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Journal of Environmental Management 86 (2008) 481497


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Wastewater treatment in molasses-based alcohol distilleries for COD


and color removal: A review
Y. Satyawali, M. Balakrishnan
TERI University, Darbari Seth Block, India Habitat Centre, Lodhi Road, New Delhi 110 003, India
Received 11 February 2006; received in revised form 12 September 2006; accepted 8 December 2006
Available online 12 February 2007

Abstract

Molasses-based distilleries are one of the most polluting industries generating large volumes of high strength wastewater. Different
processes covering anaerobic, aerobic as well as physico-chemical methods have been employed to treat this efuent. Anaerobic
treatment is the most attractive primary treatment due to over 80% BOD removal combined with energy recovery in the form of biogas.
Further treatment to reduce residual organic load and color includes various: (i) biological methods employing different fungi, bacteria
and algae, and (ii) physico-chemical methods such as adsorption, coagulation/precipitation, oxidation and membrane ltration.
This work presents a review of the existing status and advances in biological and physico-chemical methods applied to the treatment of
molasses-based distillery wastewater. Both laboratory and pilot/industrial studies have been considered. Furthermore, limitations in the
existing processes have been summarized and potential areas for further investigations have been discussed.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Decolorization; Distillery; Molasses; Spentwash

1. Introduction photosynthesis by blocking sunlight and is therefore


deleterious to aquatic life (FitzGibbon et al., 1998). Studies
Ethanol manufacture from molasses generates large on water quality of a river contaminated with distillery
volumes of high strength wastewater that is of serious efuent displayed high BOD values of 160021,000 mg/l
environmental concern. The efuent is characterized by within a 8 km radius (Baruah et al., 1993). Adequate
extremely high chemical oxygen demand (COD) treatment is therefore imperative before the efuent is
(80,000100,000 mg/l) and biochemical oxygen demand discharged. In addition to pollution, increasingly stringent
(BOD) (40,00050,000 mg/l), apart from low pH, strong environmental regulations are forcing distilleries to im-
odor and dark brown color (Central Pollution Control prove existing treatment and also explore alternative
Board (CPCB) 1994, 2003). In India, which is the second- methods of efuent management. For instance, Indian
largest producer of ethanol in Asia with a projected annual distilleries were stipulated to achieve zero discharge of
production of about 2300 million liters in 200607 spentwash to inland surface water by December 2005
(Subramanian et al., 2005), alcohol distilleries are rated (Uppal, 2004).
as one of the 17 most polluting industries. Apart from high In an earlier review on this subject, Sheehan and
organic content, distillery wastewater also contains nu- Greeneld (1980) discussed treatment options practiced
trients in the form of nitrogen (16604200 mg/l), phos- in the 1970s. More recently, Wilkie et al. (2000) have
phorus (2253038 mg/l) and potassium (960017,475 mg/l) examined characteristics and anaerobic treatment of
(Mahimairaja and Bolan, 2004) that can lead to eutrophi- efuent obtained from different feedstock used for ethanol
cation of water bodies. Further, its dark color hinders manufacture. This review focuses on the advances in
molasses-based distillery wastewater treatment in the
Corresponding author. Tel.: +91 11 2468 2100; fax: +91 11 2468 2144. last two decades and the emerging technologies in this
E-mail address: malinib@teri.res.in (M. Balakrishnan). eld.

0301-4797/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2006.12.024
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482 Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497

2. Process description manufacturing process and handling and storage (God-


bole, 2002). Table 1 summarizes the chemical composition
Alcohol manufacture in distilleries consists of four main of beet and cane molasses. Molasses is diluted to about
steps viz. feed preparation, fermentation, distillation and 2025 brix (measurement of sugar concentration in a
packaging (Fig. 1). solution) and its pH adjusted, if required, before fermenta-
tion. In India, about 90% of the molasses produced in cane
2.1. Feed preparation sugar manufacture is consumed in ethanol production
(Billore et al., 2001).
Ethanol can be produced from a wide range of feedstock.
These include sugar-based (cane and beet molasses, cane 2.2. Fermentation
juice), starch-based (corn, wheat, cassava, rice, barley) and
cellulosic (crop residues, sugarcane bagasse, wood, muni- Yeast culture is prepared in the laboratory and
cipal solid wastes) materials. Details of sugar, starch and propagated in a series of fermenters, each about 10 times
lignocellulosic biomass-based feedstock and their pre- larger than the previous one. The feed is inoculated with
treatment steps have been reviewed earlier (Wilkie et al., about 10% by volume of yeast (Saccharomyces cerevisiae)
2000). In general, sugar-based feedstock containing readily inoculum. This is an anaerobic process carried out under
available fermentable sugars are preferred since starch and controlled conditions of temperature and pH wherein
cellulosic substrates involve an additional pre-treatment reducing sugars are broken down to ethyl alcohol and
step to convert starch into fermentable sugars. Thus, cane carbon dioxide. The reaction is exothermic. To maintain
juice is a commonly used substrate in Brazil (Tano and the temperature between 25 and 32 1C plate heat exchan-
Buzato, 2003) while Indian distilleries almost exclusively gers are used; alternatively some units spray cooling water
use sugarcane molasses. Overall, nearly 61% of world on the fermenter walls. Fermentation can be carried out in
ethanol production is from sugar crops (Berg, 2004). either batch or continuous mode (CPCB, 2003). Fermenta-
The composition of molasses varies with the variety of tion time for batch operation is typically 2436 h with an
cane, the agro climatic conditions of the region, sugar efciency of about 95%. Continuous operation, involving
higher sugar concentration and an osmotolerant variety of
yeast, is faster (1624 h fermentation time) but the
Yeast Pre-fermenter efciency is marginally lower (T.R. Sreekrishnan, pers.
comm.). The resulting broth contains 68% alcohol. The
Diluted CO2 sludge (mainly yeast cells) is separated by settling and
molasses Fermenter

Analyzer Table 1
column Composition of cane and beet molasses (Curtin, 1983; Chen and Chou,
1993; Godbole, 2002)
Spentwash
Property Cane molasses Beet molasses

Rectification Brix (%) 79.5 79.5


column 8592b
Specic gravity 1.41 1.41
Spentlees 1.381.52a
Total solids (%) 75.0 77.0
7588a
Alcohol
Total sugars (%) 46.0 48.0
4460a
5090b
Crude protein (%) 3.0 6.0
Blending & Dehydration 2.54.5b
maturation (molecular sieve) Total fat (%) 0.0 0.0
Total ber (%) 0.0 0.0
Ash (%) 8.1 8.7
715b
Industrial Calcium (%) 0.8 0.2
Potable Power
alcohol alcohol Phosphorus (%) 0.08 0.03
alcohol
Potassium (%) 2.4 4.7
Sodium (%) 0.2 1.0
Chlorine (%) 1.4 0.9
Sulfur (%) 0.5 0.5
Bottling
a
Godbole (2002).
Fig. 1. Process description. b
Chen and Chou (1993).
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Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497 483

discharged from the bottom, while the cell free fermenta- (wash) is preheated to about 90 1C by heat exchange with
tion broth is sent for distillation. the efuent (spentwash) and then sent to the degasifying
Apart from yeast, the bacterium Zymomonas mobilis has section of the analyzer column. Here, the liquor is heated
also been investigated for ethanol production (Tao et al., by live steam and fractionated to give about 4045%
2005). The organism follows a simple catabolic pathway alcohol. The bottom discharge from the analyzer column is
(Toma et al., 2003) and has advantages over S. cerevisiae the spentwash. The alcohol vapors are led to the
because of its higher sugar uptake rate, lower biomass rectication column where by reux action, 96% alcohol
yields and higher ethanol production (Lin and Tanaka, is tapped, cooled and collected. The condensed water from
2006). Immobilization of Zymomonas cells has been tried this stage, known as spentlees is usually pumped back to
on support materials such as pectin because immobilized the analyzer column.
whole cells retain higher microbial activity (Siva Kesava
et al., 1996). However, formation of byproducts such as 2.4. Packaging
acetoin, glycerol, acetate, and lactate under anaerobic
conditions is a drawback associated with Z. mobilis. Rectied spirit (96% ethanol by volume) is marketed
During its growth on sucrose medium, Z. mobilis also directly for the manufacture of chemicals such as acetic
leads to formation of levan, a polymer of fructose units. acid, acetone, oxalic acid and absolute alcohol. Denatured
Further, like yeast, Zymomonas is unable to convert ethanol for industrial and laboratory use typically contains
complex carbohydrates like cellulose, hemicellulose and 6095% ethanol as well as between 1% to 5% each of
starch to ethanol. To overcome these constraints, genetic methanol, isopropanol, methyl isobutyl ketone (MIBK),
manipulation of Z. mobilis has been attempted by several ethyl acetate, etc. (Skerratt, 2004).
workers. For instance, the hydrolytic and isomerase genes For beverages, the alcohol is matured and blended with
from recombinant Escherichia coli have been transferred to malt alcohol (for manufacture of whisky) and diluted to
Z. mobilis, resulting in utilization of xylose, mannose, requisite strength to obtain the desired type of liquor. This
lactose and arabinose as the carbon source (Gunasekaran is bottled appropriately in a bottling plant. Anhydrous
and Raj, 1999). Earlier, Picataggio et al. (1996) reported ethanol for fuel-blending applications (power alcohol)
the development of genetically altered Zymomonas strain requires concentration of the ethanol to 499.5 wt% purity.
to ferment pentoses and glucose, obtained by hydrolysis of The ethanol dehydration is typically done using molecular
hemicellulose and cellulose, to produce ethanol. Here, Z. sieves; however, pervaporation has also been employed in
mobilis was transformed with combination of E. coli genes Brazil and India for this purpose (Mitsui & Co., 2003).
for xylose isomerase, xylulokinase, transaldolase, transke-
tolase, L-arabinose isomerase, L-ribulokinase, and L-ribu- 3. Wastewater generation and characteristics
lose-5-phosphate 4-epimerase. In another work aimed at
xylose utilization combined with enhanced ethanol yield, a Table 2 lists the major wastewater streams generated at
strain derived from Z. mobilis ATCC31821 was developed different stages in the alcohol manufacturing process.
(Zhang, 2000). The strain comprised of exogenous genes Table 3 summarizes the typical characteristics of spentwash
encoding xylose isomerase, xylulokinase, transaldolase and generated in Indian distilleries using sugarcane molasses.
transketolase. Values for beet molasses-based efuent are given for
comparison. The main source of wastewater generation is
2.3. Distillation the distillation step wherein large volumes of dark brown
efuent (termed as spentwash, stillage, slop or vinasse) is
Distillation is a two-stage process and is typically carried generated in the temperature range of 7181 1C (Yeoh,
out in a series of bubble cap fractionating columns. The 1997; Nandy et al., 2002; Patil et al., 2003). The
rst stage consists of the analyzer column and is followed characteristics of the spentwash depend on the raw
by rectication columns. The cell free fermentation broth material used (Mall and Kumar, 1997); also, it is estimated

Table 2
Sample quantities and characteristics of wastewater streams generated in an Indian distillery (S. Majumdar, pers. comm.)

Parameter Specic wastewater Color pH Suspended solids BOD (mg/l) COD (mg/l)
generation (kl/kl alcohol) (mg/l)

Spent wash 14.4 Dark brown 4.6 615 36,500 82,080


Fermenter cleaning 0.6 Yellow 3.5 3000 4000 16,500
Fermenter cooling 0.4 Colorless 6.3 220 105 750
Condenser cooling 2.88 Colorless 9.2 400 45 425
Floor wash 0.8 Colorless 7.3 175 100 200
Bottling plant 14 Hazy 7.6 150 10 250
Other 0.8 Pale yellow 8.1 100 30 250
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Table 3
Characteristics of spentwash generated from various feedstock (Pathade, 1999; Wilkie et al., 2000; Mahimairaja and Bolan, 2004)

Characteristics Feedstock

Cane molasses Beet molasses

Pathade (1999) Mahimairaja and Bolan (2004) Wilkie et al. (2000)

COD (mg/l) 65,000130, 000 104,000134,400 91,100


BOD (mg/l) 30,00070,000 46,10096,000 44,900
COD/BOD ratio 2.49 1.95
Total solids (mg/l) 30,000100,000
Total suspended solids (mg/l) 350
Total dissolved solids (mg/l) 80,000 79,00087,990
Total nitrogen (mg/l) 10002000 16604200 3569
Total phosphorus (mg/l) 8001200 2253038 163
Potassium (mg/l) 800012,000 960017,475 10,030
Sulfur as SO4 (mg/l) 20006000 32403425 3716
pH 35.4 3.94.3 5.35

that 88% of the molasses constituents end up as waste (Jain Spentwash


et al., 2002). Molasses spentwash has very high levels of
BOD, COD, COD/BOD ratio as well as high potassium, Biomethanation
phosphorus and sulfate content (Table 3). In addition, cane
molasses spentwash contains low molecular weight com-
pounds such as lactic acid, glycerol, ethanol and acetic acid Biocomposting Aerobic Solar Evaporation /
(Wilkie et al., 2000). treatement drying incineration
Cane molasses also contains around 2% of a dark brown
pigment called melanoidins that impart color to the
Dilution Tertiary treatment
spentwash (Kalavathi et al., 2001). Melanoidins are low
and high molecular weight polymers formed as one of the
nal products of Maillard reaction, which is a non-
Surface water
enzymatic browning reaction resulting from the reaction discharge
of reducing sugars and amino compounds (Martins and
van Boekel, 2004). This reaction proceeds effectively at Irrigation
temperatures above 50 1C and pH 47. The structure of
melanoidins is still not well known (Rivero-Perez et al., Fig. 2. Spentwash treatment options.
2002). Only 67% degradation of the melanoidins is
achieved in the conventional anaerobicaerobic efuent of inorganic fertilizers (Cortez and Perez, 1997; Rodr guez,
treatment process (Gonzalez et al., 2000). Due to their 2000). However, for the high strength molasses-based
antioxidant properties, melanoidins are toxic to many spentwash, the odor, putrefaction and unpleasant land-
microorganisms involved in wastewater treatment (Siria- scape due to unsystematic disposal are concerns in land
nuntapiboon et al., 2004a). Apart from melanoidins, application. In addition, this option is subject to land
spentwash contains other colorants such as phenolics, availability in the vicinity of the distillery; also, it is
caramel and melanin. Phenolics are more pronounced in essential that the disposal site be located in a lowmedium
cane molasses wastewater whereas melanin is signicant in rainfall area (Sheehan and Greeneld, 1980). More recent
beet molasses (Godshall, 1999). investigations have indicated that land disposal of distillery
efuent can lead to groundwater contamination (Joshi,
4. Efuent treatment 1999). Deep well disposal is another option but limited
underground storage and specic geological location limits
Till the early 1970s, land disposal was practiced as one of this alternative. Other disposal methods like evaporation of
the main treatment options, since it was found to enhance spentwash to produce animal feed and incineration of
yield of certain crops. For example, in Brazil, vinasse spentwash for potash recovery have also been practiced
generated from sugarcane juice fermentation is mainly used (Sheehan and Greeneld, 1980; Wilkie et al., 2000).
as a fertilizer due to its high nitrogen, phosphorus and Fig. 2 presents the options currently employed for
organic content. Its use is further reported to increase molasses spentwash treatment. The salient features of the
sugarcane productivity; furthermore under controlled existing options as well as the advances in this eld are
conditions, the efuent is capable of replacing application discussed in the following sections.
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Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497 485

4.1. Biological treatment retention time (SRT) so that slow growing anaerobic
microorganisms can remain in the reactor independent of
4.1.1. Anaerobic process wastewater ow. Table 4 summarizes the performance of
The high organic content of molasses spentwash makes various anaerobic reactors covering both laboratory
anaerobic treatment attractive in comparison to direct studies and pilot/commercial scale operations for treatment
aerobic treatment. Therefore, biomethanation is the of molasses-based distillery wastewaters.
primary treatment step and is often followed by two-stage
aerobic treatment before discharge into a water body or on 4.1.1.1. Suspended bed reactor. Upow anaerobic sludge
land for irrigation (Nandy et al., 2002). Aerobic treatment blanket (UASB) reactor is the most popular high rate
alone is not feasible due to the high energy consumption digester that has been utilized for anaerobic treatment of
for aeration, cooling, etc. Moreover, 50% of the COD is various types of industrial wastewaters (Akunna and
converted to sludge after aerobic treatment (Sennitt, 2005). Clark, 2000; Syutsubo et al., 1997). Treatment by a UASB
In contrast, anaerobic treatment converts over half of the reactor resulted in 75% COD removal in sugarcane
efuent COD into biogas (Wilkie et al., 2000). Anaerobic molasses spentwash and 90% COD reduction in whisky
treatment can be successfully operated at high organic pot ale (Goodwin and Stuart, 1994; Sanchez Riera et al.,
loading rates; also, the biogas thus generated can be 1985). However, dilution is required before treatment due
utilized for steam generation in the boilers thereby meeting to the presence of some inhibitory substances such as sulfur
the energy demands of the unit (Nandy et al., 2002). compounds, potassium and calcium ions and free hydrogen
Further, low nutrient requirements and stabilized sludge ions left in solution after pH correction (Sanchez Riera
production are other associated benets (Jimenez et al., et al., 1985). Wolmarans and de Villiers (2002) have
2004). reported a similar COD removal efciency of greater than
The performance and treatment efciency of anaerobic 90% over three seasons in a UASB plant treating distillery
process can be inuenced both by inoculum source and wastewater.
feed pre-treatment. In particular, thermal treatment of Most of the practical UASB systems are operated under
wastewaters can result in rapid degradation of organic mesophilic conditions; however, thermophilic operation
matter leading to lower hydraulic residence time (HRT), results in higher methanogenic activity. Mesophilically
higher loading rate and BOD reduction. Moreover the grown sludge utilized in thermophilic UASB as a seeding
methane content and caloric value of biogas produced material leads to prompt start up and stable operation with
from thermophilic systems was higher (Vlissidis and 85% COD removal efciency at a loading of 30 kg COD/
Zouboulis, 1993). On the contrary, in shake ask studies m3 d (Syutsubo et al., 1997). There are also reports on the
with an initial COD loading of 20,000 mg/l using biogas cultivation of thermophilic granular sludge for the seeding
plant sludge, Dhar et al. (1998a) observed a COD removal of thermophilic UASB reactor. Wiegant et al. (1985)
of just 6.5% with thermally pre-treated spentwash whereas reported the cultivation of thermophilic sludge on sucrose
untreated inuent displayed 30.4% COD removal. Sig- for a period of 4 months. The system after adaptation was
nicant improvement was observed using inoculum from able to take high COD loadings (86.4 kg/m3 d) and resulted
anaerobic lagoon with 27.2% COD reduction with in 60% COD removal efciency. In another study in a
thermally pre-treated wastewater and 51% reduction with thermophilic UASB reactor, Harada et al. (1996) reported
untreated wastewater. Thermal pre-treatment changes the 3967% COD removal, with a corresponding BOD
biodegradability of wastewater; thus, it acts as an entirely removal of over 80%. The results suggested that the
new feedstock for which the inoculum has to be wastewater contained high concentration of refractile
acclimatized afresh. Further, the temperature of thermal compounds; this, in turn, affected the microbial population
pre-treatment is also important. After 150 d adaptation in the sludge granules. Generally, the predominant genera
period, wastewater treated at lower temperature (170 1C) of methanogens in granular sludge are Methanobacterium,
showed 66% COD reduction (Dhar et al., 1998b). This was Methanobrevibacter, Methanothrix and Methanosarcina
nearly twice the removal obtained with treatment at 230 1C. (Bhatti et al., 1997); however, the predominance of
Further, addition of micronutrients (iron, boron and Methanothrix in granular sludge is most essential for the
molybdenum) eliminated the long adaptation periods. establishment of a high performance UASB process. In this
Anaerobic lagoons are the simplest option for the study, abundance of Methanosarcina sp. was observed
anaerobic treatment of distillery spentwash. Subba Rao whereas Methanothrix sp. was present to a lesser extent
(1972) reported that employing two anaerobic lagoons in thereby indicating that the latter are more sensitive to
series resulted in nal BOD levels up to 600 mg/l. However, refractile compounds (Harada et al., 1996).
large area requirement, odor problem and chances of
ground water pollution restrict its usage (Pathade, 1999). 4.1.1.2. Fixed bed reactor. This involves immobilization
Though anaerobic lagoons are still employed in Indian of microorganisms on some inert support to limit the loss
distilleries, high rate anaerobic reactors are more popular of biomass and enhance the bacterial activity per unit of
(Lata et al., 2002). These reactors offer the advantage of reactor volume. Moreover it provides higher COD removal
separating the hydraulic retention time (HRT) from solids at low HRT and better tolerance to toxic and organic
ARTICLE IN PRESS
486 Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497

Table 4
Performance of various anaerobic reactors for molasses distillery wastewater

Reactor conguration COD loading HRT (Days) % COD % BOD References


(kg COD/ reduction reduction
m3day)

UASB 24 75 Sanchez Riera et al. (1985)


UASBa 15 2.1 90 Goodwin and Stuart (1994)
UASBb 18 490 Wolmarans and de Villiers (2002)
Thermophilic UASB Up to 86.4 60 Wiegant et al. (1985)
Thermophilic UASB Up to 28 3967 480 Harada et al. (1996)
Thermophilic UASB Up to 30 0.3 87 Syutsubo et al. (1997)
Two-stage anaerobic treatmenta Blonskaja et al. (2003)
Anaerobic lter 2.55.1 1019 54
UASB 0.62.5 2039 93
Downow xed lm reactor 14.220.4 3.32.5 8597 6073 Bories et al. (1988)
Two-phase thermophilic process 65 85 Yeoh (1997)
Acidogenesis 4.620.0 2
Methanogenesis 15.2
Diphasic (upow) xed lm 22 3 71.8 Seth et al. (1995)
reactor (clay brick granules
support)
Diphasic (upow) xed lm 21.3 4 67.1 Goyal et al. (1996)
reactor (granular activated
carbon support)
Upow anaerobic lter (UAF)a 20 76 Tokuda et al. (1999)
Hybrid bafed reactor 20 77 Boopathy and Tilche (1991)
Downow uidized bed reactor 17 kg TOC/m3 d 0.35 7595% TOC Garc a-Bernet et al. (1998)
with ground perliteb
Downow uidized bed reactor 4.5 3.31.3 85 Garcia-Calderon et al., (1998)
with ground perliteb
Downow lter 8 5585 Athanasopoulos (1987)
Two-stage bioreactor(anaerobic) 7 71 86 Vlissidis and Zouboulis (1993)
Ist stage (upow sludge bed 11
reactor)
IInd stage (batch operated 0.10
bioreactor, occulator,
precipitator)
Anaerobic contact lter (in series) 4 7398 Vijayaraghavan and Ramanujam (2000)
Granular bed anaerobic bafed 4.75 8290 90 Akunna and Clark (2000)
reactor (GRABBR)a
Upow blanket lter 911 1112 70 Bardiya et al. (1995)
a
Malt whisky wastewater.
b
Winery wastewater.

shock loadings. In anaerobic contact lters, various higher sulfate concentration (426 mg/l), the removal
packing materials, viz. polyurethane, clay brick, granular decreased, possibly due to low SRB population in
activated carbon (GAC), polyvinyl chloride (PVC) plastic comparison to methanogens. Also the removal of sulde
media have been employed resulting in 6798% reduction was explained by stripping of hydrogen sulde from liquid
in COD (Bories et al., 1988; Seth et al., 1995; Goyal et al., to vapor phase by the carbon dioxide and methane
1996; Vijayaraghavan and Ramanujam, 2000). generated during the anaerobic process.
GAC as support media is relatively expensive but In another study, Tokuda et al. (1999) performed
because of its adsorptive properties, it contributes towards anaerobic treatment of undiluted whisky pot ale using an
improved process stability. The interference by sulfate, upow anaerobic lter (UAF) packed with special support
unionized sulte and total hydrogen sulde in anaerobic type (Pelia 4555, Herding GmbH, Germany) which
lters is reported to be negligible (Vijayaraghavan and resulted in 76% COD removal. The pilot system also
Ramanujam, 2000). It was observed that the percentage consisted of a decanter, dephosphatation or magnesium
sulfate removal increased with increasing HRT from 2 to ammonium phosphate (MAP) (MgNH4PO4) reactor,
5 d. This may be due to the utilization of sulfate as a denitrication reactor, nitrication reactor and sedimenta-
nutrient by microorganisms present in anaerobic contact tion tank for the reduction of nitrogen and phosphate.
lter and their conversion to sulde by sulfate reducing Downow lter using plastic PVC as support material
bacteria (SRB) under anaerobic conditions. However at has been employed for the treatment of beet molasses
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Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497 487

wastewater (Athanasopoulos, 1987). The system resulted in processing of beet molasses. The process consisted of two
5585% reduction in COD. Also, though high sulde stages: anaerobic digestion in upow sludge bed reactor
concentration (4250 mg) was inhibitory to the system, it followed by coagulationocculation with lime. The HRT
was not toxic at higher loadings (44 kg COD/m3 d) was 11 d in the bioreactor and 2.5 h in the occulatorpre-
probably due to high stripping of H2S. cipitator tank. On an average, the overall treatment scheme
resulted in 86% BOD and 71% COD removal. Biogas
4.1.1.3. Fluidized bed reactor. Fluidized bed reactors produced in the anaerobic reactor had a methane content
contain an appropriate media such as sand, gravel or of 76%. This conguration was reported to be efcient in
plastics for bacterial attachment and growth. The reactors treating undiluted wastewaters.
can be operated either in the upow or downow modes,
with uidization being realized by applying high uid 4.1.2. Aerobic treatment
velocities, normally by efuent recycling. Studies on The post-anaerobic treatment stage efuent still has high
distillery efuent treatment in a downow uidized bed organic loading and is dark brown in color, hence it is
system using ground perlite (an expanded volcanic rock) generally followed by a secondary, aerobic treatment. Solar
resulted in 7595% reduction in carbon content (Garc a- drying of biomethanated spentwash is one option but the
Bernet et al., 1998). The utilization of ground perlite as a large land area requirement limits this practice. Further, in
carrier material was advantageous in the downow India, solar drying beds become non-functional during the
conguration because it requires low uidization velocities rainy season (Nandy et al., 2002). The other treatment
which preclude the possibility of clogging. options that have been demonstrated for biomethanated
distillery efuent are described below.
4.1.1.4. Two-stage processes and hybrid reactors. A two-
stage process with an anaerobic lter followed by a UASB  Aquaculture: Post-biomethanted efuent has been used
reactor was investigated by Blonskaja et al. (2003). The for pisciculture near Chennai city in southern India. The
acidogenic and methanogenic phases were clearly separated biodigested efuent, which is a rich growth medium, is
ensuring better conditions for the methanogens. COD directed to bioconversion ponds after which it is spread
reduction was 54% and 93% in the rst and second stage, in about 6 ha of shponds. The BOD is reduced to
respectively. In another study on a two-phase thermophilic nearly zero and the initiative yields about 50 tons per
system, 65% COD reduction combined with a three-fold hectare per year of sh (Vorion Chemicals & Distilleries
increase in biogas yield over a single phase system was Ltd., 1999).
observed (Yeoh, 1997). Boopathy and Tilche (1991) studied  Constructed wetlands (CWs): Billore et al. (2001) have
the anaerobic digestion of 312 times diluted beet molasses demonstrated a four-celled horizontal subsurface ow
wastewater, without pH adjustment, in a hybrid anaerobic (HSF) CW for the treatment of distillery efuent after
bafed reactor (HABR). Additional nitrogen and phos- anaerobic treatment. The post-anaerobic treated efuent
phorus were provided in the form of urea (0.007 g/g of had a BOD of about 2500 mg/l and a COD of nearly
COD) and diammonium hydrogen phosphate (0.0006 g/g 14,000 mg/l. A pre-treatment chamber lled with gravel
of COD). The reactor consisted of three chambers and a was used to capture the suspended solids. All the cells
nal settler. 77% COD removal at a loading rate of were lled with gravel up to varying heights and cells
20 kg COD/m3 d was obtained. three and four supported the plants Typha latipholia and
Several variations of the UASB reactor have been Phragmites karka respectively. The overall retention
investigated for distillery wastewater treatment. In large- time was 14.4 d and the treatment resulted in 64% COD,
scale operations, highly variable process wastewater ows 85% BOD, 42% total solids and 79% phosphorus
makes it difcult to maintain suitable inlet UASB ow rate; content reduction. In another study, a laboratory scale
further, prevention of the loss of low density granules is CW employing T. latipholia was used to treat diluted
also important. To overcome these problems, Akunna and distillery efuent (Trivedy and Nakate, 2000). A root
Clark (2000) used granular-bed anaerobic bafed reactor zone of 1.5  0.3  0.3 m, lled with 75% sand and
(GRABBR). The reactor consisted of 10 equal compart- gravel and 25% soil was used and the diluted efuent
ments, each of which was further divided into two with was applied after 4 weeks of planting. The system
suitable bafes. Acidogenesis was found to be predominant resulted in 76% COD reduction in 7 d which increased
in the compartments near the inlet and methanogenesis in marginally to 78% COD reduction in 10 d. The BOD
those located near the outlet. 8290% COD reduction was reduction was 22% and 47% on days 7 and 10,
observed at a HRT of 4 d. Yet another modication is respectively. In yet another instance, a distillery in
upow blanket lter (UBF) in which the packing is limited northern India is presently employing CW for polishing
to 510% height of the reactor. This conguration resulted the efuent prior to land discharge for irrigation in the
in 70% COD removal in sugarcane molasses distillery surrounding paddy elds (M.K. Pilania, pers. comm.).
spentwash (Bardiya et al., 1995). The efuent is initially subjected to primary treatment
Vlissidis and Zouboulis (1993) have investigated the which includes settling and anaerobic digestion in
thermophilic anaerobic treatment of wastewater from the a structured media attached growth (SMAG)-type
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anaerobic reactor. The primary treated efuent, with a enhancing the effectiveness of anaerobic process (Borja
COD of 28,00035,000 mg/l, is subjected to two-stage et al., 1993).
aeration to bring down the COD to 400 mg/l. There- The following sections discuss pure culture studies on
after, it is directed to a CW before nal discharge. molasses distillery wastewater targeting both COD reduc-
 Biocomposting: The spentwash, either directly, or after tion and efuent decolorization.
biomethanation is sprayed in a controlled manner on
sugarcane pressmud. The latter is the lter cake 4.1.2.1. Fungal treatment. White rot fungus secreting
obtained during juice clarication in the manufacture ligninolytic enzymes are capable of degrading xenobiotics
of sugar. Biocomposting is an aerobic, thermophilic and organopollutants. Phanerochaete chrysosporium and
process resulting in a product rich in humus which is Trametes versicolor are the most widely studied among
thus used as a fertilizer. This is a popular option these (Gonzalez et al., 2000). P. chrysosporium JAG 40
adopted by several Indian distilleries attached to sugar resulted in 80% decolorization of diluted synthetic
mills with adequate land availability. melanoidin (absorbance unit of 3.5 at 475 nm), as well as
with 6.25% anaerobically digested spentwash (Kumar et
The most common post-biomethanation step is the al., 1998; Dahiya et al., 2001a). T. versicolor produces a
activated sludge process wherein research efforts are 47 kDa extracellular enzyme identied as peroxidase which
targeted at improvements in the reactor conguration is involved in mineralization of melanoidins. The fungus
and performance. For instance, aerobic sequencing resulted in 82% decolorization of 12.5% anaerobical-
batch reactor (SBR) is reported to be a promising solu- lyaerobically treated efuent. Of this, 90% color was
tion for the treatment of efuents originating from removed biologically and the rest by adsorption on the
small wineries (Torrijos and Moletta, 1997). The treatment mycelium (Dehorter and Blondeau, 1993; Benito et al.,
system consisted of a primary settling tank, an interme- 1997). In addition, treatment by Trametes species I-62
diate retention trough, two storage tanks and an aerobic (CECT 20197) detoxies the efuent by degrading furan
treatment tank. A start up period of 7 d was given to derivatives as observed by gas chromatography analysis
the aerobic reactor and the system resulted in 93% COD (Gonzalez et al., 2000).
and 97.5% BOD removal. Another conguration that Decolorization of melanoidin pigment has also been
has been examined is the rotating biological reactor reported by extracellular H2O2 and peroxidase produced
(RBR) (de Bazua et al., 1991). The system consisted of by Coriolus hirsutus (Miyata et al., 1998). For 6.25%
300 l anaerobic uidized bed reactor coupled with a 3000 l anaerobically digested spentwash, this species showed
RBR. Both the reactors were tested with diluted raw 7175% reduction in color and 90% reduction in COD
vinasse with a COD of 6070 g/l. At a HRT of 2 d (Kumar et al., 1998). Further, Coriolus versicolor Ps4a
and COD loading up to 20 kg COD m3/day, the anaerobic decolorizes the efuent by decomposition of melanoidins
unit resulted in 70% COD removal while a lower and not by the partial transformation of chromophores.
46% COD removal was obtained in the aerobic step. The decolorizing activity was attributed to an intracellular
Further testing in the aerobic system was planned with enzyme which is induced in the presence of melanoidin
the efuent from anaerobic reactor but no results were pigment (Aoshima et al., 1985). Treatment of biodigested
reported. distillery wastewater by C. versicolor has also been
The activated sludge process and its variations utilize investigated by Chopra et al. (2004). The fungus was able
mixed cultures. To enhance the efciency of aerobic to reduce both COD and color up to 53% in 8 d; however,
systems, several workers have focused on treatment by glucose and peptone were required as additional nutrient
pure cultures. Further, aerobic treatment has also been sources.
examined as a precursor to anaerobic treatment. In studies In another study, Raghukumar et al. (2004) used a
on both beet spentwash and molasses, aerobic pre- marine fungus, Flavodon flavus for the combined decolor-
treatment of beet spentwash with Penicillium decumbens ization and detoxication of 10% molasses spentwash. It
resulted in about 74% reduction in phenolics content and was suspected that Maillard reaction also resulted in the
40% reduction in color (Jimenez et al., 2003). Anaerobic formation of pyrogenic compounds like polycyclic aro-
digestion without aerobic pre-treatment resulted in a sharp matic hydrocarbons (PAHs) that are toxic to estuarine sh.
drop in COD removal efciencies with decreasing HRT. Treatment by F. flavus detoxied the efuent by 68%
The organic matter removal was marginally higher for beet reduction in PAH and resulted in 73% color removal. The
molasses previously fermented with P. decumbens. The fungus was more effective in decolorizing raw molasses
anaerobic reaction followed rst-order kinetics and the rate spentwash than the anaerobically and aerobically treated
constant decreased on increasing the organic loading with streams. This was possibly due to changes in the chemical
untreated molasses; however, it remained almost constant structure of the melanoidin pigments during anaerobic and
with pre-treated molasses (Jimenez et al., 2003, 2004). aerobic treatment. However, the oxygen demand of the
Geotrichum candidum is another species that resulted in fungus was reportedly high.
partial elimination of phenolic inhibitors such as gentisic The effects of lamentous fungi have also been studied
acid, gallic acid, quercetin, p-coumaric acid, etc., thereby on distillery wastewater. These are comparatively slow
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growing species and more susceptible to infection but the at 475 nm) was originally 47 for the raw spentwash but it
production of a series of extracellular hydrolytic enzymes was diluted to a value of 3.5 before use (Sirianuntapiboon
makes it easier for them to grow on starch and cellulose et al., 1988). However, a lower color removal of 6065%
substrates. Among the lamentous species, Aspergillus sp. was obtained for the wastewater from anaerobic and
is the most popular (Friedrich, 2004). A. niveus and A. niger aerobic ponds. This was possibly due to either the
resulted in 6069% reduction in color and 7595% COD formation of some toxic compounds during anaerobic
removal; also, the treated efuent enhanced the seedling and aerobic treatment or the inability of the strain to
growth in Zea mays (Angayarkanni et al., 2003; Miranda et attack the color causing compound due to a change in their
al., 1996). Immobilized fungal isolate of A. niger UM2 structure during anaerobic and aerobic treatment.
resulted in a 72% decolorization of diluted synthetic
melanoidin (absorbance unit of 3.5 at 475 nm) and 80% 4.1.2.2. Bacterial treatment. Treatment of distillery was-
decolorization of 50% biodigested efuent (Patil et al., tewater by the use of Pseudomonas putida followed by
2003). Similarly, a thermophilic strain of A. fumigatus G-2- Aeromonas sp. in a two-stage bioreactor resulted in COD
6 decolorized 75% of melanoidin pigment solution at as well as color reduction (Ghosh et al., 2002). P. putida
45 1C. Gel ltration chromatography revealed that large produces hydrogen peroxide which is a strong decolorizing
molecular weight fractions of melanoidins, in particular, agent. Since the organism cannot use spentwash as a source
were degraded rapidly (Ohmomo et al., 1987). of carbon, 1% w/v glucose supplement was provided along
Apart from white-rot and lamentous fungi, yeast has with 12.5% spentwash. Aeromonas sp. utilizes the carbo-
also been investigated for distillery wastewater treatment. naceous compounds present in spentwash as the sole
Yeast is characterized by quick growth and is less carbon source, thereby eventually reducing the efuent
susceptible to contamination by other microorganisms; COD by 66% in a 24 h period. P. putida also resulted in
further, yeast produces biomass with high nutritive value 44% COD removal accompanied by 60% color reduction.
(Friedrich, 2004). The yeast Citeromyces WR-43-6 resulted In another study on predigested distillery efuent with
in high and stable removal efciency in both color intensity Aeromonas formicans, 57% COD reduction and 55%
and organic matter. The removal efciencies for diluted decrease in color was observed after 72 h (Jain et al.,
spentwash (absorbance unit of 3.5 at 475 nm) were 75% for 2000). The color removal efciency increased up to 68%
color intensity and 76% for BOD (Sirianuntapiboon et al., using the bacteria immobilized on calcium alginate beads;
2004a). Shojaosadati et al. (1999) optimized the growth however, the COD reduction remained unchanged with
conditions for single cell protein (SCP) production and longer incubation period of up to 96 h.
COD reduction by the use of Hansenula sp. in sugar beet P. fluorescence immobilized on porous cellulose carrier
stillage. They concluded that production of SCP from resulted in 66% color removal with non-sterile diluted
stillage is one of the most promising options. Besides, the spentwash (absorbance unit of 3.5 at 475 nm) and 90%
yeast was also found to utilize lactate and acetate that are decolorization with sterile samples at 30 1C over a 4 d
inhibitory to ethanol production. As a result, the treated period (Dahiya et al., 2001b). The decolorization efciency
efuent could be used as dilution water for fermentation was further increased to 94% with cellulose carrier coated
thereby reducing the residual stillage volume by 70%. with collagen. These immobilized cells could be reused but
Another strain of Hansenula anomala J 45-N-5 and I-44 the efcacy of color removal was reduced. In another
isolated from soil, resulted in 74% reduction in total study, three different bacterial strains Xanthomonas fragar-
organic carbon (TOC) (Moriya et al., 1990). S. cerevisiae iae, Bacillus megaterium and Bacillus cereus were used both
also provides promising results on a larger scale. The use of in free form as well as after immobilization on calcium
pure culture of S. cerevisiae resulted in 82.7% decoloriza- alginate beads for the treatment of 33% predigested
tion in the 10% anaerobically treated distillery efuent distillery efuent (Jain et al., 2002). B. cereus resulted in
along with 84% reduction in COD (Selim et al., 1991; maximum COD (81%) and color (75%) reduction in free
Rajor et al., 2002). It was also reported that the nitrogen form. The reduction efciencies increased marginally with
present in the distillery efuent was sufcient for the immobilization.
growth of yeast. The decolorization activity of acetogenic bacteria has
The dye decolorizing fungus G. candidum Dec 1 been reported for the rst time by Sirianuntapiboon et al.
immobilized on polyurethane foam resulted in 80% (2004b). Acetogenic bacteria is capable of oxidative
removal in color in diluted molasses solution (4050 g/l) decomposition of melanoidins thereby removing low
(Kim and Shoda, 1999). In case of pure culture experi- molecular weight compounds in untreated molasses spent-
ments, Candida utilis and Trichoderma viridiae each showed wash and almost all the low and high molecular weight
less than 65% reduction in COD whereas C. utilis and A. compounds in anaerobically treated molasses spentwash.
niger together resulted in 89% COD removal (Nudel et al., Nearly 76% decolorization, which is possibly due to a
1987). This reduction was from sugarcane stillage-based sugar oxidase, has been observed. The nitrifying bacteria
media with an initial COD of 4075 g/kg. The fungus Nitrosococcus oceanus is capable of detoxifying the
Mycelia sterilia D90 resulted in 91% decolorization of raw spentwash accompanied by a reduction in the chloride
spentwash. The color intensity (in terms of absorbance unit content (Arora et al., 1992). However, no explanation was
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490 Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497

provided for this observation. The treated wastewater leads sulphate (OSO3 ) groups that can form complexes with
to better growth of rice plant due to adequate nitrogen cationic sites thereby resulting in occulation of organic
content and can therefore be used as a low cost fertilizer. In matter in the efuent. It was observed that the strain
yet another investigation, two aerobic bacterial strains TA Oscillatoria resulted in almost complete color removal
2 and TA 4 have been isolated from sites contaminated (96%) whereas Lyngbya and Synechocystis were less
with anaerobically treated distillery efuent (Asthana et al., effective resulting in 81 and 26% color reduction,
2001). These bacteria, which were identied to be Gram- respectively (Patel et al., 2001). The consortium of the
negative and Gram-positive, respectively, resulted in 66% three strains showed a maximum decolorization of 98%.
and 62% BOD reduction in anaerobically treated spent- This was attributed to adsorption in the initial stages
wash. However the reduction in BOD was found to be followed by degradation of organic compounds which
higher (80%) when the two were used together; further the dominated in the subsequent stages.
combination resulted in 76% color removal after 72 h.
More recently, the decolorization of four types of
4.2. Physico-chemical treatment
synthetic melanoidins i.e., glucoseglutamic-acid (GGA),
glucoseaspartic-acid (GAA), sucroseglutamic acid
Sugarcane molasses spentwash after biological treatment
(SGA), and sucroseaspartic-acid (SAA), were investigated
by both anaerobic and aerobic method can still have a
using three different isolates, viz. Bacillus thuringiensis,
BOD of 250500 mg/l (Mall and Kumar, 1997). Also, even
Bacillus brevis and Bacillus sp. (Kumar and Chandra,
though biological treatment results in signicant COD
2006). The degree of decolorization of the melanoidins
removal, the efuent still retains the dark color (Inanc et
separately by each isolate was in the 131% range;
al., 1999). The color imparting melanoidins are barely
however, when used collectively, these isolates resulted in
affected by conventional biological treatment such as
up to 50% decolorization due to the enhanced effect of
methane fermentation and the activated sludge process
coordinated metabolic interactions. The results also
(Migo et al., 1993). Further, multistage biological treat-
indicated that the GAA polymer was the most recalcitrant
ment reduces the organic load but intensies the color due
among the melanoidins tested.
to re-polymerization of colored compounds (Pena et al.,
The biodegradability of spentwash can be enhanced by
2003). In this context, various physico-chemical treatment
enzymatic pre-treatment prior to the aerobic step (Sangave
options have been explored.
and Pandit, 2006a). After 24 h of treatment with Gram-
positive bacterium ASN6, the COD reduction of cellulase
pre-treated spentwash was 28.8% in comparison to 18.3% 4.2.1. Adsorption
for untreated efuent. This was explained by the fact that Activated carbon is a widely used adsorbent for the
pre-treatment affected the metabolic value (microbial removal of organic pollutants from wastewater but the
acceptability) by generating intermediate hydrolysis pro- relatively high cost restricts its usage. Decolorization of
ducts from the parent cellulosic compounds present in the synthetic melanoidin using commercially available acti-
spentwash. The biodegradability was further enhanced by vated carbon as well as activated carbon produced from
combined ultrasound and enzymatic pre-treatment result- sugarcane bagasse was investigated by Bernardo et al.
ing in 62.2% COD reduction after 36 h as compared to (1997). The adsorptive capacity of the different activated
39.4% COD removal for the untreated efuent (Sangave carbons was found to be quite comparable. Chemically
and Pandit, 2006b). The enhancement in biodegradability modied bagasse using 2-diethylaminoethyl chloride hy-
was attributed to molecular transformation of efuent drochloride and 3-chloro-2-hydroxypropyltrimethylammo-
constituents by ultrasound pre-treatment. nium chloride was capable of decolorizing diluted
spentwash (Mane et al., 2006). 0.6 g of chemically modied
4.1.2.3. Algal treatment. The treatment of anaerobically bagasse in contact with 100 ml 1:4 (v/v) spentwash:water
treated 10% distillery efuent using the microalga Chlor- solution resulted in 50% decolorization after 4 h contact
ella vulgaris followed by Lemna minuscula resulted in 52% with intermittent swirling.
reduction in color (Valderrama et al., 2002). In another Signicant decolorization was observed in packed bed
study, Kalavathi et al. (2001) examined the degradation of studies on anaerobically treated spentwash using commercial
5% melanoidin by the marine cyanobacterium Oscillatoria activated charcoal with a surface area of 1400 m2/g (Chandra
boryana BDU 92181. The organism was found to release and Pandey, 2000). Almost complete decolorization (499%)
hydrogen peroxide, hydroxyl ions and molecular oxygen was obtained with 70% of the eluted sample, which also
during photosynthesis resulting in 60% decolorization of displayed over 90% BOD and COD removal. In contrast,
distillery efuent. In addition, this study suggested that other workers have reported adsorption by activated carbon
cyanobacteria could use melanoidin as a better nitrogen to be ineffective in the treatment of distillery efuent (Sekar
source than carbon. Further, cyanobacteria also excrete and Murthy, 1998; Mandal et al., 2003). Adsorption by
colloidal substances like lipopolysaccharides, proteins, commercially available powdered activated carbons resulted
polyhydroxybutyrate (PHB), polyhydroxy-alkanoates in only 18% color removal; however, combined treatment
(PHA), etc. These compounds possess COO and ester using coagulationocculation with polyelectrolyte followed
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Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497 491

by adsorption resulted in almost complete decolorization organic anionic polyelectrolyte, in combination with
(Sekar and Murthy, 1998). ferrous sulfate and lime. The combination resulted in
Low cost adsorbents such as pyorchar (activated carbon 99% reduction in color and 87 and 92% reduction in COD
both in granular and powdered form, manufactured from and BOD, respectively. Similar ndings have also been
paper mill sludge) and bagasse yash have also been reported by Mandal et al. (2003).
studied for this application. Ramteke et al. (1989) reported Coagulation studies on spentwash after anaerobicaero-
color removal up to 98% with pyorchar. However, to bic treatment have also been conducted using bleaching
achieve the same level of color removal, larger doses of the powder followed by aluminum sulfate (Chandra and Singh,
indigenously prepared powdered and granular pyorchar 1999). The optimum dosage was 5 g/l bleaching powder
were required in comparison to commercial activated followed by 3 g/l of aluminum sulfate that resulted in 96%
carbon. Mall and Kumar (1997) compared the color removal in color, accompanied by up to 97% reduction in
removal using commercial activated carbon and bagasse BOD and COD.
yash. 58% color removal was reported with 30 g/l of Non-conventional coagulants namely wastewater from
bagasse yash and 80.7% with 20 g/l of commercial an iron pickling industry which is rich in iron and chloride
activated carbon. Since the bagasse yash has high carbon ions and titanium ore processing industry containing
content and the adsorbed organic material further in- signicant amounts of iron and sulfate ions have also been
creases its heating value, the spent adsorbent can be used examined (Pandey et al., 2003). The iron pickling waste-
for making re briquettes. Yet another adsorbent that has water gave better results with 92% COD removal,
been examined is the natural carbohydrate polymer combined with over 98% color removal. Though the
chitosan derived from the exoskeleton of crustaceans. titanium processing wastewater exhibited similar color
Lalov et al. (2000) studied the treatment of distillery removal levels, the COD and BOD reductions were
wastewater using chitosan as an anion exchanger. At an perceptibly lower.
optimum dosage of 10 g/l and 30 min contact time, 98%
color and 99% COD removal was observed. 4.2.3. Oxidation process
Ozone destroys hazardous organic contaminants and has
4.2.2. Coagulation and flocculation been applied for the treatment of dyes, phenolics,
Inanc et al. (1999) reported that coagulation with alum pesticides, etc. (Pena et al., 2003). Oxidation by ozone
and iron salts was not effective for color removal. They could achieve 80% decolorization for biologically treated
explored lime and ozone treatment with anaerobically spentwash with simultaneous 1525% COD reduction. It
digested efuent. The optimum dosage of lime was found also resulted in improved biodegradability of the efuent.
to be 10 g/l resulting in 82.5% COD removal and 67.6% However, ozone only transforms the chromophore groups
reduction in color in a 30 min period. These ndings are in but does not degrade the dark colored polymeric com-
disagreement with those of Migo et al. (1993) who used a pounds in the efuent (Alfafara et al., 2000; Pena, et al.,
commercial inorganic occulent, a polymer of ferric 2003). Similarly, oxidation of the efuent with chlorine
hydroxysulfate with a chemical formula [Fe2 (OH)n resulted in 497% color removal but the color reappeared
(SO4)3 n/2]m for the treatment of molasses wastewater. after a few days (Mandal et al., 2003). Ozone in
The treatment resulted in around 87% decolorization for combination with UV radiation enhanced spentwash
biodigested efuents; however an excess of occulent degradation in terms of COD; however, ozone with
hindered the process due to increase in turbidity and hydrogen peroxide showed only marginal reduction even
TOC content. FeCl3 and AlCl3 were also tested for on a very dilute efuent (Beltran et al., 1997).
decolorization of biodigested efuent and showed similar In another study, Sangave and Pandit (2004) employed
removal efciencies. About 93% reduction in color and sonication of distillery wastewater as a pre-treatment step
76% reduction in TOC were achieved when either FeCl3 or to convert complex molecules into a more utilizable form
AlCl3 was used alone. The process was independent of by cavitation. Samples exposed to 2 h ultrasound pre-
chloride and sulfate ion concentration but was adversely treatment displayed 44% COD removal after 72 h of
affected by high uoride concentration. However in the aerobic oxidation compared to 25% COD reduction shown
presence of high occulent concentration (40 g/l), addition by untreated samples. These results are contrary to those of
of 30 g/l CaO enhanced the decolorization process resulting Mandal et al. (2003) who concluded ultrasonic treatment to
in 93% color removal. This was attributed to the ability of be ineffective for distillery spentwash treatment.
calcium ions to destabilize the negatively charged mela- A combination of wet air oxidation and adsorption has
noidins; further, formation of calcium uoride (CaF2) also been successfully used to demonstrate the removal of
precipitates the uoride ions. sulfates from distillery wastewater. Studies were done in a
Almost complete color removal (98%) of biologically counter current reactor containing 25 cm base of small
treated distillery efuent has been reported with conven- crushed stones supporting a 20 cm column of bagasse ash
tional coagulants such as ferrous sulfate, ferric sulfate and as an adsorbent (Gaikwad and Naik, 2000). The waste-
alum under alkaline conditions (Pandey et al., 2003). The water was applied from the top of the reactor and air was
best results were obtained using Percol 47, a commercial supplied at the rate of 1.0 l/min. The treatment removed
ARTICLE IN PRESS
492 Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497

57% COD, 72% BOD, 83% TOC and 94% sulfates. Wet western India is currently processing efuent obtained after
air oxidation has been recommended as part of a combined anaerobic digestion, followed by hold-up in a tank
process scheme for treating anaerobically digested spent- maintained under aerobic conditions, in a RO system
wash (Dhale and Mahajani, 2000). The post-anaerobic (B.P. Agrawal, pers. comm.). 290 m3/d of RO treated
efuent was thermally pre-treated at 150 1C under pressure efuent is mixed with 300 m3/d of fresh water and used in
in the absence of air. This was followed by soda-lime the process for various operations like molasses dilution
treatment, after which the efuent underwent a 2 h wet (290 m3/d), make-up water for cooling tower (178 m3/d),
oxidation at 225 1C. 95% color removal was obtained in fermenter washing (45 m3/d), etc. Yet another unit in
this scheme. Another option is photocatalytic oxidation southern India is employing disc and tube RO modules for
that has been studied using solar radiation and TiO2 as the direct treatment of the anaerobically digested spentwash
photocatalyst (Kulkarni, 1998). Use of TiO2 was found to (M. Prabhakar Rao, pers. comm.). The permeate is
be very effective as the destructive oxidation process leads discharged while the concentrate is used for biocomposting
to complete mineralization of efuent to CO2 and H2O. Up with sugarcane pressmud. In a recent study, Nataraj et al.
to 97% degradation of organic contaminants was achieved (2006) reported pilot trials on distillery spentwash using a
in 90 min. hybrid nanoltration (NF) and RO process. Both the NF
Pikaev et al. (2001) studied combined electron beam and and RO stages employed thin lm composite (TFC)
coagulation treatment of distillery slops from distilleries membranes in spiral wound conguration with module
processing grain, potato, beet and some other plant dimensions of 2.5 inches diameter and 21 inches length. NF
materials. Humic compounds and lignin derivatives con- was primarily effective in removing the color and colloidal
stitute the major portion of this dark brown wastewater. particles accompanied by 80%, 95% and 45% reduction in
The distillery wastewater was diluted with municipal total dissolved solids (TDS), conductivity and chloride
wastewater in the ratio of 3:4, irradiated with electron concentration, respectively, at an optimum feed pressure of
beam and then coagulated with Fe2(SO4)3. The optical 3050 bar. The subsequent RO operation at a feed pressure
absorption in UV region was decreased by 6570% after of 50 bar resulted in 99% reduction each in COD,
this treatment. The cost was found to be less than the potassium and residual TDS.
existing method wherein the efuent was transported about
20 km via pipeline to a facility for biological treatment 4.2.5. Evaporation/combustion
followed by sedimentation. The treatment cost was Molasses spentwash containing 4% solids can be
0.450.65 US$/m3 which dropped to 0.25 US$/m3 using concentrated to a maximum of 40% solids in a quintu-
combined electronic-beam and coagulation method. ple-effect evaporation system with thermal vapor recom-
pression (Bhandari et al., 2004; Gulati, 2004). The
4.2.4. Membrane treatment condensate with a COD of 280 mg/l can be used in
Pre-treatment of spentwash with ceramic membranes fermenters. The concentrated mother liquor is spray dried
prior to anaerobic digestion is reported to halve the COD using hot air at 180 1C to obtain a desiccated powder with a
from 36,000 to 18,000 mg/l (Chang et al., 1994). The total caloric value of around 3200 kcal/kg. The powder is
membrane area was 0.2 m2 and the system was operated at typically mixed with 20% agricultural waste and burnt in a
a uid velocity of 6.08 m/s and 0.5 bar transmembrane boiler. The use of recirculating uidized bed (RCFB)
pressure. In addition to COD reduction, the pre-treatment incinerator is recommended to overcome the constraints
also improved the efciency of the anaerobic process due to stickiness of spentwash and its high sulfate content
possibly due to the removal of inhibiting substances. (Alappat and Rane, 1995). Combustion is also an effective
Kumaresan et al. (2003) employed emulsion liquid method of on-site vinasse disposal as it is accompanied by
membrane (ELM) technique in a batch process for production of potassium-rich ash (Cortez and Perez, 1997)
spentwash treatment. Wateroilwater type of emulsion that can be used for land application.
was used to separate and concentrate the solutes resulting
in 86% and 97% decrease in COD and BOD, respectively. 5. Discussion
Electrodialysis has been explored for desalting spentwash
using cation and anion exchange membranes resulting in A range of biological and physico-chemical methods
5060% reduction in potassium content (de Wilde, 1987). have been investigated for the treatment of wastewater
In another study, Vlyssides et al. (1997) reported the from molasses-based distilleries. Because of the very high
treatment of vinasse from beet molasses by electrodialysis COD, anaerobic treatment with biogas recovery is
using a stainless steel cathode, titanium alloy anode and employed extensively as the rst treatment step. Anaerobic
4% w/v NaCl as electrolytic agent. Up to 88% COD lagoons are still used; however, most Indian distilleries
reduction at pH 9.5 was obtained; however, the COD employ high rate digesters wherein the HRT is decoupled
removal percentage decreased at higher wastewater from the SRT thereby retaining the slow growing
feeding rates. anaerobic microorganisms in the reactor even at high
In addition, reverse osmosis (RO) has also been wastewater ow. Biomethanation reduces the organic
employed for distillery wastewater treatment. A unit in pollution load and brings down BOD to 8095% of the
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Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497 493

original value; however, the biodigested efuent still 2002). Membrane operations like microltration/ultral-
contains BOD in the range of 500010,000 mg/l (Pathade, tration for spentwash treatment are characterized by
1999). Moreover, anaerobic treatment is a slow process and signicant membrane fouling that limits its applicability
typically requires long start-up periods. In addition, the (Jain and Balakrishnan, 2004). Decolorization through
problem of color associated with this efuent not only chemical treatment with ozone and chlorine leads to
remains unsolved (Patil et al., 2003) but actually gets temporary color reduction because of transformation of
aggravated since the color causing melanoidin pigment the chromophore groups so these are not preferred
intensies under anaerobic conditions (Pena et al., 2003). solutions.
Therefore anaerobically treated efuent is darker in color Thus, solutions for effective management of molasses-
compared to untreated spentwash and needs several-fold based distillery wastewaters are still evolving. Some of the
dilution by fresh water prior to discharge. The current gaps are highlighted below:
practice of using diluted, biodigested spentwash for
irrigation (ferti-irrigation) by a large number of Indian  Biomethanation of spentwash is well established com-
distilleries is reportedly causing gradual soil darkening mercially; however, there is scope for several operational
(Kumar et al., 1998). Yet another limitation is the need to improvements. These include adapting the system to
dilute the spentwash prior to biomethanation itself. Most treat the spentwash without any dilution, ensuring
distilleries follow 13-fold dilution to ensure proper shorter start-up periods and degrading refractile com-
operation of the biomethanation plant. Since 815 l ponents to improve the anaerobic treatment efciency.
spentwash is generated per liter of ethanol, dilution Also, a better understanding of the re-polymerization of
increases the load on the efuent treatment plant besides color-causing compounds during anaerobic digestion
consuming considerable amount of fresh water for this would assist in the subsequent decolorization steps.
purpose.  Biocomposting with sugarcane pressmud is increasingly
Biological treatment using aerobic processes like acti- being adopted by a number of sugar complexes as a
vated sludge, biocomposting etc. is presently practiced by method for disposing the biodigested spentwash. How-
various molasses-based distilleries. Due to the large ever, pressmud availability is limited; thus, alternative
volumes generated, only a part of the total spentwash gets materials like rice husk, wood chips, bagasse pith etc.
consumed in biocomposting. Biocomposting utilizes su- have been suggested (CPCB, 1994). This requires
garcane pressmud as the ller material; thus it is typically exploring readily available local ller materials that
employed by distilleries attached to sugar mills. Since sugar can be utilized for this purpose. Also, the issue of
manufacturing is a seasonal operation, pressmud avail- manure quality, possibly to match the requirements of
ability is often a constraint. Further, biocomposting local crops, can be addressed.
requires large amount of land; also, it cannot be carried  The structure and characteristics of the color-causing
out during the rainy season. components (melanoidins) is still not fully understood.
Though aerobic treatment like the conventional acti- This has consequently hindered the development of an
vated sludge process leads to signicant reduction in COD, appropriate process scheme for their removal.
the process is energy intensive and the color removal is still  It is established that several microorganisms (bacteria,
inadequate. Thus several pure cultures of fungi, bacteria fungi, algae), especially in pure cultures, display a
and algae have been investigated specically for their limited ability to decolorize the spentwash. A better
ability to decolorize the efuent as discussed earlier. In all understanding of the microbial enzymes/activities re-
instances, supplementation with either nitrogen or carbon sponsible for the degradation of melanoidins would
source is almost always necessary because the microbial contribute to enhancing the efciency of the decoloriza-
species are not able to utilize the spentwash as the sole tion process.
carbon source. Further, high dilution (typically up to 1:10  Investigations on pure culture aerobic systems that can
fold for untreated spentwash and 1:161:2 fold for result in both COD and color removal have been
biomethanated spentwash) is required for optimal micro- conned exclusively to laboratory scale set-ups. The
bial activity. In addition, these studies are mostly limited to issues of appropriate system design, including scale-up,
laboratory scale investigations and no pilot/commercial have not been addressed. In this context, systems like
scale operations are reported as yet. membrane bioreactors that have lower sludge produc-
Physico-chemical treatment, viz. adsorption, coagula- tion can be considered. Also, issues like minimizing
tion/occulation, oxidation processes, membrane treat- nutrient supplementation, avoiding feed dilution and
ment have been examined with particular emphasis on operation under non-sterile conditions should be exam-
efuent decolorization. Though these techniques are ined. These points are particularly signicant in
effective for both color removal as well as reduction in translating these studies into eld applications.
organic loading, sludge generation and disposal is a  Adsorbents like activated carbon that result in almost
constraint in coagulation/occulation and adsorption. complete decolorization are not cost effective for
Also, the cost of chemicals, adsorbents and membranes is treating the enormous volumes of spentwash typically
a deterrent to the adoption of these methods (Rajor et al., generated in a distillery. Thus, there is scope for
ARTICLE IN PRESS
494 Y. Satyawali, M. Balakrishnan / Journal of Environmental Management 86 (2008) 481497

examining low cost adsorbents, including wastes gener- Arora, M., Sharma, D.K., Behera, B.K., 1992. Upgrading of distillery
ated in other industrial processes/operations. In this efuent by Nitrosococcus oceanus for its use as a low-cost fertilizer.
context, appropriate sludge disposal methods should Resources, Conservation and Recycling 6 (4), 347353.
Asthana, A.K., Misra, S.K., Chandra, R., Guru, R., 2001. Treatment of
also be examined. color and biochemical oxygen demand of anaerobically treated
 Membrane processes like nanoltration and RO can distillery efuent by aerobic bacterial strains. Indian Journal of
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6. Conclusion
water advanced oxidation. Part 2. Ozone combination with
hydrogen peroxide or UV radiation. Water Research 31 (10),
The review indicates that a comprehensive treatment 24152428.
scheme for molasses distillery wastewater leading to Benito, G.G., Miranda, M.P., de los Santos, D.R., 1997. Decolorization of
effective removal of both organics and color is not wastewater from an alcoholic fermentation process with Trametes
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