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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University, Kukatpally, Hyderabad 500 085, Andhra Pradesh, India
TLGVRC, JSU Box 18739, JSU, Jackson, MS 32917-0939, USA
a r t i c l e
i n f o
Article history:
Received 14 August 2008
Received in revised form 14 November 2008
Accepted 14 November 2008
Available online 8 January 2009
Keywords:
Pharmaceutical wastewater
UASB
Organic loading rate
HRT
Thermophilic treatment
a b s t r a c t
The hybrid up ow anaerobic sludge blanket reactor was evaluated for efcacy in reduction of chemical
oxygen demand (COD) and biochemical oxygen demand (BOD) of bulk drug pharmaceutical wastewater
under different operational conditions. The start-up of the reactor feed came entirely with glucose,
applied at an organic loading rate (OLR) 1 kg COD/m3 d. Then the reactor was studied at different OLRs
ranging from 2 to 11 kg COD/m3 d with pharmaceutical wastewater. The optimum OLR was found to
be 9 kg COD/m3 d, where we found 6575% COD and 8094% of BOD reduction with biogas production
containing 6070% of methane and specic methanogenic activity was 320 ml CH4/g-VSS d. By the characterization studies of efuent using GCMS, the hazardous compounds like phenol, l,2-methoxy phenol,
2,4,6-trichloro phenol, dibutyl phthalate, 1-bromo naphthalene, carbamazepine and antipyrine were
present. After the treatment, these compounds degraded almost completely except carbamazepine. Thermophilic methanothrix and methanosaetae like bacteria are present in the granular sludge.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
The pharmaceutical wastewaters contain a variety of organic
and inorganic constituents including spent solvents, catalysts, additives, reactants and small amounts of intermediates and products,
and may therefore be high in chemical oxygen demand (COD) (Fent
et al., 2006; Oktem et al., 2007). It is estimated that approximately
half of the pharmaceutical wastewaters produced worldwide are
discarded without specic treatment (Enick and Moore, 2007).
Pharmaceutical wastewater has traditionally been treated using
physico-chemical (Kulik et al., 2008) and aerobic biological processes (Suman Raj and Anjaneyulu, 2005). Recently there are specic studies reporting the application of anaerobic technology for
the treatment of Bulk drug pharmaceutical wastewaters (Chen
et al., 2008; Gangagni Rao et al., 2005; Chelliapan et al., 2006). However, the high COD concentration in such pharmaceutical wastewaters makes them potential candidates for anaerobic technology
(Chelliapan et al., 2006). The anaerobic process is very much favorable for high strength wastewater, where aerobic oxidation of organic matter would result in high-energy consumption and
production of huge quantities of sludge. The most important merits
of anaerobic treatment are the ability to treat high strength wastes,
low energy input, low sludge yield, low nutrient requirement, low
operating cost, low space requirement and net benet of energy
* Corresponding author. Tel./fax: +91 040 23156133.
E-mail addresses: vurimindihimabindu@yahoo.com, sri_jntures@yahoo.co.in (V.
Himabindu).
0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.11.028
2. Methods
2.1. Experimental setup
Lab scale experiments were conducted in lab scale HUASB reactor of 17 l capacity. The reactor is a circular column with a length of
90 cm, internal diameter of 10 cm and wall thickness of 2 mm. The
reactor was provided with hopper bottom. Four sampling ports are
provided along its length at equal distance. Inlet end opens towards the bottom of the reactor, so the feed strikes at the bottom.
An outlet was provided at the top, which is connected to the efuent tank. On the top of the reactor a gas solid separator is provided
to separate gas and solid raised due to the upward movement of
the feed. The gas outlet was connected through rubber tubing to
the liquid displacement system to measure the gas production.
The amount of gas produced is directly proportional to the amount
of liquid displaced and hence gas produced can be measured at
regular intervals of time. A lter media made up of PVC rings
was provided at the middle of the reactor. The reactors were operated at thermophilic temperature (55 3 C) by a water-jacket.
Heated water was pumped from a recirculation water bath through
the constant temperature jacket surrounding the reactor. Synthetic
wastewater comprising substrates, glucose, plus balanced nutrients and alkalinity was used to feed the reactor using a peristaltic
pump.
2.2. Wastewater source and characterization
The wastewater for this study was obtained from a local bulk
drug pharmaceutical unit in Hyderabad, from which the main
product was terbinane hydrochloride and characterized using
standard methods (APHA, 2000). The characteristics of bulk drug
pharmaceutical wastewater used for the study were (mg/l): colour
(orange), total dissolved solids (85009000), total suspended solids
(28003000), COD (13,00015,000), BOD (70007500), volatile
fatty acids (600750), alkalinity as CaCO3 (25003000), chlorides
(200250), nitrates (120170), sulphates (300450), phosphates
(100120), phenol (2530), 2-methoxy phenol (2025), 2,4,6-trichloro phenol (2025), dibutyl phthalate (3040), 1-bromo naphthalene (510), antipyrene (510) and carbamazepine (1015).
The pH of the bulk drug pharmaceutical wastewater was 7.07.5.
The BOD: COD ratio of the wastewaters was in the range 0.45
0.6, which is amenable to biological treatment. All the chemicals
used were of analytical reagent grade. Water used in all the experiments was laboratory distilled water with pH (7.28.0), Alkalinity
(40120 mg/l), chlorides (2030 mg/l). Tap water from a ground
water source is used for the dilution of raw efuent.
2.3. Inoculum
The inoculum for seeding the reactor was brought from a fullscale UASB reactor, which was in use for treatment of wastewater
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the reactor performance for a short period after initial loading. This
may be an indication to the increase in the substrate concentration,
which requires sufcient acclimatization period for native micro
ora to nurture to the changed environmental conditions of the
system. From the data, we can assess that the period required for
acclimatization is directly related to the OLR. The performance of
the reactor at various OLR levels were consolidated and presented
in Fig. 2. During the reactor operation there was a reduction in COD
and BOD levels up to 4766% and 8386%, respectively. It is evident from the table that increment in loading rate has shown gradual increment in substrate removal rate up to 10 kg COD/m3 d and
subsequently substrate removal rate dropped, indicating the inhibition of the biomass activity at that concentration. It explains that
the designed reactor can be operated up to 10 kg COD/m3 d without system inhibition and subsequent increase in OLR lead to
reduction in overall process efciency. Throughout the reactor
operation biogas production and a consistent value in the range
of 0.30.5 ml/mg COD reduction was observed irrespective of the
operated OLR. In the present study, ORP values are varied between
35 and 61. The anaerobic bacteria function best between ORP
values of +30 mV and 400 mV (Reddy et al., 1995). On analysis
of biogas, we observed gases in varying composition among them
most abundant are in range of 6570% methane and 3035% CO2.
Hydraulic retention time (HRT) considerably affects biogas composition, and in the present study a HRT of 1.7 days is found to be
optimum to retard the CO2 toxicity with relatively uniform CO2
content (3035%) at all the studied OLR. These values are similar
to that of Gangagni Rao et al. (2005), where they treated the bulk
Fig. 1. Performance of the hybrid UASB reactor for the removal of COD and BOD
during the period of operation.
2537
450 mg/l present in the efuent, after treatment the sulphate concentration was reduced to 250 mg/l. The efuent was characterized
for hazardous compounds before and after treatment using GC
MS. From the characterization studies using GCMS, the hazardous
compounds identied in the efuent were phenol, 2-methoxy phenol, 2,4,6-trichloro phenol, dibutyl phthalate, 1-bromo naphthalene and antipyrine. After the treatment these hazardous
compounds degraded almost completely except carbamazepine
was not degraded (Clara et al., 2004; Carballa et al., 2006).
3.2. Performance of the reactor under shock loading
In the present study, organic shock load tests were carried out
to assess the reactor stability at two stable OLR (Table 1). The reactor is stabilized at 1.0 COD/m3 d and the OLR is increased to
5 kg COD m3 d to observe the reactor performance for organic
shock loading. It can be observed from the table that due to organic
shock loading, the reactor performance signicantly dropped with
respect to carbon removal and specic methanogenic activity.
Therefore, again the OLR is brought back to 1.0 kg COD m3 d where
in the reactor performance is restored to normal stage. The reactor
is again subjected to organic shock loading of 13 kg COD m3 d
when the reactor is operating at stable OLR of 9 kg COD m3 d with
consistently steady state performance. In this case also reactor performance dropped with respect to carbon removal and is restored
when the organic loading is again decreased. It can be deduced
from the above results that reactor can withstand shock loads
and can be brought back to normalcy quickly during the operating
phase. This result is in agreement with the experiment undertaken
by Gangagni Rao et al. (2005), who exposed an anaerobic xed lm
reactor treating pharmaceutical wastewater to organic shock loads
and showed that the reactor performance dropped with respect to
carbon removal and was restored when the organic loading was
again decreased to normal stabilized OLR.
3.3. Characteristics of granular thermophilic sludge
Fig. 4. Variation of VFA concentration and variation of SMA during the period of
operation.
At the end of the 200 days operation the granular sludge was taken from the bottom of the reactor for the measurement of its
characteristics using scanning electron microscope. It showed that
over all surface of the granules were rough and uneven. The visual
examination of granular biomass revealed a black colour with a
spherical shape. Large cavities were present on the surface. The
physico-chemical characteristics of granules were studied during
the start-up and steady state operation at various organic loading
rates. SVI of the sludge in the reactors decreased from a value of
1620 to 1112 mL/g SS in the entire reactor. The plausible reason
for the decrease in the SVI is the increased settleability of the
sludge due to the pelletization of sludge occurring in the reactor.
Increase in organic loading rate resulted in an increase in the
sludge bed height. The sludge bed height increased from 14% to
18% at 1 kg COD m3 d to about 3536% at 12 kg COD m3 d in the
reactor. The average size of the sludge granule before treatment
was found to be 0.20 mm in diameter and after the treatment
was found to be 1.8 mm. Ash content of the granules decreased
with increase in the organic loading. Ash content of the granules
decreased from 1520% at 1 kg COD m3 d to 1113% at
12 kg COD m3 d. The observed ash fraction in the sludge is in
agreement with the values reported earlier (Sreekanth et al.,
2008). There are different groups of bacteria belonging to different
shapes in anaerobic granules. According to Michael (2003), methanogens could be present as rod, curved, spiral and coccus or spherical forms and their growth pattern may be irregular clusters or
lamentous chains. In the present study SEM observations demonstrated that Methanosarcina like coccoides were present in abundance, where as methanothrix like bamboo shaped rods existed
2538
Table 1
Performance of UASB at different organic shock loadings.
Organic shock
loads
Inlet OLR
(kg COD/m3 d)
Shock load at
5 OLR
Outlet OLR
(kg COD/m3 d)
COD
reduction
(%)
2.0
0.7
65
0.4
356
5.0
2.0
4.0
0.8
5
7
20
60
0.2
0.4
90
350
9.0
2.6
71
0.4
345
13.0
9.0
10.0
2.5
5
5
23
72
0.2
0.4
85
350
Shock load at
9 OLR
tor within the range. Scanning electron micrographs show that the
granules were composed of thermophilic Methanosarcina and
thermophilic methanothrix like bacteria.
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