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Bioresource Technology 99 (2008) 4621–4626

Anaerobic treatment of distillery spent wash – A study


on upflow anaerobic fixed film bioreactor
Bhavik K. Acharya, Sarayu Mohana, Datta Madamwar *

BRD School of Biosciences, Sardar Patel Maidan, Vadtal Road, Sattelite Campus, P. Box No. 39, Sardar Patel University,
Vallabh Vidyanagar 388120, Gujarat, India

Received 1 November 2006; received in revised form 27 April 2007; accepted 15 June 2007
Available online 31 August 2007

Abstract

Anaerobic digestion of wastewater from a distillery industry having very high COD (1,10,000–1,90,000 mg/L) and BOD (50,000–
60,000 mg/L) was studied in a continuously fed, up flow fixed film column reactor using different support materials such as charcoal,
coconut coir and nylon fibers under varying hydraulic retention time and organic loading rates. The seed consortium was prepared
by enrichment with distillery spent wash in a conventional type reactor having working capacity of 3 L and was used for charging
the anaerobic column reactor. Amongst the various support materials studied the reactor having coconut coir could treat distillery spent
wash at 8 d hydraulic retention time with organic loading rate of 23.25 kg COD m3 d1 leading to 64% COD reduction with biogas
production of 7.2 m3 m3 d1 having high methane yield without any pretreatment or neutralization of the distillery spent wash. This
study indicates fixed film biomethanation of distillery spent wash using coconut coir as the support material appears to be a cost effective
and promising technology for mitigating the problems caused by distillery effluent.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Distillery spent wash; Anaerobic fixed film bioreactor; Charcoal; Coconut coir; Nylon fibers

1. Introduction friendly and socio economically acceptable technology.


The anaerobic digestion is particularly suitable for winery
Distillery industries in India pose a very serious threat to and distillery waste water because their COD/N/P ratio is
the environment because of the large volume of wastewater unbalanced for aerobic treatments which need phosphorus
they generate which contains significant amount of recalci- and nitrogen addition (Moletta, 2005). Anaerobic digestion
trant compounds. Distillery spent wash is considered as a of biodegradable wastes involves a large spectrum of bacte-
very high strength wastewater having very high COD and ria of which three main groups are distinguishable. The
BOD with low pH and dark brown color (Goel and Chan- first group comprises fermenting bacteria which perform
dra, 2003). The pollution caused by the disposal of hydrolysis and acidogenesis. Acetogenic bacteria constitute
untreated or inadequately treated wastewater into fresh the second group and are responsible for breaking down
and marine water bodies is gradually becoming a major the products of the acidification step to form acetate. The
hazard to aquatic organisms. Bioremediation of distillery third group involves methanogenic bacteria which convert
spent wash by anaerobic digestion is an attractive primary acetate or carbon dioxide and hydrogen into methane
treatment due to its reputation as a low cost, environment (Kansal et al., 1998).
All modern high rate biomethanation processes are
*
based on the concept of retaining high volume of viable
Corresponding author. Tel.: +91 2692 234402; fax: +91 2692 236475/
237258.
biomass by some mode of bacterial sludge immobilization.
E-mail addresses: acharyabhavik@yahoo.com (B.K. Acharya), datta_ It can be very well done by entrapment of sludge aggre-
madamwar@yahoo.com (D. Madamwar). gates between packing material supplied to the reactor,

0960-8524/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.06.060
4622 B.K. Acharya et al. / Bioresource Technology 99 (2008) 4621–4626

e.g. down flow anaerobic reactor and up flow anaerobic


reactor (Rajeshwari et al., 2000).
The fixed film reactors offer distinct advantages over
other anaerobic systems such as simplicity of construction,
elimination of mechanical mixing, better stability at higher
loading rates and capability to withstand large toxic shock
loads.
The solid support filling within reactor is the most
important component of an anaerobic fixed film reactor.
Some ideal characteristics of the packing material are high
porosity, large surface area, adequate surface properties for
B
adherence light weight and economical (Agamuthu, 1999).
The main objective of the present study was to investi-
gate the role of an appropriate support material which
would allow more bacterial biomass to sustain in the reac-
tor and thus leading to efficient biodegradation of distillery
spent wash.
G
H1 H2
2. Methods C D E A F

2.1. Substrate
Fig. 1. Schematic diagram of up flow anaerobic fixed film bioreactor: (A)
Distillery spent wash was collected from a distillery sit- anaerobic fixed film reactor; (B) packing material; (C) untreated waste-
uated at Ankleshwar, GIDC, Gujarat, India. The charac- water; (D) treated effluent; (E) peristaltic pump; (F) rubber bungs; (G)
teristics of the wastewater are given in Table 1. Teflon plate; (H1 and H2) water displacement units.

2.2. Experimental set-up slurry were used as inoculum along with distillery spent
wash.
Laboratory scale anaerobic upflow fixed film glass col-
umn reactors (Fig. 1) were used in the present study. Each 2.4. Start up of fixed film reactors
reactor was constructed using a glass column having fol-
lowing specifications. Reactor height: 4800 , media height: Upflow anaerobic fixed film reactors were charged with
4000 , inner diameter: 4.5 cm, total volume: 2 L and working the enriched anaerobic culture from the conventional type
volume: 1 L. Reactors were packed with different packing of reactors as inoculum and biofilm was allowed to develop
materials namely charcoal, coconut coir and nylon fibers. by incubating at 37 °C for 35–40 d. During incubation per-
iod facultative anaerobes utilized the organic matter pres-
2.3. Enrichment of anaerobic consortia ent in the substrate and created anaerobic conditions for
strict anaerobic bacteria. Biofilm development was assessed
Anaerobic seed consortium was prepared by enrichment by gas production and visual observation in change of
in conventional type reactors having 3 L working volume. color. Initially biogas production was low because of accli-
Anaerobic sludge from an ongoing reactor and cattle dung matization and adaptation of the bacteria on support
materials. After the establishment of all the group of bac-
Table 1 teria biogas production increased, and as the organic mat-
Characteristics of distillery spent wash ter present in the substrate depleted biogas production
Parameters Values of distillery spent wash decreased gradually. Then the effluent was slowly replaced
with distillery spent wash of pH 4.5 without neutralization
pH 3.0–4.5
BOD5 (mg L1) 50,000–60,000 and any pretreatment. Initially all the reactors were oper-
COD (mg L1) 1,10,000–1,90,000 ated at HRT of 30 d for at least three retention times after
Total solid (TS) (mg L1) 1,10,000–1,90,000 reaching steady state condition. Subsequently HRT was
Total volatile solid (TVS) (mg L1) 80,000–1,20,000 decreased and accordingly OLR was increased gradually
Total suspended solid (TSS) (mg L1) 13,000–15,000
and reactors operated at 20 d, 15 d, 10 d, 8 d and 6 d. All
Total dissolved solids (TDS) (mg L1) 90,000–1,50,000
Chlorides (mg L1) 8000–8500 the reactors were allowed to reach to steady state condi-
Phenols (mg L1) 8000–10,000 tion. They were run at least for 3–4 RT after reaching
Sulfate (mg L1) 7500–9000 steady state condition. Steady state condition was judged
Phosphate (mg L1) 2500–2700 by stable gas production and constant COD and BOD of
Total nitrogen (mg L1) 5000–7000
the effluent (Patel and Madamwar, 2002). All the reactors
B.K. Acharya et al. / Bioresource Technology 99 (2008) 4621–4626 4623

were operated on a continuous basis at the desired reten- ciency of the process because the initial biomass of film
tion time and spent wash was fed into the reactor in an may be of major importance for further biofilm growth
upward direction at the required rate using peristaltic and stability.
pump (Gilson Minipuls 3, France). Our results also differ significantly amongst the three
reactors as the packing material varied. During initial incu-
2.5. Analytical methods bation period the biofilm development was visually more
detectable on, coconut coir and charcoal but on nylon
Biogas production was measured by the displacement of fibers the thickness of the biofilm was very poor. This dif-
acidified water (pH 2–2.5). Gas composition was deter- ference in biofilm development may be attributed to the
mined with gas liquid chromatograph (Sigma, Baroda hydrophobic nature and smoothness of the material (nylon
(India) Model M505) equipped with 2 m stainless steel col- fibers) that prevented the substrate from reaching the inner
umn packed with Porapak R (80–100 mesh) at 50 °C and a surfaces. Predominance of organisms in the biofilm is influ-
thermal conductivity detector, nitrogen was served as a car- ence by porosity and surface area of support material. High
rier gas at a flow rate of 30 mL min1. The injector and porosity and higher surface area of coconut coir help meth-
detector temperatures were kept at 125 °C. Feed and reac- anogenic bacteria to predominate in the biofilm along with
tor effluent samples were routinely analyzed for pH, O/R acidogenic bacteria and favour efficient biomethanation
potential, COD, BOD, volatile fatty acids, alkalinity, total process. This was supported by best performance of coco-
solids, total dissolved solids, total volatile solids, total nut coir bedded bioreactor as indicated by efficient COD
nitrogen, sulphates and phosphates according to Standard and BOD reduction, higher gas production with high meth-
Methods for Examination of Water and Wastewater ane yield even at lower retention time. However, reactor
(APHA, 1995). COD was measured using Hach DR 2010 could not be operated below 20 d HRT when bedded with
spectrophotometer and Hach COD reactor following the nylon fibers.
instructions for the Hach higher range test. Dissolved oxy-
gen for BOD was measured by YSI 5100 Dissolved Oxygen 3.2. Effect of OLR and HRT on COD and BOD reduction
Meter. Volatile Fatty Acids were determined using the
same gas liquid chromatograph equipped with flame ioni- The performance of the wastewater treatment system
zation detector and 3 mm diameter, 3 m stainless still col- can be related directly to the COD removal efficiency
umn packed with 10% FFAP (Sigma, Baroda, India.). achieved in the process (Wolmarans and de Villiers,
Nitrogen served as the carrier gas at a flow rate of 2002). There have been few investigations especially
30 mL min1, column temperature was kept at 180 °C. devoted to the stability of anaerobic fixed film process
The injector and detector temperature were 200 °C and under hydraulic shock loadings (Chua et al., 1997).
250 °C, respectively. Tables 2–4 as well as Figs. 2–4 summarize the steady
state performance of anaerobic up flow fixed film reactors
3. Results and discussion with different packing materials namely charcoal, coconut
coir and nylon fibers operated at 37 °C in a temperature
3.1. Effect of packing material controlled chamber under different organic loadings. All
reactors were initially operated at an HRT of 30 d by con-
Considerable work has been reported on biomethana- tinuous feeding of distillery spent wash without any dilu-
tion using up flow anaerobic reactors with a variety of sup- tion or neutralization. In order to study the effect of
port media having porous and non porous structures (Seth OLR and HRT, flow rates were increased in a stepwise
et al., 1995). A porous inert media enhances biofilm devel- manner i.e., HRT from 30 to 20 d then 15, 12, 10, 8 and
opment considerably as compared to more smooth media 6 d. After each change in HRT the reactors were allowed
(Patel and Madamwar, 2002). The support material has to reach steady state conditions, and they were allowed
always had a large influence on the start up and on the effi- to run at each HRT for at least 3–4 cycles. The higher

Table 2
Values of an up flow anaerobic fixed film reactor effluent operated at 37 °C with charcoal as packing material at varying hydraulic retention times under
steady state conditions
HRT (d) 30 20 15 12 10 8 6
OLR (kg COD m3 d1) 6.2 9.3 12.4 15.5 18.6 23.25 31
TS (g L1) 43.50 ± 1.50 52.55 ± 1.85 57.5 ± 2.25 70.5 ± 2.15 110.5 ± 2.20 125.10 ± 3.50 –
TDS (g L1) 14.0 ± 1.05 18.0 ± 2.28 22.5 ± 2.50 26.5 ± 3.55 48.0 ± 3.20 60.5 ± 3.80 –
TVS (g L1) 38.0 ± 1.50 47.0 ± 3.25 51.0 ± 4.25 55.5 ± 3.80 63.0 ± 4.25 70.5 ± 4.20 –
O/R potential (mV) 065 ± 002 064 ± 002 060 ± 003 067 ± 003 069 ± 002 055 ± 005 –
Sulfates (mg L1) 6500 ± 90.55 5979.15 ± 94.12 6000 ± 73.75 4025.15 ± 100.10 3700 ± 102.50 3750 ± 100.85 –
Phosphates (mg L1) – 2350 ± 80.80 2585.66 ± 94.62 2465.75 ± 35.50 2450.85 ± 50.55 2460.75 ± 35.75 –
Nitrogen (mg L1) – 3250.75 ± 50.80 3200.25 ± 50.40 2800.50 ± 30.80 2650.80 ± 30.75 2600.50 ± 40.45
TVA (mg L1) ND ND ND 850 ± 50.40 1150 ± 65.40 6350 ± 102.25 –
4624 B.K. Acharya et al. / Bioresource Technology 99 (2008) 4621–4626

Table 3
Values of an up flow anaerobic fixed film reactor effluent operated at 37 °C with coconut coir as packing material at varying hydraulic retention times
under steady state conditions
HRT (d) 30 20 15 12 10 8 6
OLR (kg COD m3 d1) 6.2 9.3 12.4 15.5 18.6 23.25 31
TS (g L1) 42.0 ± 3.50 50.8 ± 3.80 54.2 ± 4.05 65.5 ± 5.10 101.2 ± 10.10 106.5 ± 10.15 123 ± 11.50
TDS (g L1) 13.8 ± 2.50 15.5 ± 2.85 18.7 ± 2.70 24.8 ± 3.05 49.8 ± 4.05 47.5 ± 5.50 55.8 ± 5.50
TVS (g L1) 36.5 ± 2.50 43.8 ± 2.75 49.2 ± 3.25 54.5 ± 3.50 59.9 ± 4.55 62.5 ± 5.00 65.5 ± 6.15
O/R potential (mV) 065 ± 002 061 ± 002 062 ± 003 065 ± 003 067 ± 003 097 ± 002 076 ± 003
Sulfates (mg L1) – 6000 ± 40.80 5050 ± 45.25 6150 ± 50.90 5000 ± 40.50 4750 ± 25.90 4500 ± 50.25
Phosphates (mg L1) – 2350 ± 50.55 2380 ± 30.80 2480 ± 60.50 2450 ± 70.60 2490 ± 50.70 2380 ± 50.75
Nitrogen (mg L1) – 2450 ± 40.40 2480 ± 40.45 2300 ± 40.85 2350 ± 30.35 1156 ± 35.85 1140 ± 40.45
TVA (mg L1) – ND ND ND ND 750 ± 40.85 1200 ± 80.55

Table 4
Values of an up flow anaerobic fixed film reactor effluent operated at 37 °C with nylon fibers as packing material at varying hydraulic retention times under
steady state conditions
HRT (d) 30 20 15 12 10 8 6
OLR (kg COD m3 d1) 6.2 9.3 12.4 15.5 18.6 23.25 31
TS (g L1) 70.0 ± 5.85 123.6 ± 30.50 – – – – –
TDS (g L1) 59.5 ± 6.75 101.8 ± 32.75 – – – –
TVS (g L1) 60.05 ± 4.50 110.8 ± 20.75 – – – – –
O/R potential (mV) 060 ± 010 +110 ± 005 – – – – –
Sulfates (mg L1) 4500.85 ± 120.25 – – – – – –
Phosphates (mg L1) 2350.50 ± 95.75 – – – – – –
Nitrogen (mg L1) – – – – – – –
TVA (mg L1) 1250 ± 50.55 – – – – – –

100 100 8 5
Total gas production

80 80
% COD reduction

% BOD reduction

4
6

Methane yield
(m3mm-3d )
-1

(m3m-3m )
60 60

-1
3
4
40 40 2

20 20 2
1

0 0
0 5 10 15 20 25 30 35 0 0
-1 0 5 10 15 20 25 30 35
OLR (kgCODm-3d ) -1
OLR (kgCODm-3d )
Fig. 2. Effect of OLR on % COD reduction and % BOD reduction.
%COD reduction: (j) charcoal; () coconut coir; (m) nylon fibers; % Fig. 3. Effect of OLR on total gas production and methane yield. Total
BOD reduction: (h) charcoal; (e) coconut coir; (4) nylon fibers. gas production: (j) charcoal; () coconut coir; (m) nylon fibers; methane
yield: (h) charcoal; (e) coconut coir; (4) nylon fibers.

the HRTs less the time required for reaching the steady gas production of 6.2 m3 m3 d1 at 12 d HRT in the reac-
state and the lower the HRTs the more the time required tor having charcoal as packing material. More distur-
to reach the steady state. The steady state data revealed bances were observed at 10 d HRT and 8 d HRT. COD
that charcoal and coconut coir provided good support reduction was 50% at 10 d HRT and at 8 d HRT it
for biomass compared to nylon fibers. Reactor having decreased and reached to only 16% with gas production
charcoal as packing material was able to reduce about of 0.5 m3 m3 d1.
80% COD and 88% BOD of the spent wash at 30 d HRT The performance of the reactor with coconut coir was
and OLR of 6.2 kg COD m3 d1 with total gas produc- much better than with charcoal, at 30 d HRT with OLR
tion of 2.4 m3 m3 d1 with high methane yield. At each of 6.2 kg COD m3 d1 COD and BOD reduction were
change in HRT and OLR, COD as well as BOD reduction 80% and 89%, respectively, and gas production was
decreased, due to the higher organic load applied at each 2.9 m3 m3 d1. In this case also COD and BOD reduction
stage, total gas production increased due to the faster met- decreased with increase in OLR but more stability was
abolic rate of the organisms. It is shown that 60% COD observed, and no noticeable disturbance occurred in the
reduction and 73% BOD reduction was observed with system. More than 60% COD and 67% BOD reduction
B.K. Acharya et al. / Bioresource Technology 99 (2008) 4621–4626 4625

9000 10 and coconut coir respectively. Solid removal efficiency


was very poor in reactor having nylon fibers. About 3–
7500
8 3.5% non volatile matter found in the reactors during the
-1
Alkalinity mgL

6000 study which indicates very high amount of metals present


6 in the effluent. At lower HRTs more solids were found in

pH
4500 the effluent due to the washout of the biofilm.
4
3000
3.4. pH, alkalinity and volatile acids
2
1500

0 0
The anaerobic digestion process is known to be extre-
0 5 10 15 20 25 30 35 mely sensitive to pH and optimum operational pH range
OLR kgCODm-3d
-1 is 6.0–8.0. It is known that methanogenesis appears to be
an alkalizing step, as it consumes hydrogen and H3O+ ions
Fig. 4. Effect of OLR on alkalinity and pH. Alkalinity: (j) charcoal; (r) (Patel and Madamwar, 2000). During the course of study,
coconut coir; (m) nylon fibers; pH: (h) charcoal; (e) coconut coir; (4)
nylon fibers.
in all the reactors pH remained between 8.0 and 8.5 except
the critical HRT i.e., in reactor having charcoal pH
decreased to 6.5 at 8 d HRT due to the accumulation of
were observed at 8 d HRT with gas production of acids and in case of reactor with nylon fibers pH drop
7.25 m3 m3 d1. At 6 d HRT OLR was increased to was observed during 20 d HRT (Fig. 4).
31 kg COD m3 d1 but COD reduction decreased to Data show that the reactors with charcoal and coconut
50% and gas production was also decreased to 3.5 m3 coir provided better buffering capacity (from the data of
m3 d1 (Figs. 2 and 3). Kalyuzhnyi et al. (2005) studied alkalinity) in comparison to the reactor having nylon
biological treatment of baker’s yeast wastewater in UASB fibers. In reactors with charcoal and coconut coir, alkalin-
reactor and reported 50% COD reduction at OLR of 16 kg ity was in the range of 6000–8000 mg L1. Akalinity
COD m3 d1. These result shows that our reactor showed decreased to 1500 mg L1 at 8 d HRT due to the accumu-
same COD reduction at almost double organic load. lation of volatile acids and washout of methanogenic pop-
On observing the performance of the reactor packed ulation in reactor with charcoal (Fig. 3). The reactor with
with nylon fibers, it can be concluded that the reactor nylon fibers showed very poor buffering capacity and the
was not stable even at high HRT. At 30 d HRT 62% reactor became acidic at 20 d HRT with OLR of 9.3 kg
COD and 68% BOD reduction was observed with gas pro- COD m3 d1. Accumulation of VFA was not observed
duction of 1 m3 m3 d1, and drastic disturbances were at higher HRT in reactors except reactor with nylon fibers.
observed when HRT was decreased to 20 d as COD and Little amount of VFA was observed at 12 d HRT but it
BOD reduction decreased to 30% with gas production of did not affect the reactor condition and pH was also
0.2 m3 m3 d1. stable in reactor packed with charcoal. At 8 d HRT,
Trnovec and Britz (1998), Gangagni Rao et al. (2004), VFA accumulation was observed and VFA concentration
Perez-Garcia et al. (2005) have reported optimum condi- was 6350 mg L1 with decrease in pH to 6.5. More buffer-
tions for biomethanation of distillery spent wash to be ing capacity was observed in reactor having coconut coir
between OLR of 8 and 10.5 kg COD m3 d1 and on fur- due to the high amount of retained biomass. No VFA
ther increasing the OLR, hydraulic shock loading condi- accumulation was observed till 8 d HRT due to the high
tions would result with sharp drop in methanogenic buffering capacity. With nylon fibers very little buffering
activity. In our study better performance was observed in capacity was observed as results shows that even at higher
terms of the, removal of COD, BOD and biogas produc- HRT of 30 d VFA concentration was 1000 mg L1 and at
tion against OLR applied. 20 d HRT VFA accumulation was so high that pH of the
The reactor with coconut coir could withstand much reactor dropped to 5.0, resulting in the failure of the
higher hydraulic and organic loadings. This may be due reactor.
to its physical characteristics, which makes it a better sup-
port material for biomass development and attachment. 3.5. Sulfates, phosphorus and nitrogen

3.3. Effect of OLR on solid removal Biological treatment of sulfate rich wastewater was
rather unpopular because of the production of H2S under
Distillery spent wash contains very high amount of sol- anaerobic conditions. Under anaerobic conditions, sulfate
ids and the major part of it as dissolved solids. In reactor reducing bacteria (SRB) use sulfate as a terminal electron
with charcoal and coconut coir as packing material, at acceptor for the degradation of organic compounds and
30 d HRT, TS of the effluent were 43.50 g L1 and hydrogen. In the presence of sulfate, methanogenic bacte-
42.0 g L1, respectively, but as the loading rate increased ria compete with SRB for the available substrates. The out-
solid removal decreased and at 8 d HRT, TS were come of this competition is important as it will determine
125.10 g L1 and 106.5 g L1 in reactor with charcoal to what extent sulphide and methane, the end products
4626 B.K. Acharya et al. / Bioresource Technology 99 (2008) 4621–4626

of the anaerobic mineralization processes, will be produced post-methanation effluent still needs to be treated to meet
(Hulshoff Pol et al., 1998). In the present study sulfate the pollution control standards.
reduction was not observed at higher HRTs and the reac-
tors showed higher methanogenic activity from 30 d HRT References
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strength distillery spent wash for biomethanation using canning factory effluent. Water SA 24, 1147–1152.
upflow fixed film anaerobic bioreactor employing coconut Wolmarans, B., de Villiers, H.G., 2002. Start-up of a UASB effluent
coir as packing material under high organic loading. The treatment plant on distillery wastewater. Water SA 28, 63–68.

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