Innovative Technology of COD and BOD Reduction

from Coffee Processing Wastewater Using Avocado Seed

Carbon (ASC)
Rani Devi
Received: 23 January 2009 / Accepted: 24 June 2009 / Published online: 8 August 2009
# US Government 2009
Abstract The study estimated the efficiency of
Avocado seed carbon (ASC) for chemical oxygen
demand (COD) and biochemical oxygen demand
(BOD) reduction from coffee processing wastewater.
It was performed under batch mode conditions to
investigate the optimum operating conditions and
efficiency for COD and BOD reduction with ASC
compared with commercial activated carbon (CAC).
Adsorption isotherm study was also performed and it
was found that the values of regression coefficient
(r
2
), adsorption capacity (k), and adsorption intensity
(1/n) for COD and BOD reduction with ASC were
comparable to those of CAC. Under optimum
operating conditions, the maximum percentage reduc-
tion of COD and BOD concentration using ASC was
98.28% and 99.19%, respectively and with CAC was
99.12% and 99.45%, respectively and hence adsorp-
tion capacity of ASC is comparable with that of CAC.
Thus, this technique may be a good option for
treatment of domestic wastewater.
Keywords Adsorption
.
Avocado
.
BOD
.
COD
.
Coffee processing wastewater/effluent
1 Introduction
The place of coffee origin in the world is Ethiopia as
the first coffee plant was initially found there only and
it is the worlds third largest coffee exporter after
Burundi and El Salvador. Jimma zone is one of the
important coffee producing zones and wet coffee
processing method has been adopted here. This coffee
processing method needs mechanical removal of pulp
with the help of water and due to this, a considerable
amount of wastewater is generated (Enden 2002;
Murthy et al. 2003, 2004). About half of the water is
consumed in pulping process only (Fresner and
Schnitzer 1996; GTZ-PPP 2002; Enden and Calvert
2002).
There is a high concentration of organic matter in
the wastewater generated from coffee processing plant
(Matos et al. 2001; INEP 2001; MoEF Ministry of
Environment and Forest, 2003) like pectin, proteins,
and sugars (Adams 1980; Calvert 1997; Mendoza and
Rivera 1998; Deepa et al. 2002). Due to this, its
disposal without treatment has become undesirable
(Rolz 1982) as it can impacts the water bodies and
human health. Thus, prior to discharge to water
bodies, it needs a proper treatment.
The treatment of this wastewater with conventional
methods is very expensive (Piet et al. 1994; Mazumder
and Roy 2000). Therefore, to meet the environmental
standards and to protect environment, it has become
necessary to find suitable environmental friendly and
economically viable treatment technologies.
Water Air Soil Pollut (2010) 207:299306
DOI 10.1007/s11270-009-0137-2
R. Devi (*)
Department of Energy and Environmental Sciences,
Ch. Devil al University,
Sirsa, Haryana, India
e-mail: rani_sahu@yahoo.com
A number of research efforts are in progress
(Mohammed et al. 1998; Wang et al. 2005) for
development of such types of wastewater treatment
technologies. Various low-cost adsorbents like chitin,
chitosan, corn stalks, peat, rice husk, and wood have
been used for removal of organic matter from
industrial effluents (Poots et al. 1976; Mckay et al.
1980; Sharma and Sharma 1994). Discarded material-
based low-cost adsorbents of different origins like
industrial waste material, bagasse fly ash, and jute-
processing waste can also be used for removal of
organic matter from wastewater (Patnaik et al. 1996;
Pala and Tokat 2002; Srivastava et al. 2005; Wang and
Wu 2006; Bhatnagar 2007).
Adsorption-based technique (Devi et al. 2002;
Devi and Dahiya 2006) developed with low-cost
carbonaceous materials showed good potential, more
so for chemical oxygen demand (COD) removal from
domestic wastewater. Such adsorption approach can
offer an easy and economic solution to these
environmental challenges. Moreover, activated carbon
is considered very effective in reduction of color,
absorbable organic halides and non-biodegradable
pollutants present in such wastewater but this process
also has some additional costs associated with the
production of activated carbon.
The purpose of this study was to evaluate the
potential of Avocado seed carbon for treatment of
coffee processing wastewater and also to compare its
results with commercial activated carbon.
2 Materials and Methods
2.1 Selection and Preparation of Adsorbent
Wastewater samples were collected from a coffee
processing plant and were stored at 23C to avoid
any change in their physico-chemical character-
istics. Adsorbent used in the present study was
derived from Avocado seed. Since the raw dis-
carded material was available free of cost but its
transportation and processing costs were to be
taken into account and thus the resulting adsorbent
was expected to be economically viable for the
wastewater treatment. This is a quite efficient
method specifically for removing the organic sub-
stances from coffee processing wastewater. For
standardization of the results, same types of experi-
ments were conducted with commercial activated
carbon also.
The seeds of Avocado fruits were separated from
the pulp and then crushed in a crushing mill (Model-
BB 100 Rosrfrei, Retsch Germany). The resulting
product was washed several times with distilled water
to eliminate water soluble impurities and then oven-
dried at 105C for 24 h. Two hundred fifty grams
small pieces of this oven-dried Avocado seeds were
mixed with 30 ml of concentrated sulphuric acid
(H
2
SO
4
). The mixture was carbonized at 600C for
12 h. Then sample was withdrawn from furnace and
cooled in a desiccator. After cooling, this sample was
rinsed several times with distilled water till its pH
became 6 to 7. The wet sample was dried at 105C for
24 h. It was further crushed and filtered. The particles
of size ranging from 0.75 to 0.25 mm were recovered
and were used throughout the study.
Characterization of so prepared discarded material-
based carbonaceous adsorbents was done using
standard methods (Indian Standard Methods 1986).
The commercial activated carbon (Calgon Co-
Filtrasorb 400) was purchased from a local chemical
supplier. The important physical properties were
surface area, bulk density, porosity, moisture content,
contents of carbon, hydrogen, oxygen, and nitrogen as
shown in Table 1.
2.2 Analysis of Wastewater
The pH and temperature of the wastewater samples
were measured on collection site to avoid the change
in their values. The wastewater samples for measure-
ment of electrical conductance, turbidity, total solids,
total suspended solids, total dissolved solids, bio-
Table 1 Characteristics of the commercial activated carbon
and Avocado seed carbon
Parameters ASC CAC
Surface area of sample, m
2
/kg 750 1,000
Bulk density, kg/m
3
165 180
Porosity, % 75.00 85.00
Moisture content, % 8.5 4.50
Carbon content, % 88 92.00
Hydrogen content, % 2.82 1.80
Nitrogen content, % 3.70 3.20
Oxygen content, % 6.44 5.00
300 Water Air Soil Pollut (2010) 207:299306
chemical oxygen demand (BOD), COD, and most
probable number (MPN) were stored at 4C and were
analyzed in laboratory according to the well-known
methods prescribed by APHA (American Public
Health Association 1998) handbook. But for the
present study, only the removal of COD and BOD
were taken under consideration. The COD and BOD
of the wastewater samples were measured in labora-
tory before and after its treatment with adsorbents.
2.3 Batch Mode Treatment of Wastewater
The complete experimental study was conducted at
ambient temperature (25C) in batch mode. The batch
experiments were conducted in different flasks of
250 ml capacity using an average speed shaker.
Adsorption experiments were conducted in different
batches for all the experimental conditions like
adsorbent treatment time, adsorbent dose, pH of the
solution, initial COD and BOD concentrations,
agitation speed, and adsorbent particle size.
Varying one parameter and keeping others
constant studied the influence of various operating
parameters. Stirring speed of the shaker was kept
constant for each run throughout the experiment
thus ensuring equal mixing, except for those, which
were meant for investigating the effects of agitation
speed. The desired pH was maintained using dilute
NaOH (0.1 N)/HCl (0.1 N) solution. Each flask
was filled with a known volume of sample having
desired pH and stirring was initiated. The sample
was withdrawn from the shaker at predetermined
time intervals, filtered through Whatmann No. 44
filter paper and analyzed for COD and BOD
concentrations.
Effect of contact time of the adsorbents with waste-
water sample was investigated by agitating 100 ml
sample and adding 2 g adsorbent for different time-
periods varying from 10 to 100 min. Initial COD and
BOD concentration of the sample was 22,000 mg/l
and 12,000 mg/l respectively, pH of 7, agitation speed
800 rpm, and adsorbent particle size 0.75 mm. The
treated samples were withdrawn from shaker at
predetermined time intervals, filtered, and the resid-
ual COD and BOD concentrations were measured.
To determine contribution of the adsorbent dose on
COD and BOD reduction, 100 ml of sample was
treated with different doses of adsorbent ranging from
0.1 to 10 g/100 ml; the other conditions were:
treatment time of 70 min, pH7, initial COD and
BOD concentration of the sample of 22,000 mg/l and
12,000 mg/l respectively, agitation speed 800 rpm,
and adsorbent particle size 0.75 mm. The samples
were agitated for specific time intervals, filtered, and
then analyzed for the residual COD and BOD
concentration.
The effect of pH was studied with constant initial
concentration, adsorbent dose, and contact time but
varying the pH values from 1 to 12 using dilute
NaOH or HCl solution. The samples were agitated for
specific time, filtered, and then analyzed for residual
COD and BOD concentration and data was fitted into
Freundlich adsorption isotherm (Faust and Aly 1986).
The effect of initial COD and BOD concentration
was studied by keeping all other conditions constant
except changing the initial COD and BOD concen-
tration ranging from 15,000 mg/l to 30,000 mg/l and
3,000 mg/l to 18,000 mg/l, respectively.
The effect of agitation speed and adsorbent particle
size on the COD and BOD reduction was also
Parameters Characteristics of effluent WHO permissible limits
pH 4.5 6.88.5
Electrical conductance (mho/cm) 3.110
4
110
3
Temperature (C) 25 20
Turbidity (nephalometer turbidity Unit) 430 510
Total solids (mg/l) 2,050 650
Total suspended solids (mg/l) 700 200
Total dissolved solids (mg/l) 1,350 450
Chemical oxygen demand (mg/l) 22,000 300
Biochemical oxygen demand (mg/l) 12,000 100
MPN (coliform cells/100 ml) 110
9
1.510
7
Table 2 Physicalchemical
properties of effluent of
coffee processing plant
along with WHO permissi-
ble limits (WHO 1995) for
the discharge of treated
effluent to irrigation channel
Water Air Soil Pollut (2010) 207:299306 301
studied. As usual, one parameter is varied for one set
of experiments. Discrete values of the agitation speed
were kept from 100 rpm (revolution per min) to
1,000 rpm and adsorbent particle size as category A
(0.75 mm), B (0.55 mm), C (0.35 mm), and D
(0.25 mm), respectively.
3 Results and Discussions
The physico-chemical analysis of the wastewater
collected from the coffee processing plant was done
as shown in Table 2. It was evident that this
wastewater was polluted with organic load besides
dissolved and suspended matter. Organic load was
presented in terms of COD, BOD, and MPN. In this
paper, study was done only for reduction of COD and
BOD concentrations using discarded material-based
carbon made up of Avocado seed.
The COD and BOD concentrations were very high
compared to their permissible limits to discharge this
water for irrigation and horticultural uses as pre-
scribed by WHO as shown in Table 1. The wastewa-
ter was treated at 25C under batch mode operation
with ASC and its COD and BOD concentrations were
measured before and after treatment with adsorbent.
The important operating parameters taken under
consideration for the present study were; adsorbent
treatment time, adsorbent dose, pH of the medium,
initial COD/ BOD concentration of the wastewater,
agitation speed, and adsorbent particle size.
Adsorbent Treatment Time The percentage COD and
BOD reduction as a function of treatment time with
ASC was shown in Fig. 1. Test with commercial
activated carbon was also done for comparing the
60
65
70
75
80
85
90
95
100
0 20 40 60 80 100 120
Treatment Time (min)
%

r
e
d
u
c
t
i
o
n
% COD by CAC
% BOD by CAC
% COD by ASC
% BOD by ASC
Fig. 1 Effect of treatment time on percent COD and BOD
reduction using ASC and CAC adsorbents. Initial COD and BOD
concentrations, 22,000/12,000 mg/l; adsorbent dose, 2 g/100 ml of
wastewater; pH7; agitation speed, 800 rpm; and particle size of
adsorbent, 0.75 mm
30
40
50
60
70
80
90
100
110
0 1 2 3 4 5 6 7 8 9 10 11 12
Adsorbent dose (g/l)
%

r
e
d
u
c
t
i
o
n
% COD by CAC
% BOD by CAC
% COD by ASC
% BOD by ASC
Fig. 2 Effect of adsorbent dose on percent COD and BOD
reduction using ASC and CAC adsorbents. Initial COD and
BOD concentrations, 22,000/12,000 mg/l; treatment time,
70 min; pH7; agitation speed, 800 rpm; and particle size of
adsorbent, 0.75 mm
Freundlich adsorption isotherm for COD concentration reduction by ASC
2.5
3
3.5
4
4.5
5
5.5
1 2 3 4 5 6 7
log Ce
l
o
g

x
/
m
COD by ASC
Linear (COD by ASC)
Freundlich adsorption isotherm for BOD concentration reduction by ASC
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
1 2 3 4 5 6 7
log Ce
l
o
g

x
/
m
BOD by ASC
Linear (BOD by ASC)
Fig. 3 Freundlich plot for COD and BOD reduction using
ASC adsorbent. Initial COD and BOD concentrations, 22,000/
12,000 mg/l; treatment time, 70 min; pH7; agitation speed,
800 rpm; and adsorbent particle size, 0.75 mm
302 Water Air Soil Pollut (2010) 207:299306
results. The percentage reduction of COD and BOD
with ASC was 84.92% and 86.09% after a treatment
time of 70 min whereas the maximum reduction of
COD and BOD concentrations with commercial
activated carbon was 89.15% and 93.97%, respectively
after a treatment time of 70 min. As the treatment
time progressed, the adsorbent sites had the tendency
towards saturation. Difference between the adsorp-
tion capacities could be attributed due to the
difference in number of carbonaceous adsorption
sites in the different adsorbents.
Adsorbent Dose The effect of adsorbent dose on
percent reduction of COD and BOD concentrations
with ASC and CAC was shown in Fig. 2. Here the
treatment time was kept constant at 70 min. Equilib-
rium was reached corresponding to 4 g/100 ml of
adsorbent dose for both ASC as well as CAC. Percent
reduction of BOD concentration was greater than that
of COD concentration for all the adsorbent doses and
was also comparable to CAC.
The adsorption studies conducted at fixed initial
COD and BOD concentration and varying adsorbent
dose were fitted to Freundlich isotherm (Faust and
Aly 1986) of the form:
x
m
k C
1=n
e
where, x/m (mg/g) was the amount of COD and BOD
removed (x) per unit mass of adsorbent (m), C
e
(mg/l)
was residual COD and BOD concentration of aqueous
solution, k and 1/n were Freundlich constants and
measure of adsorption capacity and adsorption inten-
sity, respectively.
The Freundlich isotherm corresponding to the
experimental measurements for ASC and CAC were
plotted on log scales as shown in Figs. 3 and 4,
respectively. Values of regression coefficient (r
2
) had
been calculated from the linear fit and based on the
fit, the respective values of the slope 1/n, and
intercept on Y-axis taken as k were also calculated as
shown in Table 3. Values of 1/n, k, and regression
coefficient r
2
for ASC were 0.2401, 4.7786, and
0.8636 corresponding to COD concentration reduc-
tion and 0.2497, 4.5886, and 0.8645 corresponding
to BOD concentration reduction respectively and
those for CAC were 0.02658, 4.9472, and 0.8435
corresponding to COD concentration reduction and
0.2698, 4.7302, and 0.8599 corresponding to BOD
concentration reduction respectively. CAC and ASC
had the comparable values of 1/n and k. Thus, ASC
showed the comparable adsorption capacity and
adsorption intensity with CAC.
Freundlich adsorption isotherm of BOD concentration reduction by CAC
1.5
2
2.5
3
3.5
4
4.5
5
l
o
g

x
/
m
BOD by CAC
Linear (BOD by CAC)
Freundlich adsorption isotherm of COD concentration reduction by CAC
2
2.5
3
3.5
4
4.5
5
1 2 3 4 5 6 7
log Ce
1 2 3 4 5 6 7
log Ce
l
o
g

x
/
m
COD by CAC
Linear (COD by CAC)
Fig. 4 Freundlich plot for COD and BOD reduction using
CAC adsorbent. Initial COD and BOD concentrations, 22,000/
12,000 mg/l; treatment time, 70 min; pH7; agitation speed,
800 rpm; and particle size of adsorbent, 0.75 mm
Table 3 Effect of adsorbent particle size on percent COD and BOD reduction by ASC and CAC
Adsorbent particle ASC CAC
Size % COD reduction % BOD reduction % COD reduction % BOD reduction
A (0.75 mm) 51.34 59.02 58.19 63.78
B (0.55 mm) 69.09 74.26 75.54 80.59
C (0.35 mm) 91.95 94.03 95.56 97.15
D (0.25 mm) 98.20 99.28 99.12 99.45
Water Air Soil Pollut (2010) 207:299306 303
The constant 1/n and k are of definite importance
in determining the adsorption capacity of organic
pollutants from wastewater and reduction of COD and
BOD concentrations by adsorbents. The slope 1/n is
dependent on the order of the change of reduction in
COD and BOD concentrations with the adsorbent
dose, while k is dependent on the extent of removal of
COD by the adsorbents.
pH It has an important effect on the adsorption
capacity of CAC and ASC and hence COD concen-
tration and BOD concentration reduction from waste-
water and was shown in Fig. 5. The optimum pH for
maximum adsorption of organic impurities and COD
concentration and BOD concentration reduction from
wastewater of coffee processing plant by CAC and
ASC was 7.
Initial CODConcentration and BODConcentration The
investigation was also made for the effect of initial
COD and BOD concentration of the wastewater
solution on the percent COD and BOD reduction by
CAC and ASC as was shown in Fig. 6. The percent
COD concentration and BOD concentration reduction
with ASC and CAC was found to increase with
increase in the initial COD concentration and BOD
concentration and after reaching to saturation levels, it
started decreasing. The rate of adsorption increased
because of the increasing driving force. But at
24,000 mg/l of initial COD concentration and
30
40
50
60
70
80
90
100
2000 7000 12000 17000 22000 27000 32000
Initial COD and BOD Concentration
%

r
e
d
u
c
t
i
o
n
% COD by CAC % BOD by CAC
% COD by ASC % BOD by ASC
Fig. 6 Effect of initial COD and BOD concentration on percent
COD and BOD reduction using ASC and CAC adsorbents.
Treatment time, 70 min; adsorbent dose, 4 g/100 ml; pH7;
agitation speed, 800 rpm; and particle size of adsorbent,
0.75 mm
30
50
70
90
0 2 4 6 8 10 12 14
pH
%

r
e
d
u
c
t
i
o
n
% COD by CAC
% BOD by CAC
% COD by ASC
% BOD by ASC
Fig. 5 Effect of pH on percent COD and BOD reduction using
ASC and CAC adsorbents. Initial COD and BOD concen-
trations, 22,000/12,000 mg/l; treatment time, 70 min; adsorbent
dose, 4 g/100 ml; agitation speed, 800 rpm; and particle size of
adsorbent, 0.75 mm
50
60
70
80
90
100
110
50 250 450 650 850 1050
Agitation speed (rpm)
%

r
e
d
u
c
t
i
o
n
% COD by CAC
% BOD by CAC
% COD by ASC
% BOD by ASC
Fig. 7 Effect of agitation speed on percent COD and BOD
concentration using ASC and CAC adsorbents. Initial COD and
BOD concentrations, 22,000/12,000 mg/l; treatment time,
70 min, adsorbent dose, 4 g/100 ml; pH7; and particle size of
adsorbent, 0.75 mm
Table 4 Residual COD and BOD concentration after treatment
with ASC and CAC under batch mode operation under
optimum operating conditions
Adsorbents Residual COD
concentration
Residual BOD
concentration
ASC 294 98.2
CAC 216.3 78.38
304 Water Air Soil Pollut (2010) 207:299306
12,000 mg/l of initial BOD concentration, the curves
reached their saturation points. It was because of
saturation of adsorbent sites and hence the ratios of
the initial number of adsorbate molecules to the
available adsorption sites of the adsorbent diminished
accordingly.
Agitation Speed The effect of agitation speed on
percent COD and BOD reduction with ASC and
CAC was investigated by changing speed from
100 rpm to 1,000 rpm. Figure 7 showed that there
was a good trend for the percent COD and BOD
concentration reduction with the agitation speed for
CAC and ASC. Maximum COD concentration and
BOD concentration reduction were observed around
800 rpm for both the adsorbents. But at higher
agitation speeds, the loosely attached molecules might
re-enter into the adsorbate, hence lowering the percent
COD concentration and percent BOD concentration
reduction. Therefore, the agitation speed was kept at
800 rpm to see the effect of percent COD and BOD
concentration reduction by both the adsorbents.
Adsorbent Particle Size From the study, it was found
that adsorbent particle size had significant influence
on percent reduction of COD and BOD concentration
with ASC and CAC. The percent COD and BOD
concentration reduction for both the adsorbents were
maximum for particle size of category D and the
minimum reductions in COD and BOD was obtained
corresponding to particles of category A for both the
adsorbents as shown in Table 3. The values for
maximum percent COD concentration and percent
BOD concentration reduction with ASC and CAC
were 98.20% and 99.28% and 99.12% and 99.45%,
respectively corresponding to category D. It was
observed that smaller particles showed better adsorp-
tion than the larger ones because surface area is
directly related with adsorption capacity. This could
be explained on the basis of net surface area, as
smaller particles in a given quantity of powder would
have larger surface area than the case when bigger
particles are taken.
Optimum Operating Conditions for Wastewater
Treatment The optimum operating conditions for
getting maximum COD/BOD concentration reduction
from coffee processing effluent with ASC and CAC
were same and these conditions were treatment time of
70 min, adsorbent dose of 4 g/l00 ml, pH of 7, initial
COD/BOD concentration of 22,000/12,000 mg/l,
respectively, agitation speed of 800 rpm, and adsorbent
particle size of 0.25 mm. It could be inferred from the
experimental results presented in this paper that
residual concentrations of COD and BOD after
treatment with ASC under optimum operating con-
ditions were 294 mg/l and 98.2 mg/l respectively and
were well within the permissible limits of WHO
standards as shown in Table 4. These results could
be utilized for working out the design parameters of
an adsorption-based industrial wastewater treatment
system. Moreover, if ASC was added in secondary
treatment tank for the effluent treatment, there would
be a good saving of energy, which otherwise could
have been consumed in aeration process.
4 Conclusion
It was found in the present study that ASC is an
effective adsorbent for the reduction of COD and
BOD concentration from effluent of coffee processing
plant. Removal of COD and BOD concentrations with
ASC and CAC were found to be dependent on
treatment time, adsorbent dose, pH, initial COD and
BOD concentration, agitation speed, and adsorbent
particle size. The data of this adsorption study is
obeying the Freundlich Adsorption Model. The
results of treatment of wastewater generated in coffee
processing industry with adsorbent made up of
Avocado seed could be a good alternative to expen-
sive activated carbon. The quality of water after
treatment with ASC was found well within the
permissible limits prescribed by WHO for discharging
the treated water in irrigation drain.
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