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Proceedings of the 9th International Conference on Environmental Science and Technology

Rhodes island, Greece, 1 3 September 2005

REMOVAL OF ALKYLBENZENE SULFONATE (ABS) FROM DETERGENT


INDUSTRIES WASTEWATER BY ACTIVATED SLUDGE
S.N. HOSSEINI 1 and S.M. BORGHEI 2
1

Department of Environmental Engineering, Hamadan Azad University, Hamadan Iran


Department of Chemical Engineering, Sharif University of Technology, Tehran, Iran
E-mail: seyyednezam@yahoo.com

EXTENDED ABSTRACT
Linear and branched alkylbenzene sulfonate (LABS and ABS) are the most important
anionic surfactants which, widely applied in the formulation of household detergent and
industrial institutional cleaning products. The concentration of this anionic material in the
detergent industries wastewater is too high and discharge of this compound in to the
environment could be generated critical problem and unrestorable damages such as
poisoning of water life, pollution of ground water, and formation of foam in rivers. In this
condition some methods was used for elimination foam-producing substances in addition to
decreasing the load of organic materials. Due to this regards, various methods have been
proposed for treatment of detergent industries wastewater, the most common of which is
biological treatment.
The objective of this work was to develop a high performance process for the treatment of
detergent industries wastewater containing LABS and ABS.
The experiment for ability of LABS and ABS degradation was carried out by a continuous
activated sludge pilot plant. The pilot is a rectangular bioreactor with volume 11.7 L, sludge
recycle ratio QR/Q= 0.85, retention time 36 hr and two different volumetric loading 0.46 and
0.73 kg COD applied / m3.d.
In this study wastewater with initial concentration of 15 mg/l of detergent enter to the pilot
and after adaptation the dosage of detergent increase to 400 mg/l.
During 90 days, different parameters such as COD, (LABS and ABS), DO (Dissolved
Oxygen), MLSS (Mixed Liquor Suspended Solid), TKN and Phosphorous were measured.
Results shown that the wastewater of detergent industries have average biological oxygen
demand (BOD) concentration of 1910 mg/l, chemical oxygen demand (COD) concentration
2500 mg/l and detergent concentration as (DDBS, LABS) 1050 mg/l.
Results shown also that about 80 percent of detergents (mixed of LABS and ABS) are
degraded by this process. The detergent concentration in the pilot effluent change from less
than 2 mg/l (initial concentration of feed equal 15 mg/l) to 86.9 mg/l (final concentration of
feeding equal 400 mg/l).
This study demonstrated that biological treatment is very efficient to treatment of
wastewater polluted with low concentration of detergent. This study also demonstrated that
the wastewater including high detergent concentration more than 500 mg/l could not be
treated by biological treatment method only. In this condition, physical and chemical
treatment methods should be required for decreasing the detergent concentration before the
biological unit.
Key words: Biological Treatment, Activated Sludge, Alkylbenzene Sulfonate, wastewater,
Detergent Industry.

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INTRODUCTION
Rapid population growth and improvement of public health level has resulted in the increase
of production and consumption of various detergents. Regarding their ingredients, the
pollution resulting from the consumption of such substances severely endangers the
bioenvironmental. The main ingredient of detergents is alkyl benzene sulfonate.
The first alkylbenzene sulfonate (ABS) was obtained by the Friedle-Crafts alkylation of
benzene with propylene tetramer. The tetramer is a mixture of C12 olefins. A as result, the
corresponding alkylbenzene sulfonate is highly branched. The detergent product is then
made by sulfonation of the dodecylbenzenes with oleum or sulfur trioxide followed by
neutralization with sodium hydroxide or soda ash. The active-detergent could be formulated
in to the commercial product. Although the dodecyle benzene was an effective detergent, it
has slow rates of biodegradation in the environment. It became apparent that
dodecylbezene based detergents were contributing to pollution of lakes and streams by
forming relatively stable foams [1].
The resistance of branched ABS to biochemical degradation in aquatic environments also
posed a threat to municipal drinking water supplies, which were using surface water as a
source for drinking water production [2].
Linear alkylbenzene sulfonats(LAS, Fig 1) that are produced from linear paraffin-based
alkylbenzene, can be readily destroyed by microorganism action, and the years following
the switch from ABS to LAS, the surfactant levels in surface waters dropped significantly
and foam related environmental problems almost disappeared. The switch, however, to
better degradable LAS was not carried out by all nations, i.e. the ABS is still in extensive
use in some countries. Although LAS offer advantages in term of performance
characteristics, such as foam generations and detergency, ABS favorable physical
properties in special formation, like synthetic laundry bars. Another decisive argument for
the use of ABS arises from cheaper raw materials, which can be of importance, particularly
in loss economically favored countries [3].
Wastewater produced in many detergent industries often contain linear alkylbenzene (LAS)
and branched alkylbezene(ABS) compounds, that are not amenable to direct biological
treatment. Although physico-chemical processes, the latter are considered, to be generally
loss environmentally friendly, generating large volume of chemical sludge and often
requiring a pre-dilution of the detergent bearing wastewater to be treated.
An attractive potential alternative to complete treatment by means of chemical oxidation
would be the use of an integrated physical, chemical and biological treatment process
comprising a physical and chemical pre treatment steps to decrease bioresistant compound
concentrations [4].
Biological operation is known to remove different organic molecules from wastewater. In this
study, application of activated sludge in removing anionic surfactant was evaluated.

Figure 1: Different form of alkylbenzene sulfonate

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MATERIALS AND METHODS


Chemicals:
All solvents and chemicals used were reagent grade. K2Cr2O7, N-cetyl-N,N,N-tri methyl
ammonium bromide, methylene blue, chloroform, H2SO4, were purchased from Sigma and
Merck company.
Sampling:
Samples for the ABS and COD removal experiment were taken randomly at 2 different
times from the waste of detergent powder production plant. Properties of the final sample
are presented in table 1. Samples were stored in a fridge to prevent any biological activity
[5].
Quality parameters of the wastewater treated by activated sludge, in biological method
were calculated using standard methods.
The parameters analyzed were pH, organic compounds measured by Chemical Oxygen
Demand (COD) and (LAS, ABS) concentration. The pH was measured by using a SP-701
SUNTEX pH/mV/TEMP meter.
Chemical Oxygen Demand (COD) was determined by potassium dichromate reflux method
ABS concentration measured by methylene blue method [6].
Table1: Characteristics of mixed sample
Parameters
COD (mg/lit)
BOD(mg/lit0
LAS,ABS
TDS(mg/lit)
Odor
Temperature(Co)
Discharge (m3)
Products

Sample 1
2500
1820
1000
2760
Very bad
30
90
Sulfonic acid , powder
detergents and
dishwashing liquid

Sample 2
2550
1910
1100
2900
Surfactant
34
150
Sulfonic acid , powder
detergents, dishwashing
liquid and soap

Pilot Plant:
In order to evaluate the efficiency of degradation of surfactant compounds by
microorganisms, a pilot system includes two tanks for aeration (bioreactor) and
sedimentation was constructed as follow:
Aeration tank: a rectangular polyethylene tank with 11.7 liters volume equipped with
inlet silicon pipe and peristaltic pump for feeding.
Sedimentation tank: A cylindrical polyethylene tank with 4.64 liters volume and
equipped with recycle line and polyethylene pipe and connections.

RESULT AND DISCUSSION


Whereas it is well reported that LAS is readily degradable under aerobic conditions [7-9] but
microorganisms may falling in trouble in the present of ABS loading from anionic
compounds include branched alkylbenzene sulfonate. During the experiment on the

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activated sludge pilot plant, inlet and outlet detergent concentration, inlet and outlet COD,
MLSS, pH, Nitrogen and phosphorous were measured and recorded.
Because of the characteristics of detergent industrial wastewaters that is showed in table1
and the high concentration of detergent materials (LAS and ABS) in the waste, loading of
this liquid to the activated sludge before adaptation of microorganisms with new media and
laboratory conditions was not recommended, therefore bioreactor was fed with a synthetic
wastewater that was prepare according to the specification of real wastewater.
Operation condition of pilot plant activated sludge is shows in the table 2 and this data are
base of all table and curves.
Table2: Operation condition of pilot plant
COD loading
Aeration
Recycle
(kg
rate(mg/L)
sludge
ratio
COD/m3.day)

Minimum
DO (mg/L)

Flow
regime

3.0

Completely
mixed

0.2

0.85

Retention
time(hr)

Discharge
(L/min)

36

0.325

0.46
0.73

Fig 2:Activated sludge pilot plant`s behavior during 95 days


2500

2000

mg/L

1500

1000

500

0
0

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Time(day)
COD in

COD out

(LABS,ABS)in conc.

(LABS,ABS)out conc.

MLSS

Figure 2. Operation of activated sludge process


The fig 2 shows operation of activated sludge process during 90 days.
The curve can be divided in the four parts. Part one from first day to twentieth day was for
adaptation of microorganisms with medium and new condition that the low COD (0.46 kg
COD/m3.day) was loading to pilot plant. Part two (10th-28th ) day, microorganisms have
been adapted with this condition and the outlet COD decreased with time, this part shows
that microorganisms are ready to received wastewater with more COD concentration or
more organic material concentration (COD loading equals 0.73(kg COD/m3.day)) , in the
twentieth day COD concentration reduced from 888 mg/L to 145 mg/L .
This operation was continuing until 28th day of experiment and obtained results from pilot
showed the high performance of microorganism.
Part three; activated sludge pilot plant was fed with (LABS, ABS) as main pollutant with
concentration of 15 mg/L.
Surfactant outflow concentration was less than 2.0 mg/L, during days (28-32). It was not
clear that all decreased surfactant were degraded by microorganisms and maybe a portion

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of this surfactant was adsorbed on the surface of microorganisms, previous reports


indicated that partially of linear alkylbenzene sulfonate adsorbed to sludge [10], the
experiment was continued by increasing in the surfactant concentration during time, 60
mg/L, 120, 250,350, 450 and 500 mg/L at days 32, 44, 56, 68, 76 and 90 respectively.
Results showed that efficiency of process was very high (90%) in the first days of detergent
injection. The reason of this matter was low concentration and adsorption of detergent
material by microorganisms. In addition, results showed that increasing in inlet detergent
concentration, the concentration of detergent in outflow increase and efficiency of detergent
removal decrease around 75%, and in the present of inflow with high detergent
concentration more than 450 mg/L the efficiency of process for detergent degradation fall to
60% (Part 4), Abdelafidh reported degradation rate of sodium lauryl ether sulfate (SLES) by
Citrobacter baarkii was 65 (mg.l-1.h-1) [11].
The major reason for reducing in efficiency of process with increase detergent concentration
was foam formation in the pilot plant and floatation of microorganism and other reason was
resistance of microorganisms that showed respect to the branched alkylbenzene sulfonate.

CONCLUSION:
The present study demonstrates that activated sludge is a good choice to degradation of
wastewater containing mix of ABS and LABS.
The obtained results recommended that the maximum concentration of detergent in the
activated sludge process must not more than 500 mg/L. In addition, this study shows that
chemical or physical treatment methods are necessary to reduce the concentration of
detergent material before biological treatment.

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