5 carbon side chain, whereas
P P A B S is best with a n average 13.5 carbon side
chain.
Dishwashing foamability is markedly different
f o r the different isomers contained in LAS. When
the phenyl g r o u p it attached to the middle o f the
alkyl c h a i n , surprisingly high results are ob-
tained. This dishwashing difference is g r e a t
enough to be noticeable when the i s o m e r d i s t r i b u -
tion ehanges in whole products made u s i n g differ-
ent alkylation catalysts. Detergency a n d washing
machine f o a m are not affected enough to see dif~
ferences between whole alkylates.
L A S solubility is g r e a t e r than P P A B S a n d is
influenced by i s o m e r distribution.
Introduction
IIERE ItAVE BEEN* m a n y reports on various aspects
T of the
propy/ene
performance o f detergents containing t e t r a -
ABS since it has been the roost Mdely used
synthetic anionic s u r f a c t a n t f o r m a n y years. In the
last few y e a r s the performance of some o f the com-
mercial polypropylcne alkylates has been improved b y
Present address: W, Reg Res. Lab., USDA, Albany. Calif.
815
h)w level o f many eontamilmnts be allowed to remain
in water. W e need a n arseHM of highly efficient t r e a t -
meat methods to cope wilh all types of contaminants.
There is no question t h a t o u r technology can develop
such methods. W e nmst provide the t r e a t m e n t m e a n s
if the clean w a t e r needed and demanded by the public
is 1o be available.
REFERENC~ES
1. Anon., Chem. Eng. News 40, 48 (Oct. 29, 1962).
2. Ylynn, J. M., and B. Andres, Water Pollution Control Federation,
5ournM SS. 783 (1963).
3. ramifies. W. R., I b i d . a4, 1070 (1962).
4. Robeek, G, G,, a. M. Cohen, W. T. Sugars and R. In. W~mdward.
Ibid. gS, 1225 (1963).
5. Public Health Service Publication No, 999-~.VP~5, "0ontaminant
Removal from Sewage P l a n t Efliuents by Foaming," A~WTR.5 (1963).
6, Sharmin, S. H., W. R~ Seixuett, D. Kyriacou and W. A. Swesney.
"Foam Recycle: A ~et~hod for Improved Removal of Detergents from
Sewage," pre~ented at the 147th ACS ~eeting, Phi]adelphla, Pa. April,
I964.
[Received June 17, ]964~Aecepted October 22, 1964]
raising the average moI wt to equal about a 13.5
carbon side chain (1).
There ha~'e m)t been m a n y r e p o r t s on performance
o f LAS. Gray et al. (2,3) p r e p a r e d several pure
compounds arid obtained w e t t i n g time, detergency
and f o a m d a t a . B a m a g a r t n e r (4) p r e p a r e d and tested
a n u m b e r o f dodeeylbenzene isomers. Koelbet and
coworkers (5) reviewed the literature on t h e effect o f
s t r u c t u r e on properties of a n u m b e r o f straight-chain
and branched-chain alkylbenzcne sulfonates a n d o t h e r
anionies. Most of the d a t a are on physical properties,
sueh as s u r f a c e tension and eritieat mieelle eoneentra-
tion (CMC). Recently, Stanberry e t al. (6) presented
some d a t a on perfomnanee of L A S vs. moI w t , but the
L A B source was not specified and no direct compari-
son with polypropylene products was given.
Therefore, the question o f how L A S performs in
heavy-duty formulas in "praetieal-type" tests in
direet comparison with P P A B S has not previously
been answered. The present report comes to b e a r
on this question and on w h e t h e r there is a n oppor-
t u n i t y to tailor straight-chain alkylbenzene s h i r e -
n a r e s t o obtain the s u p e r i o r properties o f the h i g h e r
reel wt polypropyleue products. The dishwashing foam
test is o f p a r t i e n l a r interest because it was folmd t o
be a sensitive test f o r showing the improvement as
reel wt was bmreased in the polypropylene ease.
U n f o r t u n a t e l y , polypropytene alkylbenzene sulfo-
nate has become generally known simply as "ABS."
Therefore, to avoid a n y confusion between materials
and to emphasize the considerable difference between
polypropylene and straight-chain products, we will
refer to Ghe l a t t e r as LAS, standing f o r linear alkylate
sulfonate, The polypropylene p r o d u c t will be called
PPABS.
Experimental
PreparaHo~ of Materials. The alkylbenzenes used
in this work originated from several sources as sum-
marized in Table I. They were bateh sulfonated with